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Tekst voor de cursus Grondstoffen en het Systeem Aarde (HD 698) H.E.Rondeel, december 2001
Teksten gebaseerd op: Blackbourn, G.A. (1990) Cores and core logging for geologists. Whittles Publ.,Caithness. 113 pp. Shauer Langstaff, C. & D. Morrill (1981) Geologic cross sections. IHRDC, Boston. 108 pp. Stoneley, R. (1995) An introduction to petroleum exploration for non-geologists. Oxford University Press, Oxford. 119 pp. Waples, D. (1981) Organic geochemistry for exploration geologists. Burgess Publ. Co., Mineapolis. 151 pp. Waples, D.W. (1985) Geochemistry in petroleum exploration. Reidel Publ. Co, Dordrecht & IHRDC, Boston. 232 pp.
1 - INTRODUCTION............................................................................................................................. 5 FORMATI0N OF 0IL AND GAS......................................................................................................... 5 2 - ORGANIC FACIES.......................................................................................................................... 6 THE CARBON CYCLE ....................................................................................................................... 6 FACTORS INFLUENCING ORGANIC RICHNESS............................................................................ 7 PRODUCTIVITY .............................................................................................................................. 7 PRESERVATION.............................................................................................................................. 8 DILUTION ..................................................................................................................................... 11 SUMMARY ....................................................................................................................................... 12 3 - ORGANIC CHEMISTRY .............................................................................................................. 13 INTRODUCTION.............................................................................................................................. 13 NAMES AND STRUCTURES........................................................................................................... 13 HYDROCARBONS ......................................................................................................................... 13 NONHYDROCARBONS ................................................................................................................. 15 4 - KEROGEN...................................................................................................................................... 17 INTRODUCTION.............................................................................................................................. 17 KEROGEN FORMATION................................................................................................................. 17 KEROGEN COMPOSITION ............................................................................................................. 18 KEROGEN MATURATION .............................................................................................................. 20 INTRODUCTION ........................................................................................................................... 20 EFFECTS OF MATURATION ON KEROGENS ............................................................................. 21 HYDROCARBON GENERATION................................................................................................... 22 SUMMARY ....................................................................................................................................... 23 5 - BITUMEN, PETROLEUM, AND NATURAL GAS...................................................................... 24 INTRODUCTION.............................................................................................................................. 24 COMPOUNDS PRESENT IN BITUMEN AND PETROLEUM ......................................................... 24 GENERAL CLASSES OF COMPOUNDS ....................................................................................... 24 SPECIFIC COMPOUNDS.............................................................................................................. 25 FACTORS AFFECTING COMPOSITION OF BITUMEN AND PETROLEUM................................ 25 SOURCE AND DIAGENESIS ......................................................................................................... 25 RESERVOIR TRANSFORMATIONS ............................................................................................... 26 COMPARISON OF BITUMEN AND PETROLEUM ....................................................................... 27 NATURAL GAS .............................................................................................................................. 28 SUMMARY ....................................................................................................................................... 28 6 - MIGRATION.................................................................................................................................. 29 DEFINITIONS................................................................................................................................... 29 PRIMARY MIGRATION................................................................................................................... 29 MECHANISMS............................................................................................................................... 29 DISTANCE AND DIRECTION ....................................................................................................... 30 SECONDARY MIGRATION............................................................................................................. 31 MECHANISM................................................................................................................................. 31
DISTANCE AND DIRECTION ....................................................................................................... 31 ACCUMULATION............................................................................................................................ 32 INTRODUCTION ........................................................................................................................... 32 CLASSICAL TRAPS........................................................................................................................ 33 KINETIC TRAPS ............................................................................................................................ 33 TAR-MAT TRAPS ........................................................................................................................... 34 GAS HYDRATES ............................................................................................................................ 34 EFFECTS ON OIL AND GAS COMPOSITION ................................................................................ 34 SIGNIFICANCE FOR EXPLORATION ............................................................................................ 35 7 - PETROLEUM TRAPS ................................................................................................................... 36 THE REPRESENTATION OF TRAPS .............................................................................................. 36 STRUCTURAL TRAPS ..................................................................................................................... 37 STRATIGRAPHIC TRAPS ................................................................................................................ 41 COMBINATION TRAPS................................................................................................................... 42 HYDRODYNAMIC TRAPS .............................................................................................................. 43 THE RELATIVE IMPORTANCE OF TRAPS ................................................................................... 43 EXERCISES ...................................................................................................................................... 45 8 - SOURCE-ROCK EVALUATION.................................................................................................. 49 DEFINITION OF SOURCE ROCK.................................................................................................... 49 PRINCIPLES OF SOURCE-ROCK EVALUATION .......................................................................... 49 QUANTITY OF ORGANIC MATERIAL .......................................................................................... 49 MATURITY OF ORGANIC MATERIAL.......................................................................................... 49 CONTAMINATION AND WEATHERING....................................................................................... 52 ESTIMATION OF ORIGINAL SOURCE CAPACITY ...................................................................... 52 INTERPRETATION OF SOURCE-ROCK DATA ............................................................................. 53 QUANTITY OF ORGANIC MATERIAL .......................................................................................... 53 TYPE OF ORGANIC MATTER....................................................................................................... 53 MATURITY..................................................................................................................................... 54 COALS AS SOURCE ROCKS ......................................................................................................... 54 SUMMARY ....................................................................................................................................... 55 EXERCISES ...................................................................................................................................... 56 9 - PREDICTING THERMAL MATURITY ...................................................................................... 60 INTRODUCTION.............................................................................................................................. 60 CONSTRUCTION OF THE GEOLOGICAL MODEL ....................................................................... 60 BURIAL-HISTORY CURVES.......................................................................................................... 61 TEMPERATURE HISTORY............................................................................................................ 61 SPECIAL CONSIDERATIONS ABOUT BURIAL-HISTORY CURVES ............................................ 62 CALCULATION OF MATURITY..................................................................................................... 63 FACTORS AFFECTING THERMAL MATURITY............................................................................ 64 POTENTIAL PROBLEMS WITH MATURITY CALCULATIONS ..................................................... 65 EXERCISES ...................................................................................................................................... 66 10 - QUANTITATIVE ASSESSMENT ............................................................................................... 69 OIL IN PLACE .................................................................................................................................. 69 RESERVES........................................................................................................................................ 69 DISCOVERED RESERVES............................................................................................................. 70 UNDISCOVERED RESERVES ....................................................................................................... 72 ULTIMATE RESERVES.................................................................................................................. 73
more mobile molecules. These changes lead to a gradual cessation of microbial activity. Certain microorganisms. In the late stages of catagenesis and in the final transformation stage. or under different diagenetic conditions. are chemically distinct from each other. Many of the chemical compounds present in sediments are in fact derived from bacteria. These differences can have a significant effect on hydrocarbon generation.Introduction FORMATI0N OF 0IL AND GAS Proponents of the organic origin of oil and gas have given us a general picture of how organic matter derived from dead plants is converted to hydrocarbons. In the early stages of catagenesis most of the molecules produced from kerogen are still relatively large. During this second transformation phase. Most of this organic matter is transformed during diagenesis info very large molecules. thermal reactions become increasingly important. . however. the principal products consist of smaller gas molecules. kerogen begins to decompose into smaller. As temperature rises. with many details still poorly understood. it is known that organic debris derived from plants and algae is best preserved in fine-grained sediments deposited in the absence of oxygen. but only within the last few years have we realized that in many areas a large portion of the natura!-gas reserves are biogenic. and temperature increases. and were formed as dead organic matter was converted to microbial tissues. these are the precursors for petroleum. convert some of the organic debris to biogenic methane. The earliest stage of hydrocarbon generation occurs during diagenesis. called methanogens. Low-temperature chemical and biological reactions (called diagenesis) that occur during transport to and early burial in the depositional environment modify this organic matter. porosity and permeability decrease. Once formed. In recent years this relatively simple picture of hydrocarbon generation has been complicated slightly by our growing awareness that kerogens formed from different kinds of organic matter. As burial depth increases.Organic Facies . called catagenesis.5 1 . Although the transformation process is very complex. and are called bitumen . where hydrocarbon movement ceases and accumulation occurs. Migration through these conduits often leads to traps. and thus eventually bring organic diagenesis to a halt. called metagenesis. These play a key role as the precursors for oil and much natural gas. oil and gas molecules can be expelled from the source rock into more permeable carrier beds or conduits. Formation of biogenic methane has been recognized for a long time. the largest of which are called kerogen.
Organic Facies . Oxidative decay of dead organic matter is a highly efficient process mediated largely by microorganisms. A large fraction. the yearly productivity of both groups is about equal. Despite the great imbalance in biomass between terrestrial plants (450 billion metric tons [t]) and aquatic phytoplankton (5 billion t). as a consequence of the much more rapid reproduction of simple aquatic organisms. comprises microbial tissue formed within the sediments by the bacterial transformation of plant and algal debris. we need to understand how this organic matter came to be preserved in the rocks. Preservation of organic material is actually a rare event. Most organic carbon is returned to the atmosphere through the carbon cycle.6 2 . Zooplankton and higher animals contribute relatively little organic matter to sediments.Organic Facies THE CARBON CYCLE Because oil and gas are generated from organic matter in sedimentary rocks. less than 1% of the annual photosynthetic production escapes from the carbon cycle and is preserved in sediments. Some of the organic material in sediments consists of fragments of plants or algae that derived their energy from the sun. Because of . The recently discovered deep-sea ecosystems in the Pacific Ocean that derive their energy from oxidation of sulfides in hydrothermal vents are interesting but volumetrically unimportant. Preservation of organic matter begins with photosynthesis. however.
Shallowmarine environments. and general water chemistry.1%. significant amounts of organic matter must be deposited and protected from diagenetic destruction. Each factor may be dominant under different conditions.7 extensive oxidation of land-plant debris in soils. suggesting that either depth or organiccarbon content eventually limits diagenesis. Nutrients dissolved in waters below the photic zone therefore go unutilized. accumulation of organic-rich sediments cannot occur. a great deal of the oxidation of organic matter occurs within the sediments themselves. FACTORS INFLUENCING ORGANIC RICHNESS In order for organic-rich rocks to be formed. and that the microbes have given up trying to digest it.000 billion t. Each of these categories could in turn be further subdivided. The three primary factors influencing the amount of organic matter in a sedimentary rock are productivity. where there is local recycling of nutrients from decaying organisms and influx of fresh nutrients from terrestrial sources. in fact. Nutrient availability is. orogeny and erosion. watercirculation patterns are particularly important for supplying nutrients and thus controlling productivity. Only a small fraction of this (10. In relatively unrestricted marine environments. however. because under normal circumstances they cannot move upward into the zone of photosynthesis. Only where there is upwelling of subsurface waters can these nutrients return to the photic zone. are therefore much more productive than the open ocean. predators. If this deeper water is enriched in nutrients.Organic Facies . For example. and Northwest Africa that result from the movement of surface waters away from these coasts. In the modern world there are zones of intense seasonal upwelling off the west coasts of California. much of the terrestrial organic material is already highly oxidized when it arrives in the sediments. nutrient availability would depend on such factors as water circulation patterns. Although oxidative decay destroys most of the yearly production. Depth could interfere with microbial diagenesis when compaction reduces pore sizes and nutrient fluxes in interstitial waters. On the other hand. Productivity is the logical place to begin our analysis. with a preference for horizontal water movement within each density layer. because without adequate productivity. When we consider inefficiencies in discovery and recovery. high photosynthetic productivity will occur at the site of upwelling.000 billion t) dispersed in fine-grained sedimentary rocks. volcanism. There is another zone of seasonal upwelling off the Horn of Africa in the Indian Ocean as a result of . Total Organic Carbon (TOC) values decrease monotonically through the first 300 meters of burial before levelling out at about 0.05%) occurs in economic deposits of fossil fuels. Namibia. over vast amounts of geologic time the small fraction that escaped the carbon cycle has built up extremely large quantities of organic matter (20. Upwelling occurs where bulk movement of surface water away from a particular area allows deeper water to ascend to replace it. only one molecule out of about every one million successfully negotiates the journey from living organism to the gasoline pump. Bodies of water naturally develop density stratification. Peru. the low TOC values could indicate that the remaining organic matter has no more nutritional value. light intensity. temperature. carbonate supply. preservation.000. and dilution. and recycling by organic decay. one of the critical parameters governing productivity. or about 0. paleoclimate. PRODUCTIVITY A partial listing of the many factors influencing productivity would include nutrient availability. Although some destruction of organic material occurs during transport to the depositional environment.
There are many more organic-rich facies resulting from excellent preservation than from extremely high productivity.5 milliliters (mL) per liter (L)). The presence of undegraded marine organic material is a strong indication of anoxia. and because most biological oxidation processes require molecular oxygen. productivity is probably not as important a factor as preservation. These anaerobic processes are inefficient compared with aerobic diagenesis. PRESERVATION The principal control on organic richness is the efficiency of preservation of organic matter in sedimentary environments. Its presence in . microorganisms that utilize materials like sulfate or nitrate ions instead of molecular oxygen as electron acceptors in their metabolic processes. and all the other factors that influence upwelling loci is severely limited. paleoclimatic conditions. preservation of organic matter will be much enhanced. Because most of the oxidation occurring in the water column. At lower levels of dissolved oxygen. the simplest way to limit oxidation is to limit the supply of oxygen.8 monsoonal winds that drive surface waters away from the coast. Secondly.2 mL/L is called the anoxic zone. some problems associated with their application. because when the availability of oxygen is limited. soils. many species disappear. However. and the sediment-accumulation rate. and we could coin the term dysoxic to describe the zone itself. the type of organic matter deposited. All these areas exhibit high productivity when upwelling occurs.2 mL/L. Such models are interesting.Organic Facies . and sediments is biological. Of these. The term dysaerobic has been used to describe processes occurring in the transitional zone (0. and paleoclimates. especially of woody origin." hut because of the radical change in biota that occurs at about 0. Processes that occur in these two zones are called aerobic and anaerobic. respectively. diagenesis is restricted to anaerobic processes. ANOXIA. We call the zone in which oxygen contents are high the oxic zone. the remaining individuals often become dwarfed in an effort to survive in a hostile environment. After all. because marine organic matter is consumed preferentially by organisms. Anoxia is of tremendous importance in the preservation of organic matter in sediments. wind and water circulation patterns. There are. the accuracy with which we can reconstruct continental positions. Three factors affect the preservation (or destruction) of organic matter: the concentration and nature of oxidizing agents. Thus if anoxia can develop. because some of the commonly used indicators of anoxia may be misleading. At dissolved oxygen levels below about 0. First. much oxic sediment also contains large amounts of organic matter. although some species can tolerate extremely low oxygen levels (0. the zone where oxygen falls below 0. TOC values alone must therefore be used with caution. and may in fact prove useful in future exploration efforts. and are usually limited in scope by the availability of sulfate or nitrate. increasing preservation rates is a very efficient way to increase organic richness. Anoxic sediments are not always easy to recognize.2-0.5 mL/L). landmasses. if on the average only 1% of organic matter is preserved. oxidizing agents are probably the most crucial factor. essentially the only viable organisms are those that we call anaerobes. Theoretical models have been developed to predict upwelling (and consequent productivity) in ancient seas from input data on continental configurations.2 mL/L. All large organisms require oxygen in order to live. however. The term "anoxic" literally means "having no oxygen. Anoxic sediments always contain elevated TOC values (generally above 2% and always above 1% ). especially in the Palaeozoic. its use in practice has been expanded to include very low oxygen levels as well.
Depths in excess of 200 m are required to prevent mixing during storms. particularly in understanding lacustrine beds. very dark. Although pyrite does indeed form under anoxic conditions. it may well have developed after burial. The oxygen minimum layer usually begins immediately below the photic zone. Wyoming). are anoxic in some of the places where they have been penetrated. there is no guarantee that anoxia was present at the sea floor. then permanent density stratification will arise as a result of temperature differences within the water column. anoxia can be very local. The presence of pyrite itself can also be deceptive. Color should be used mainly as a negative criterion: If a rock is not very. no more oxygen can enter. once the original oxygen has been consumed in oxidizing organic matter. intense pyritization of benthic bivalves is testimony to the fact that pyrite is not a good indicator of bottom-water anoxia at the time of deposition. it is instructive to consider complete stagnation. If an isolated body of water is deep enough. Truly stagnant basins are actually quite rare. All anoxic sediments will be very dark gray or black when deposited. Marine basins are seldom isolated enough to fit well into the stagnant-basin model.2 mL/L. denser waters remain at the bottom. anoxic sediments show preserved depositional laminae on a millimeter or submillimeter scale. Lakes in failed rifts can also contain organic-rich. The supply of fresh oxygen is therefore limited to horizontal . leading to the eventual development of a pycnocline (density interface) which prevents interchange between the two layers. Consumption of oxygen results from decay of dead organisms that have sunk from the photic zone above. The cooler. that most of the world's oil was generated from source beds deposited under anoxic conditions. where photosynthesis and turbulence can no longer contribute oxygen to the water. Many black rocks. it cannot represent an anoxic facies. in fact. Nevertheless. STAGNANT BASINS. but limnic environments often are. Nevada). and therefore that dissolved-oxygen levels were below 0.Organic Facies . OXYGEN-MINIMUM LAYER (OML). Lakes of the Rift Valley of East Africa are excellent modern analogs receiving much attention from both researchers and explorationists at the present time. although stunted burrows can be used as evidence of dysoxia. most likely by absence of oxygen. Color is not a reliable indicator. the Elko Formation (Eocene/Oligocene. This oxygen minimum develops when the rate of consumption of oxygen within that layer exceeds the rate of influx of oxygen to it. Lake deposits associated with continental rifting. Among the ancient lake beds thought to have been deposited in permanently stratified waters are the well-known Green River Shale (middle Eocene. Therefore. and strata from several basins in China. and its presence indicates that the anaerobic reduction of sulfate ion did occur. Lack of communication between the layers prohibits replenishment of oxygen in the bottom layer. and both the waters in the bottom layer and the underlying sediments will become anoxic. they often owe their dark color to finely divided pyrite or to particular chert phases. The ultimate implications of anoxia for petroleum exploration are great. Finally. anoxic sediments. especially during the Triassic along the margins of the developing Atlantic Ocean. The laminae prove that burrowing fauna were absent.9 rocks therefore indicates that diagenesis was stopped prematurely. and warm climates are necessary to avoid overturn caused by freeze-thaw cycles. however. The oxygen-minimum layer is a layer of subsurface water that has a lower dissolved-oxygen content than the water layers either above or below. Furthermore. Conversely. are not rich in organic carbon. It therefore behoves us to understand the conditions under which anoxia develops. the presence of bioturbation indicates that the bottom waters were not anoxic. it has been estimated. and if the climate is subtropical or tropical. slow circulation or turnover of the water column occurs almost everywhere.
the oxygen they can contribute is limited. Shallow Silling. its intensity varies greatly. Late Devonian) the world oceans were severely depleted in dissolved oxygen. and diminished bacterial activity. Late jurassic. those environments can also incorporate the features of an oxygen-minimum-layer model. During those times the OML expanded both upward and downward because of poor supply of oxygen to subsurface waters. However.g. Nutrients are concentrated by evaporation. Where the sill is shallow. Anoxia . The result is often deposition of organic-rich laminae within evaporites. because of their connection with the open-marine realm. In times like the mid-Cretaceous. In actuality there is a lazy turnover of the bottom waters. Intensely developed OMLs occur in areas of high productivity and. high influxes of organic matter. Bottomset beds associated with prograding delta systems can be rich in organic matter if they are laid down within a well-developed oxygen-minimum layer. Furthermore. Large amounts of organic material are preserved in coal swamps as a result of the combined effects of poor water circulation. foreset beds within the same system are leaner in organic matter because they are deposited above the OML. permanent density stratification will develop. Circulation is often restricted by the presence of a sill. Coal Swamps. Although circulation in coal swamps is generally sluggish. to a lesser extent. Below the OML oxygen levels again increase. In an evaporitic environment (Karabogaz in the Caspian Sea) there is a net flow of water into the basin.10 movement of oxygen-bearing waters. In either case. Settings in which circulation is restricted are much more common than stagnant basins. It has been proposed that at certain times in the past (e. with the bottom layer almost isolated from the open-marine waters. Coal swamps can develop under a variety of conditions in both marine and non-marine environments. sediments will be deposited under low-oxygen conditions. since most organic matter was destroyed within the overlying OML. whereas in a fluvially dominated system (Black Sea) the net flow of surface water is out over the sill.Organic Facies .. an upward expansion of the OML led to a tremendous increase in the surface area covered by anoxic bottom waters. Although an oxygen-minimum layer exists virtually everywhere in the ocean. because these horizontally moving waters also lie within the oxygen minimum layer. if the basin is deep enough. Wherever an intensely developed OML intersects the sediment-water interface. Shallowly silled basins often yield evaporites. In contrast. which could be excellent hydrocarbon source rocks. the shallowness of the swamps prevents the waters themselves from becoming anoxic. This depletion was probably the result of the complex interplay of several factors. mid-Cretaceous. in areas of poor circulation. Evaporitic environments combine the opportunity for abundant growth of algae with ideal conditions for preservation. It is not coincidental that these were times of deposition of large amounts of organic-rich rocks in many parts of the world. including paleoclimate and water circulation. These include the modern Peru-Chile shelf (high productivity associated with upwelling) and occurrences of black sediments of Aptian to Turonian age in the North Atlantic. the point of connection between the restricted area and the open-marine environment. or as lateral facies equivalente thereof. RESTRICTED CIRCULATION. and high hydrogen-sulfide concentrations create conditions poisonous to predators. and grazers and predatory organism are eliminated by the high salinities. Any organic matter arriving in those sediments will have an excellent chance to escape oxidation. when a major transgression had greatly increased the continental shelf area. the waters entering or leaving the basin are near surface. but it is too slow to disturb the anoxia which develops in the bottom layer. There are other ancient and modern examples of organic-rich rocks deposited under anoxic or near-anoxic conditions associated with OMLs. High productivity reduces oxygen levels. as a result of diminished oxygen demand.
but their supposedly low potential for generating oil is to be reconsidered. The hydrocarbon-source potential of all of these oxidizing facies is low. Furthermore. Most depositional settings not specifically catalogued above will be more or less well oxygenated. thus preventing extensive diagenesis of such material. In fact. The extremely high accumulation rates for biogenic carbonates and siliceous sediments in zones of high productivity promote preservation of the associated algal protoplasm. which settle several orders of magnitude faster than individual phytoplankton. or organic material. and therefore wi11 contain primarily oxidized organic matter. the phenolic components present in lignin-derived terrestrial material are toxic to many micro-organism. cellulosic. Rapid burial is accomplished by a high influx of inorganic detritus. DILUTION Although high sediment-accumulation rates enhance preservation of organic matter. forest fires. Nitrogen and phosphorus are in particular demand. Rapid settling of organic debris through the water column is also important. biogenic inorganic sediment. or resinous material.Organic Facies . with their high concentrations of organic matter. It may also contain very resistent organic debris derived from erosion of ancient rocks. TOC values increase as sediment-accumulation rates increase. Rapid sedimentation and burial con also enhance preservation. much of the organic material that does reach the bottom in deep waters arrives in relatively large fecal pellets. Abyssal sediments are notoriously low in organic carbon as the result of the combined effects of high oxygen levels in abyssal waters. and more favorable for gas than for oil. but the organic material is almost invariably woody. That material which remains is dominantly of terrestrial origin. Lack of sulfate in non-marine swamps further prevents anaerobic microbial destruction of the organic matter. all of which are chemically quite distinct from each other. because its chemical components are digestible and provide precisely the nutrients required by scavengers and predators. Organic matter of algal (phytoplanktonic) origin is consumed more readily by organisms than are other types of organic material. TYPE OF ORGANIC MATTER. as a result of more rapid removal of organic material from the zone of microbial diagenesis. . provide an ideal means of maintaining low-oxygen conditions. their virtual absence in much terrestrial organic material. but it does spread that organic material through a larger volume of rock. Oxic Settings. Rapid deposition of inorganic detritus is common in turbidites and in prodelta shales. renders it of little nutritional value. at very high accumulation rate dilution may become a more important factor than increased preservation. Any extensive organic diagenesis is therefore likely to eliminate algal organic matter first. Near-shore oxidizing facies sometimes have high TOC values. and low productivity in the overlying pelagic realm. because extensive decomposition occurs during its fall to the ocean floor. and other oxidative processes. cuticular. The net result is a reduction in TOC values. Coals are important source rocks for gas accumulations. RAPID SEDIMENTATION AND BURIAL. lignitic. Phenolic bactericides derived from lignin hinder bacterial decay in the water and throughout the sediment column. very slow sedimentation rates. Coals also accumulate very rapidly and. and may include woody. especially in structural (woody) material. Dilution does not reduce the total amount of organic matter preserved.11 develops within the sediments rather than in the water column.
Organic Facies . and the presence of high TOC values coupled with the occurrence of undegraded marine organic matter. It is important to be able to distinguish local anoxia or anoxia developed deep within sediments from anoxia induced by anoxic bottom waters. . where sediment-accumulation rates are directly proportional to organic-carbon-accumulation rates. There are a number of mechanisms by which oxygen depletion may be fostered and maintained. and rapid burial. anoxic sediments were deposited discontinuously through time and space. In biogenic sediments or coals. dilution is far less marked. such events were often interrupted for long periods before anoxia was reinduced. To derive maximum value from our analyses. Consequently. As in the modern oceans. Direct control of the anoxia was thus probably local. Of these. show strong dilution effects when accumulation rates are very high. Biogenic sediments. lack of knowledge of seawater chemistry and nutrient availability at those times.12 Dilution effects depend upon rock lithology. anoxia in bottom waters is a phenomenon whose effects we should learn to recognize in ancient rocks. Although certain periods undeniably contain more than their share of anoxic rocks. dilution effects may lead to lower TOC values in spite of enhanced preservation rates. Because of its role in creating rocks with excellent hydrocarbon-source potential. Productivity can be predicted by locating ancient sites of marine upwellings. we should always strive to place the organic rich rocks in the larger context of basin evolution through time and space. Anoxic events in the past were probably not as large in scale or as long lasting as some workers have suggested. Rapid accumulation of sediment shortens the residence time of organic matter in the zone of diagenesis and thus promotes preservation. however. SUMMARY There are three principal factors that affect the amount of organic matter in sedimentary rocks: primary photosynthetic productivity. Shales. and dilution by inorganic material. effectiveness of preservation. including stagnancy or near-stagnancy. and a very imperfect understanding of oceanic. Some of the commonly applied criteria are apt to be misleading. Models that integrate the concepts of organic richness with depositional cycles and facies analysis will be valuable tools for understanding hydrocarbon systems in basins. in contrast. by uncertainties about exact continental positions and configurations in the past. however. a strongly developed oxygen-minimum layer.and atmospheric-circulation patterns. such models are not yet of much practical value for the distant past. as a result of high productivity or sluggish circulation. however. Our ability to make accurate predictions is limited. preservation is generally the most important. in which the organic and inorganic materials arrive together. in contrast. Facies changes from carbonates to shales may create large dilution effects that can be wrongly interpreted as indicating changes in oxygen levels. If the rapidly accumulating sediment is mainly clastic. Preservation is best accomplished where oxygen is excluded from bottom waters. The most reliable criteria for bottom-water anoxia are the preservation of fine depositional laminae. It is often very difficult to separate the influences of these various factors in a particular depositional environment. are not as strongly affected by dilution.
creating long chains and ring structures. except carbon dioxide. especially if one has to do it only occasionally. We can make other logical simplifications for longer carbon chains. ethane. All compounds containing carbon atoms. every carbon atom forms four bonds. and organic geochemistry the study of organic compounds present in geological environments. The chemical reactions of interest to us are very few and are discussed only briefly. and metal carbides. This objective is very different trom that of a normal course in organic chemistry. .Organic Chemistry . and other elements. and nitrogen.Organic Chemistry INTRODUCTION Anyone who uses petroleum geochemistry must be familiar with basic chemical terminology. and indeed in every carbon compound (except a few highly unstable ones created only in laboratories). in which one must also learn all the reactions of many classes of compounds. the explicit inclusion of every atom and every bond becomes extremely tedious. oxygen. using a subscript on the H to denote the total number of hydrogens around that atom. Examples of hydrocarbons are methane. three bonds. The objective of this chapter is to acquaint the reader with the names of common compounds and with several different conventions for drawing their structures. Petroleum and natural gas are themselves often referred to as "hydrocarbons." but that usage is incorrect trom the chemist's point of view because those materials often contain substantial amounts of nitrogen. carbonates. This usage is historical and does not imply that all such compounds are necessarily derived from living organisms. The structures of methane and ethane are thus represented by CH4 and CH3CH3 respectively. If one wants to draw large molecules.13 3 . In this chapter we restrict the usage of the term hydrocarbon to the standard chemical one. two bonds. trace metals. Carbon atoms like to form bonds with each other. The following representations of n-pentane are equivalent: CH3CH2CH2CH2CH3 or CH3(CH2)3CH3. Organic chemistry is thus the study of carboncontaining compounds. In each of these compounds. however. are termed organic. oxygen and sulfer. Writing the detailed structure of a simple molecule like methane is no problem. whose structures are shown below. sulfur. elsewhere in this text usage will vary. NAMES AND STRUCTURES HYDROCARBONS In chemical terms a hydrocarbon is a compound containing only the elements carbon and hydrogen. as it does in the real world. and cyclohexane. One common convention is to represent all the hydrogen atoms attached to a given carbon atom by a single H. Similarly. hydrogen always forms one bond. This unique property of carbon is responsible for the existence of literally millions of different organic compounds. Several different types of shorthand have therefore developed to facilitate drawing organic molecules.
The simplest series of hydrocarbons has linear structures. which. Because we know that each carbon atom forms four bonds and each hydrogen atom forms one bond. and carbon-carbon bonds are shown as lines connecting those points. These cyclic compounds (called naphthenes) are named by counting the number of carbon atoms in the ring and attaching the prefix cyclo. All the compounds mentioned above are called saturated hydrocarbons or saturates. Regular isoprenoids consist of a straight chain of carbon atoms with a methyl branch on every fourth carbon. The letter n stands for normal. That is. Isoprenoids ranging in length from six to forty carbon atoms have been found in petroleum and rocks. is the adjectival form of the word methane. n-pentane and cyclohexane are represented by the line structures shown below. which we used earlier. Among the most important branched hydrocarbons in organic geochemistry are the isoprenoids.Organic Chemistry . but the prefixes denoting the number of carbon atoms in the other alkanes are derived from Greek numbers. Branching can occur. no more hydrogen can be incorporated into the molecule without breaking it apart. The term methyl. For example. Other adjectival forms are made by dropping the -ane ending and adding yl (for example. and indicates that there is no branching in the carbon chain. Hydrogen atoms and bonds to hydrogen atoms are not shown at all. giving rise to a vast number of possible structures. We have also seen that carbon atoms can be arranged in rings. ethyl and propyl). In the case of 2methylhexane (C7H16) the basic structure is hexane. as in "alkane. We have ahready encountered n-pentane. Many unsaturated compounds have carbon-carbon double . simple inspection shows how mant' hydrogen atoms each carbon atom must have. The zigzag configuration illustrated for n-pentane is adopted to show clearly each carbon atom. are able to combine with additional hydrogen. Each carbon atom is represented by a point. a CH3 (methyl) group is attached to the second carbon atom. these molecules are called n-alkanes or nparains." The first four names are irregular. Names and formulas of the ten smallest n-alkanes Methane CH4 CH4 Ethane C2H6 CH3CH3 Propane C3H8 CH3CH2CH3 Butane C4H10 CH3 (CH2)2 CH3 Pentane C5H12 CH3 (CH2)3 CH3 Hexane C6H14 CH3 (CH2)4 CH3 Heptane C7H16 CH3 (CH2)5 CH3 Octane C8H18 CH3 (CH2)6 CH3 Nonane C9H20 CH3 (CH2)7 CH3 Decane C10H22 CH3 (CH2)8 CH3 Carbon atoms need not always bond together in a linear arrangement. in contrast. Note that the name of each compound ends in -ane.14 An even quicker shorthand that uses no letters at all has evolved. the names of the other nine simplest n-alkanes are given in the following table. because they are saturated with respect to hydrogen. Another important group of hydrocarbons is the unsaturates.
these compounds are called alkenes. these compounds are quite different trom the majority of the organic molecules found in living organisms. Most biological molecules are larger and more complex than the simple hydrocarbons. including hydrogenafion. of which some are biogenic and others are formed during diagenesis. and oxygen. sulfur. A simplified notation for drawing these molecules permits us to represent the double-bond system by a circle within the ring. By hydrogenation ethene thus reacts to form ethane. they do not long persist in geologic environments. Their stability permits aromatics to be important constituents of oils and sediments. they do not add hydrogen easily. It is this delocalization of electrons which makes aromatic compounds very stable. In the laboratory they are readily converted to alkanes by the addition of hydrogen in the presence of a catalyst. Aromatics form an extremely important class of unsaturated hydrocarbons. they are free to move throughout the cyclic system instead of being held between two particular carbon atoms.Organic Chemistry . highly aromatic materials of . and kerogen are called heteroatoms. or other elements. In fact. the compounds in which they occur are called heterocompounds. Many of the heterocompounds present in organisms are converted to hydrocarbons during diagenesis and catagenesis. nitrogen. but they actually have completely different chemical properties from alkenes and are unusually stable. that is. Although they are very important constituents of petroleum. Fossil organic matter often contains a vide variety of heterocompounds. The extreme case is graphite.15 bonds. The hydrocarbons we discussed so far are relatively simple molecules. which are large. Heterocompounds are also called NSO compounds. Some aromatic molecules are very large. NONHYDROCARBONS Atoms other than hydrogen and carbon that occur in petroleum. The circle indicates that the electrons in the double bonds are delocalized. the structures of which are shown below. At first glance aromatics appear to be nothing more than cyclic alkenes containing several double bonds. Among the most important NSO compounds are the asphaltenes. Examples are ethene (C2H4) . propene (C3H6). because the most common heteroatoms are nitrogen. the majority contain oxygen. Although they are unsaturated. some complex hydrocarbons that are found in fossil organic material can be related directly to individual biological precursors. Polycyclic aromatic hydrocarbons having fused ring structures are quite common. Because alkenes are highly reactive. The hydrocarbons present in petroleum are mostly the end products of extensive degradation of biogenic molecules. converts alkenes to alkanes and cyclic compounds during diagenesis. bitumen. Many common NSO compounds are not directly related to biogenic precursors. A variety of reactions. which is an almost-endless sheet of aromatic rings. Aromatics possess a system of alternating single and double bonds within a cyclic structure. phosphorus. sulfur. They are named in a similar manner to the alkanes. and cyclohexene (C6H10). except that the ending -ene indicates the presence of a double bond.
Because phenols are potent bactericides. They have many characteristics in common with kerogen. sugars. Like lignin. They are rapidly metabolized by virtually all organisms. It is a polymer consisting of many repetitions and combinations of three basic aromatic subunits. but asphaltene molecules are smaller and more aromatic than most kerogens.16 varying structure.Organic Chemistry . lignin is rather resistant to degradation. however. Lignin monomers are linked topether to form molecules having molecular weights from 3000 to 10. and thus tends to become concentrated as other organic matter is decomposed. most carbohydrates are attacked readily by microorganisms. providing much of the structural support for large land plants. Although cellulose is quite resistant to decomposition under some conditions. it is an important constituent of terrestrial organic matter. Lignin is an important component of wood. and amino acids. Upon decomposition lignin forms phenolic compounds. which are aromatics having a hydroxyl group (OH) attached. and cellulose. Amino acids are the building blocks of proteins. Among these are lignin. where small amounts of preserved amino acids can be used to date specimens) . Lignin and cellulose are major constituents of humic coals. and thus are seldom preserved in sediments (exceptions occur in shell material and in bones. Carbohydrates include starch. carbohydrates. Many nonhydrocarbon molecules common to living organisms are also present in sediments.000 atomic mass units. the latter is the most abundant organic compound in the biosphere.
called bitumen. Lack of solubility is a direct result of the large size of kerogen molecules. because it has patchwork structures formed by the random combination of many small molecular fragments. whether these hydrocarbons are mainly oil or gas. with some of the inorganic matrix often being contributed by the algae themselves. will be discussed in a following chapter. 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 transformafions of those organic molecules. develop after tens or hundreds of meters of burial. A basic understanding of how kerogen is formed and transformed in the subsurface is therefore important in understanding how and where hydrocarbons are generated. oil. The detailed chemistry of kerogen formation need not concern us greatly. which are reflected in their chemical and physical properties. for example) are partially or completely dismantled. soils. and the individual component parts are either destroyed or used to construct new geopolymers.17 4 . which have molecular weights of several thousand or more. KEROGEN FORMATION The process of kerogen formation actually begins during senescence of organisms. large molecules that have no regular or biologically defined structure. Coals are a subcategory of kerogen. Large organic biopolymers of highly regular structure (proteins and carbohydrates. more complex. have more mineral matter than algal coals. Subsurface heating causes chemical reactions that break off small fragments of the kerogen as oil or gas molecules. in contrast. Algal (boghead) coals are formed in environments where the source phytoplankton lack both calcareous and siliceous skeletal components. Today it is used to describe the insoluble organic material in both coals and oil shales. The soluble portion.Kerogen INTRODUCTION Kerogen is normally defined as that portion of the organic matter present in sedimentary rocks that is insoluble in ordinary organic solvents. Diagenesis results mainly in loss of water. The residual kerogens also undergo important changes. The smallest of these geopolymers are usually called fulvic acids. If anaerobic sulfate . and how much oil or gas can be expected. and less regular in structure. carbon dioxide. and natural gas. humins. humic acids. True kerogens. Diagenetic and catagenetic histories of a kerogen. strongly influence the ability of the kerogen to generate oil and gas. These geopolymers are the precursors for kerogen but are not yet true kerogens. and ammonia from the original geopolymers. having very high molecular weights. and sediments.Kerogen . Oil shales. Each kerogen molecule is unique. During the course of diagenesis in the water column. Kerogen is of great interest to us because it is the source of most of the oil and some of the gas that we exploit as fossil fuels. Coals and oil shales should therefore be viewed merely as sedimentary rocks containing special types of kerogens in very high concentrations. as well as dispersed organic matter in sedimentary rocks. the geopolymers become larger. and still larger ones. slightly larger ones. The term kerogen was originally coined to describe the organic matter in oil shales that yielded oil upon retorting. when the chemical and biological destruction and transformation of organic tissues begin. as well as the nature of the organic matter from which it was formed. The amount of organic matter tied up in the form of kerogen in sediment is far greater than that in living organisms or in economically exploitable accumulations of coal. Humic coals are best thought of as kerogens formed mainly from landplant material without codeposition of much mineral matter. Kerogen composition is also affected by thermal maturation processes (catagenesis and metagenesis) that alter the original kerogen.
In an oxidizing environment many of the small biogenic molecules will be attacked by bacteria before they can form geopolymers. What is within our reach. Geopolymers are more or less immune to bacterial degradation. better organic preservation. it would not be of great and direct significance to exploration geologists. Kerogen formation competes with the destruction of organic matter by oxidative processes. in contrast. They identified three main types of kerogen (called Types I. it is somewhat fruitless to attempt a detailed discussion of the chemical composition of kerogens. is developing a general method of describing gross kerogen composition and relating it to hydrocarbon-generative capacity. In a low-oxygen (reducing) environment. which are highly reactive.18 reduction is occurring in the sediments. The amount of sulfur contributed by the original organic matter itself is very small. and their organic precursors Transformation of organic material in sediments and sedimentary rocks. because the bacterial enzyme systems do not know how to attack them.Kerogen . Microorganisms prefer to attack small molecules that are biogenic. are converted into saturated or cyclic structures. in contrast. The four types of kerogen. the subdued level of bacterial activity allows more time for the formation of geopolymers and. Most organic oxidation in sedimentary environments is microbially mediated. Even if such a description were possible. Kerogens formed under reducing conditions will be composed of fragments of many kinds of biogenic molecules. contain mainly the most resistant types of biogenic molecules that were ignored by microorganisms during diagenesis. or at least look very much like biogenic molecules. About a decade ago workers at the French Petroleum Institute developed a useful scheme for describing kerogens that is still the standard today. the macerals that they are composed of. Those kerogens formed under oxidizing conditions. and III) and have studied the chemical characteristics and the nature of the organisms from which all types of kerogens were derived. and if the sediments are depleted in heavy-metal ions (which is often the case in nonclastic sediments but is seldom true in shales). II. . One way that we can begin is by classifying kerogens into a few general types. KEROGEN COMPOSITION Because each kerogen molecule is unique. and ultimately of much greater practical value. Carboncarbon double bonds. large amounts of sulfur may become incorporated into the kerogen structure. Subsequent investigations have identified Type IV kerogen as well. therefore.
unless they have small inclusions of Type II material. Cellulose and lignin are major contributors. and Colorado. Type I and Type II kerogens.Kerogen . have the lowest hydrogen contents. pollen and spores. Type IV kerogens. Most Type II kerogens are found in marine sediments deposited under reducing conditions. are normally considered to generate mainly gas. The shaded areas approximately represent diagenesis. from Wyoming. and metagenesis. . cellulose. Heteroatom contents of kerogens also vary with kerogen type. Type IV kerogens contain mainly reworked organic debris and highly oxidized material of various origins. In the immature state. Type III (humic) kerogens. Type II kerogens arise from several very different sources. despite their very disparate origins. and fossil resin. have lower hydrogen contents because they contain extensive aromatic systems. in contrast. Type IV kerogens are highly oxidized and therefore contain large amounts of oxygen. They are generally considered to have essentially no hydrocarbon-source potential. contain far less oxygen because they were formed from oxygen-poor lipid materials. which mainly contain polycyclic aromatic systems. Type III kerogens have high oxygen contents because they are formed from lignin. The best-known example is the Green River Shale. catagenesis. They also include contributions from bacterial-cell lipids. Extensive interest in those oilshale deposits has led to many investigations of the Green River Shale kerogens and has given Type I kerogens much more publicity than their general geological importance warrants. because they all have great capacities to generate liquid hydrocarbons. Type III kerogens are composed of terrestrial organic material that is lacking in fatty or waxy components. Type I kerogens have high generative capacities for liquid hydrocarbons.19 Type I kerogen is quite rare because it is derived principally from lacustrine algae. successively. Occurrences of Type I kerogens are limited to anoxic lakes and to a few unusual marine environments. phenols. Type III kerogens have much lower hydrocarbon-generative capacities than do Type II kerogens and. The various Type II kerogens are grouped together. Type I (algal) kerogens have the highest hydrogen contents because they have few rings or aromatic structures. of middle Eocene age. Utah. in contrast. including marine algae. and carbohydrates. leaf waxes. Hydrogen contents of immature kerogens (expressed as atomic H/C ratios) correlate with kerogen type. Type II (liptinitic) kerogens are also high in hydrogen. Van Krevelen diagram showing maturation pathways for Types 1 to IV kerogens as traced by changes in atomic HIC and OIC ratios.
The division of kerogens into Types I-IV on the basis of chemical and hydrocarbon-generative characteristics has been supported by another independent scheme for classifying kerogens using transmitted-light microscopy. in some cases. In this text we shall use the terms somewhat interchangeably. they represent fundamentally different perspectives. but it also continues through the metamorphic stage. most terrestrially influenced kerogens are low in nitrogen. Catagenesis and hydrocarbon generation occur concurrently. nonclastic sediments). In principle. High-sulfur kerogens (and coals) are almost always associated with marine deposition. The small molecules eventually become petroleum and natural gas. Because lignins and carbohydrates contain little nitrogen. however. the materials from which a maceral was derived. In many cases the original cellular structure is still recognizable. The kerogen in a given sedimentary rock includes many individual particles that are often derived from a variety of sources. Thus few kerogens consist of a single maceral type. Although the terms catagenesis and oil generation are often used synonymously. The different types of kerogen particles are called macerals.20 Sulfur and nitrogen contents of kerogens are also variable and. Despite its name. metagenesis is not equivalent to "metamorphism. A list of the most common macerals and their precursors is given in the table presented earlier in this chapter. Nitrogen is derived mainly from proteinaceous material. In others the original fabric has disappeared completely. especially when we are discussing both aspects simultaneously. they are to kerogen what minerals are to a rock. which is destroyed rapidly during diagenesis. is derived mainly from sulfate that was reduced by anaerobic bacteria. represents drygas generation. called catagenesis and metagenesis. break off small molecules and leave behind a more resistant kerogen residue. marine. called maturation. The biggest problem comes in identifying Type III kerogen. Maceral names were developed by coal petrologists to describe. Metagenesis. Most high-nitrogen kerogens were therefore deposited under anoxic conditions where diagenesis was severely limited. By convention the term catagenesis usually refers to the stages of kerogen decomposition during which oil and wet gas are produced. in contrast. wherever possible. but they really represent different aspects of the same process. they are not precisely equivalent. whereas hydrocarbon generation focuses on the production of hydrocarbon molecules. a term taken trom coal petrology. forcing us to make assumptions about the source organisms.Kerogen . because fresh waters are usually low in sulfate. What appears to be vitrinite (Type III kerogen) by visual analysis may have chemical characteristics intermediate between Type II and Type III kerogens because of the presence of small amounts of resin or wax. Kerogen types are defined by the morphologies of the kerogen particles. Sulfur is only incorporated into kerogens in large quantities where sulfate reduction is extensive and where Fe +2 ions are absent (organic-rich. occur when a kerogen is subjected to high temperatures over long periods of time. . Kerogen sulfur." Metagenesis begins long before true rock metamorphism. Macerals are essentially organic minerals. It is possible to make a reasonably good correlation between kerogen type based on chemical characteristics and kerogen type based on visual appearance. Many high-sulfur kerogens are also high in nitrogen. KEROGEN MATURATION INTRODUCTION Very important changes. interrelated. Thermal decomposition reactions. proving the origin of the particle. Microscopic organic analysis has reached a fairly high level of refinement and is often capable of assessing kerogen type with good accuracy. The correspondence is not perfect. anoxic. which occurs after catagenesis. because there is not a perfect biological separation of the various types of living organic matter. Catagenesis refers to transformations of kerogen molecules. however.
Thus the steady decrease in hydrogen content of a kerogen (usually measured as the atomic hydrogen/carbon ratio) during heating can be used as an indicator of both kerogen catagenesis and hydrocarbon generation. the residual kerogen gradually becomes more aromatic and hydrogen poor as catagenesis proceeds. however. is to monitor hydrocarbon generation. but it also states that at any temperature above absolute zero reactions will be occurring at some definable rate. II. Furthermore. Because many of the light product molecules are rich in hydrogen. Kerogen particles become darker during catagenesis and metagenesis. and gas) will be discussed in a following chapter. This complex interplay between the effects of time and temperature on maturity is discussed in a later chapter. oil. Kerogen maturation is not a reversible process-any more than baking a cake is reversible. Old rocks will often generate hydrocarbons at significantly lower temperatures than young rocks. it is also true that other changes in kerogen properties have little or nothing to do with it. Nitrogen and sulfur are also lost from kerogens during catagenesis. The real reason for following kerogen catagenesis. high-sulfur oils found in a number of areas. and III kerogens will therefore be very similar chemically. The more hydrogen a kerogen contains. as evidenced by low maturity. The composition of the products (bitumen. possessing essentially no remaining hydrocarbon generative capacity. much as a cookie browns during baking. because time also plays a role. It is impossible to set precise and universal temperature limits for catagenesis. As we saw earlier. even if drastic decreases in temperature occur. but they are not necessarily identical with hydrocarbon generation. thus allowing us to judge the extent to which kerogen maturation has proceeded. the rates of catagenesis are generally not important at temperatures below about 70° C. All kerogens become increasingly aromatic and depleted in hydrogen and oxygen during thermal maturation. Some of these changes can be measured quantitatively. Nitrogen loss occurs primarily during late catagenesis or metagenesis. Types I. the more hydrocarbons it can yield during cracking. For practical purposes. In contrast. Furthermore. of course. Although it is obvious that many measurable changes in kerogens are related to hydrocarbon generation. after hydrogen loss is well advanced. in most cases decreases of temperature in excess of about 20°-30° C due to subsurface events or erosional removal will cause the rates of catagenesis to decrease so much that it becomes negligible for practical purposes. There is a steady color progression yellow-goldenorange-light brown-dark brownblack as a result of polymerization and aromatization reactions.21 This chapter will focus on those changes in the residual kerogen that accompany catagenesis. the chemical process of maturation never stops completely. In the late stages of maturity. simply because the longer time available compensates for lower temperatures. including the Miocene Monterey Formation of southern California. and thus are not necessarily valid indicators of hydrocarbon generation. These reactions are intimately related to important changes in the chemical structure of kerogen.Kerogen . much of the sulfur is lost in the earliest stages of catagenesis. The most important implication of these chemical changes is that the remaining hydrocarbongenerative capacity of a kerogen decreases during catagenesis and metagenesis. the cracking of any organic molecule requires hydrogen. There is therefore no necessary cause-and-effect relationship . We shall look now at the various techniques for estimating the extent of hydrocarbon generation from kerogen properties and see how closely each of them is related to hydrocarbon generation. provided that the hydrogen content of the kerogen was known prior to the onset of catagenesis. Chemical reaction-rate theory requires that the rates of reactions decrease as temperature decreases. EFFECTS OF MATURATION ON KEROGENS Kerogen undergoes important and detectable changes during catagenesis and metagenesis.
HYDROCARBON GENERATION As kerogen catagenesis occurs. the visual appearance of kerogen also does not change during catagenesis: kerogen types are generally recognizable until the particles become black and opaque. called vitrinite reflectance. contain large numbers of unpaired electrons. small molecules are broken off the kerogen matrix. the technique. which are unpaired electrons not yet involved in chemical honds. especially highly aromatic ones. and because vitrinite particles also occur in kerogens. is that some of the bitumen is expelled from the source rock or cracked to gas. carbon-isotopic compositions of kerogens are affected little by maturation. its structure becomes more ordered. and no guarantee that a particular kerogen color always heralds the onset of oil generation. The difference between the two curves represents bitumen expelled from the rock or cracked to light hydrocarbons. Some properties of kerogen change very little during catagenesis. Both curves are highly . while others are small heterocompounds. These small compounds are much more mobile than the kerogen molecules and are the direct precursors of oil and gas. somewhat beyond the oil-generation window. Plot of bitumen generation as a function of maturity (dashed fine) compared to bitumen remaining in rock (solid line). Bitumen generation occurs mainly during catagenesis. Half a century ago coal petrologists discovered that the percentage of light reflected by vitrinite particles could be correlated with coal rank measured by other methods. Kerogens often fluoresce when irradiated. The intensity and wavelength of the fluorescente are functions of kerogen maturity. Because coal rank is merely a measure of coal maturity. For example. Except for darkening. and the less it will be reflected. the more an incident light beam will be scattered. The concentration of free radicals in a given kerogen has been found to increase with increasing maturity. As kerogen matures and becomes more aromatic. because the flat aromatic sheets can stack neatly. The more random a kerogen's structure. is the ability of kerogen particles to reflect incident light coherently. Free-radical concentrations can be measured by electron-spin resonance. has been widely and successfully applied in assessing kerogen maturity. One property that is strongly affected.22 between kerogen darkening and hydrocarbon generation. These structural reorganizations bring about changes in physical properties of kerogens. resulting in lower bitumen contents in the source. Some of these are hydrocarbons. and which can be used to gauge the extent of molecular reorganization.Kerogen . If neither expulsion from the source rock nor cracking of bitumen occurred. A general name tor these molecules is bitumen. during metagenesis the chief product is methane. however. What actually occurs. Kerogens. there would be a large and continuous build-up of bitumen in the rock as a result of catagenetic decomposition of kerogen. Cracking often produces free radicals.
23 idealized. We shall consider the latter briefly here. as measured by parameters such as vitrinite reflectance. Catagenesis of kerogen produces a more aromatic. Timing and efficiency of expulsion depend on a number of factors. hydrogen-poor. In such cases the expelled products will be mainly gas. Sulfur-rich kerogens decompose easily because carbon-sulfur hbonds are weaker than any bonds in sulfur-poor kerogens. Conversely. High-sulfur kerogens generate heavy. Numerous methods exist for tracing the history of a kerogen and determining its original chemical and physical characteristics. however. Kerogens formed from lipid-rich organic material are likely to generate liquid hydrocarbons. this result is hardly surprising. The chemical composition and morphology of kerogen macerals depend both on the type of original organic matter and on diagenetic transformations. Kerogens formed from resinite will generate condensates or light oils quite early. . because natural variations among samples cause much scatter in experimental data. In very lean rocks expulsion may occur so late that cracking of the generated bitumen is competitive with expulsion. Given the significant chemical differences among the various types of kerogens. Thus. Resinite and sulfur-rich kerogens are able to generate liquid hydrocarbons earlier than other kerogens because of the particular chemical reactions occurring in those two materials. Effective generation of hydrocarbons requires that the generated products be expelled from the source-rock matrix and migrated to a trap. which in turn is partly attributed to hydrocarbon generation itself. we cannot always define the limits of hydrocarbon generation with great confidence. but none of these measurements is closely linked to the actual process of hydrocarbon generation. when large geopolymers are created from biological molecules. including rock physics and organic-geochemical considerations. Resinite consists of polymerized terpanes (ten-carbon isoprenoids) that can decompose easily by reversing the polymerization process. those rocks that generate few hydrocarbons may not expel them until they have been cracked to gas. Microfracturing is related to overpressuring. whereas those kerogens that contain few lipids will generate mainly gas. The chemical composition of a kerogen controls the timing of hydrocarbon generation and the type of products obtained. although we know that oil generation does occur during the phase we call catagenesis. high-sulfur oils at low levels of maturity. SUMMARY Kerogen begins to form during early diagenesis. Candidates for early expulsion would be very organic rich rocks and those containing resinite or high-sulfur kerogens. Several methods exist for estimating the extent to which hydrocarbon generation has occurred in a given kerogen. Source rocks that generate large amounts of hydrocarbons early are likely to expel those hydrocarbons early. It has become apparent in recent years that not all kerogens generate hydrocarbons at the same catagenetic levels. Rich rocks will become overpressured earlier than lean ones and thus will also expel hydrocarbons earlier.Kerogen . Many workers now believe that microfracturing of source rocks is very important tor hydrocarbon expulsion. residual kerogen as well as small molecules that are the direct precursors for petroleum and natural gas. Other kerogens usually follow a more traditional model.
n-alkanes. Petroleum. we must separate the characteristics related to kerogen composition from those related to the transformation of bitumen to petroleum and from those related to changes occurring in reservoirs. NSOs.Bitumen. In order to understand bitumen and petroleum compositions and to use them for exploration. This chapter will compare and contrast bitumen and petroleum compositions and examine the factors responsible for the observed differences. contains a wide variety of small and medium-sized molecules with one or more heteroatoms. have been studied in petroleums. Saturated hydrocarbons are the most thoroughly studied of the components of petroleum and bitumen because they are the easiest to work with analytically. however. The large sizes of asphaltene units render . One fraction consists mainly of saturated hydrocarbons. Each of the fractions contains certain types of chemical compounds. Both bitumens and petroleums exhibit a wide range of compositions. The lighter of these fractions. In order to investigate the individual compounds present. and cyclics. The final fraction contains very large.24 Bitumen. and Natural Gas - 5 . Heavier aromatic and naphthenoaromatic hydrocarbons. and form complexes with molecular weights of perhaps 50. indeed. A second fraction consists of aromatic hydrocarbons and some light sulfur-containing compounds. branched hydrocarbons (including isoprenoids). Maturity also exerts control over bitumen and petroleum composition. variously called polars. and how much is due to physical separation of chemical compounds having very different properties. but we are not certain whether they occur mainly within the source rock or during migration through the reservoir rock. Asphaltenes tend to aggregate into stacks because of their planarity. Petroleum. Such correlations can be particularly useful in establishing genetic relationships among samples.000. many unanswered questions remain about the processes that transform bitumen into petroleum. There is no doubt that they are related. and steranes. Much of this variety is related to source-rock facies and the composition of the kerogens that generated the bitumens. triterpanes. highly aromatic asphaltene molecules that are often rich in heteroatoms. but they also exhibit many important differences. Major compositional changes occur in going from bitumen to petroleum. We also do not know how much of the change involves chemical reactions. while others are only trace contributors. Few of these heterocompounds have been studied carefully. bitumen is almost universally accepted as the direct precursor for petroleum. we first separate a crude oil or a bitumen into several fractions having distinct properties. and resins. and Natural Gas INTRODUCTION Petroleum obtained from reservoir rocks and bitumen extracted from fine-grained rocks have many similarities. Bitumen and petroleum compositions can also be used as tools in correlating samples with each other. Light aromatic hydrocarbons. Some of these are present in relatively large quantities. However. but these compounds are lost from bitumens during evaporation of the solvent used in extracting the bitumen from the rock. COMPOUNDS PRESENT IN BITUMEN AND PETROLEUM GENERAL CLASSES OF COMPOUNDS Both bitumen and petroleum contain a very large number of different chemical compounds. Most of the NSO compounds appear in the remaining two fractions. Reservoir transformations in some cases greatly affect oil composition and properties. The influence of the lithologies of source and reservoir rocks on these compositional changes is poorly understood. particularly those derived from diterpanes. like benzene and toluene. are more commonly studied.
Many other types of organic compounds in crude oils and bitumens are not considered to be biomarkers because they cannot be related directly to biogenic precursors. For the most part n-alkanes present in terrestrial plants have odd numbers of carbon atoms.) Even-carbon preferences occur principally in evaporitic and carbonate sediments. The average of two ranges is taken to minimize bias produced by the generally decreasing n-alkane concentrations with increasing number of carbon atoms. (Among the acids and alcohols present in living organisms. These n-alkanes are believed to be formed by hydrogenation (reduction) of longchain fatty acids and alcohols having even numbers of carbon atoms. which are derived from biogenic precursor molecules. of course. are essentially molecular fossils. Another important indication of the origin of n-alkanes is the distribution of individual homologs. of biological origin. Many of the compounds and classes of compounds that we find in crude oils and bitumens are called biomarkers. Many sediments. or CPI. even-carbon homologs predominate as strongly as do the oddcarbon homologs among the n-alkanes. because the concentration of n-alkanes often decreases with increasing carbon number. and Natural Gas . These compounds. or of the diagenetic conditions under which the organic matter was buried. The distributions are quite sharp. Asphaltenes can thus be removed from oils or bitumens in the laboratory or refinery by adding a light hydrocarbon. 25. In most cases. Their n-alkane distributions reflect this mix.and even-carbon members is equal. receive contributions of n-alkanes from both terrestrial and marine sources. the lower-carbon homologs are given more weight in the calculation. Sediments are also known that exhibit a strong preference for n-alkanes having an even number of carbon atoms. but their sources are simply no longer recognizable due to diagenetic and catagenetic transformations. In contrast. was developed as a measure of the strength of the odd-carbon predominance in n-alkanes over the even alkanes (in the series from 23 upwards).Bitumen. however.0. SPECIFIC COMPOUNDS Biomarkers. however. and 31 atoms. especially 23. and no preference for either odd. If odd-carbon homologs predominate. FACTORS AFFECTING COMPOSITION OF BITUMEN AND PETROLEUM SOURCE AND DIAGENESIS Biomarkers n-Alkanes were among the first biomarkers to be studied extensively. the CPI is greater than 1. If the number of odd. 29. The most useful biomarkers serve as indicators of the organisms from which the bitumen or petroleum was derived. Because of their molecular complexity and heterogeneity. where input of terrestrial n-alkanes is minimal and diagenetic conditions are highly reducing. In a few cases specific precursor organisms or molecules can be identified. or members of the n-alkane series. CPI values can therefore . Other compounds. They are. and by their catagenetic formation from long-chain compounds such as fatty acids and alcohols. Their high concentration in bitumens and oils is best explained by their existence in plant and algal lipids.0. marine algae produce n-alkanes that have a maximum in their distribution at C-17 or C22. 27.or even-carbon homologs is evident. such as pentane or propane. asphaltene molecules have not been studied in detail.25 them insoluble in light solvents. although we know for certain that the biomarker molecule is biogenic. Carbon Preference Index. we are unable to use it as an "index fossil" for specific organisms. However. Petroleum. an abbreviation for biological markers. the CPI is 1. depending upon the species present. whereas in other instances we may be able to limit the possible precursors to only a few species.
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deviate from 1.0 even when no preference is distinguishable by visual inspection of the distribution curve. n-Alkane distributions are greatly modified by thermal maturity. Chain lengths gradually become shorter, and the original n-alkanes present in the immature sample are diluted with new n-alkanes generated during catagenesis. Because the newly generated n-alkanes show little or no preference for either odd- or even-carbon homologs, CPI values approach 1.0 as maturity increases. n-Alkane distributions in bitumens and oils derived from algae do not show the influences of maturity as clearly because the original CPI values are already very close to 1.0. It is therefore often difficult to estimate maturity levels in pelagic rocks on the basis of n-alkane data. Parameters other than Biomarkers. Sulfur contents are also strongly influenced by diagenetic conditions. For economic and environmental reasons, oils having more than about 0.5% sulfur are designated as high-sulfur. Many high-sulfur oils contain 1% sulfur or less, but in some areas sulfur contents can reach 7% (Monterey oils from the onshore Santa Maria area, southern California, for example). A few oils contain more than 10%. These high-sulfur bitumens and crude oils are derived from high-sulfur kerogens. As we saw earlier, sulfur is incorporated into kerogens formed in nonclastic sediments that accumulate where anaerobic sulfate reduction is important. Most oils and bitumens derived from lacustrine or ordinary clastic marine source rocks will be low in sulfur content, whereas those from euxinic or anoxic marine source rocks will be high-sulfur. Sulfur occurs predominantly in the heavy fractions of oils and bitumens, particularly in the asphaltenes. High-sulfur oils therefore have elevated asphaltene contents.
Introduction. There are two main types of reservoir transformations that can affect crude oils (reservoir transformations are not applicable to bitumen because, by definition, the material in a reservoir is petroleum). Thermal processes occurring in reservoirs include cracking and deasphalting. Nonthermal processes are water washing and biodegradation. Of these, cracking and biodegradation are by far the most important. Cracking and Deasphalting. Cracking, which breaks large molecules down into smaller ones, can convert a heavy, heteroatom-rich off into a lighter, sweeter one. Waxy oils become less waxy. API gravities increase, and pour points and viscosities decrease. When cracking is extreme, the products become condensate, wet gas, or dry gas. Cracking is a function of both time and temperature, as well as of the composition of the oil and the catalytic potential of the reservoir rock. It is therefore impossible to state that cracking always occurs at a certain depth or reservoir temperature. Most oils, however, will be reasonably stable at reservoir temperatures below about 90° C, regardless of the length of time they spend there. On the other hand, a reservoir above 120° C will contain normal oil only if the oil is a recent arrival. Although the role of catalysis in hydrocarbon cracking in reservoirs has not been proven, many workers suspect that clay minerals are important facilitators of hydrocarbon breakdown. Catalytic effectiveness varies greatly from one clay mineral to another, however, and our partial understanding of this difficult subject is not of much practical use at the present time. Cracking also brings about deasphalting, because asphaltene molecules become less soluble as the oil becomes lighter. Precipitation of asphaltenes in the reservoir will lower sulfur content and increase API gravity appreciably. Biodegradation and water washing. Water washing involves selective dissolution of the most soluble components of crude oils in waters that come in contact with the oils. The smallest hydrocarbon molecules and the light aromatics, such as benzene, are the most soluble. The effects of water washing are rather difficult to determine because they do not affect the oil fractions that
Bitumen, Petroleum, and Natural Gas - 27
are most frequently studied. Furthermore, in most cases the effects are quite small because of the low solubilities of all hydrocarbons in water. Finally, water washing and biodegradation often occur together, with the more dramatic effects of biodegradation obscuring those of water washing. Biodegradation is a transformation process of major importance. Under certain conditions some species of bacteria are able to destroy some of the compounds present in crude oil, using them as a source of energy. The bacteria responsible for biodegradation are probably a mixture of aerobic and anaerobic strains. Only aerobic bacteria are believed to actually attack hydrocarbons, but anaerobes may consume some of the partially oxidized byproducts of initial aerobic attack. Because biodegradation changes the physical properties of oils, it can have serious negative financial implications. Heavily biodegraded oils are often impossible to produce (Athabasca Tar Sands of Alberta, Canada, and the Orinoco heavy oils of Venezuela, for example). If production is physically possible, it may be expensive or uneconomic. It is therefore important to understand where and why biodegradation occurs, and what its effects are on oil composition. Biodegradation may actually start during oil migration (provided required temperature and oxygen conditions are met), because oil-water interactions are maximized then. Most biodegradation probably occurs within reservoirs, however, since the length of time an oil spends in a reservoir is usually much longer than its transit time during migration. Biodegradation can vary in intensity from very light to extremely heavy. Because the chemical and physical properties of an oil change dramatically in several predictable ways during biodegradation, biodegraded oils are easily recognized. Many basins have at least a few biodegraded oils, and in some areas they are epidemic. Bacteria that consume petroleum hydrocarbons have strong preferences. Hydrocarbons are not their very favorite foods, and they eat them only because there is nothing else available. The preferred hydrocarbons are n-alkanes, presumably because their straight-chain configurations allow the bacterial enzymes to work on them most efficiently. Also attractive to the "bugs" are long, alkyl side-chains attached to cyclic structures. After the n-alkanes and alkyl groups are consumed, the bacteria begin to destroy compounds having only a single methyl branch or those having widely spaced branches. Then they move on to morehighly branched compounds, such as the isoprenoids. In the last stages of biodegradation, polycyclic alkanes are attacked. Because the hierarchy of bacterial attack on crude oils is well known, it is possible to assess the degree of biodegradation by observing which compounds have been destroyed. Sulfur contents of crude oils also increase as a result of biodegradation. In a heavily biodegraded oil the sulfur content may increase by a factor of two or three. Sulfur is undoubtedly concentrated in the oil by selective removal of hydrocarbons, and may also be added by bacterially mediated sulfate reduction.
COMPARISON OF BITUMEN AND PETROLEUM
Although bitumens and crude oils contain the same compounds, the relative amounts are quite different. In the process of converting bitumen to petroleum, either the NSO compounds are lost in large quantities, or they are converted to hydrocarbons. In actuality, both processes probably occur, although selective loss of nonhydrocarbons during expulsion is probably most effective in concentrating the hydrocarbons. Bitumen composition depends strongly on the lithology of the host rock. Carbonates contain bitumens that are much richer in heterocompounds than are shales, and their hydrocarbon fractions are more aromatic. These differences are the result of the higher sulfur contents of kerogens in carbonates. Oils derived from carbonate sources are also richer in heterocompounds than oils sourced from shales.
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Natural gas contains many different compounds, although most of them are present only in trace quantities. The principal components with which we shall be concerned are light hydrocarbons (methane through butanes), C02, H2S, and N2. Carbon dioxide and N2 are generally associated with very hot reservoirs. C02 is derived either by oxidation of oil or gas or by decomposition of carbonates. The origin of the C02 can be determined easily by carbon-isotope measurements: the very different isotopic compositions of organic-carbon species and carbonates are carried over into any C02 derived from these materials. Nitrogen is thought to be an indicator of high levels of maturity formed primarily by metagenetic transformation of organic nitrogen and ammonia bound to clay minerals. Hydrogen sulfide is usually derived from high-sulfur kerogens or oils. These in turn are formed most readily in carbonates. Thus sour gas is most common in carbonate reservoirs or in places where the source rock was a carbonate. H2S could also be formed by the reaction of hydrocarbons with sulfate in reservoirs, especially carbonates containing anhydrite. Biogenic gas, most of which occurs at shallow depths, but which can apparently form (or at least persist) at depths of a few thousand meters, is very dry, containing only trace amounts of hydrocarbons heavier than methane. In contrast, the first gas produced during catagenesis is quite wet. With increasing maturity, gas again becomes progressively drier as a result of cracking of the heavier hydrocarbons to methane.
Bitumens and crude oils contain the same classes of compounds, but their relative concentrations are quite different. These differences are in some cases related to differences in maturity; in other examples they are probably a result of preferential expulsion of hydrocarbons from source rocks. Individual compounds occur in quite variable proportions in bitumens. Source, diagenesis, and maturity all exert control over these distributions. When source and diagenetic influences have been removed, the porphyrins, steranes, triterpanes, and n-alkanes in mature bitumens are found to be very similar to those in crude oils and quite different from those in immature bitumens. Oil compositions can also be strongly affected by reservoir transformations, including biodegradation, water washing, cracking, and deasphalting. Many of the factors that influence the composition of oils and bitumens are well understood and predictable, and can be used to obtain information about paleoecology, thermal history, and reservoir conditions. Gas composition is governed first of all by whether the gas is of biogenic or thermal origin. Biogenic gas is always dry, whereas thermal gas may be wet or dry. Carbon-isotope ratios are good indicators of the source of gas; biogenic gas is much lighter isotopically than thermal gases. Other important components, such as CO2, N2, and H2S, are indicative of high temperatures or sulfur-rich source material.
Today there are only three mechanisms of primary migration that are given serious consideration by most petroleum geochemists: diffusion. where pre-existing light hydrocarbons bleed out of the rocks prior to the onset of significant generation and expulsion. PRIMARY MIGRATION MECHANISMS Many theories about primary migration (expulsion) have been popular at various times. but will describe the most widely held views on the dominant mechanisms of primary and secondary migration and accumulation. By far the most popular mechanism invoked today to explain primary migration is expulsion of hydrocarbons in a hydrophobic (oily) phase. lowpermeability source rock into a carrier bed having much greater permeability. Momper (1978) suggested that in most cases no microfracturing or expulsion could occur until a threshold amount of bitumen had been generated in the source rock. The hydrocarbons within the pores then become isolated again because of the impermeability of the waterwet source rocks to hydrocarbons. it involves expulsion of hydrocarbons from their fine-grained. Diffusion has been shown to be active on at least a minor scale and over short distances in carefully studied cores. expulsion. This chapter wi11 not go into the physics and chemistry of migration in detail. and pressure release can be repeated. An important implication of the microfracturing model is that expulsion cannot take place until the strength of the source rock has been exceeded. In order to understand the complex sequence of events that we call migration. Diffusion would therefore have to be coupled with a powerful concentrating force to yield accumulations of appreciable size. and solution in gas. and overpressuring commences anew. any contribution by diffusion will be overwhelmed by that from other expulsion mechanisms. it is probably most effective in immature rocks. The main problem with diffusion as an important mechanism of migration is that diffusion is by definition a dispersive force. Once the internal pressure has returned to normal. Furthermore.29 6 . Its importance is probably limited to the edges of thick units or to thin source beds.Migration DEFINITIONS Migration is the movement of oil and gas within the subsurface. we must look at each of these steps separately. Many cycles of pressure buildup. Laminated source rocks may therefore expel hydrocarbons with greater efficiency than massive rocks. Primary migration is the first phase of the migration process. There appear to be three distinct ways in which oilphase expulsion can occur. Secondary migration is the movement of oil and gas within this carrier bed. oil-phase expulsion. During intense hydrocarbon generation. Accumulation is the concentration of migrated hydrocarbons in a relatively immobile configuration. Each of these steps is quite distinct from the others. . particularly along lines of weakness such as bedding planes. but those that have been discounted will not be discussed here. Traps are the means by which migration is stopped and accumulation occurs. whereas accumulation of hydrocarbons requires concentration. Momper's value has been widely accepted as a reasonable average.Migration . microfracturing occurs. When the internal pressures exceed the strength of the rock. Although the exact threshold value must vary considerably as a function of rock lithology and other factors. Based on empirical evidence. One occurs most commonly as a result of microfracturing induced by overpressuring during hydrocarbon generation. where they can be preserved over long periods of time. the microfractures heal. microfracturing.
Therefore the threshold must represent not only a hurdle to be cleared by the bitumen before it can leave the source rock. A second way in which oil-phase expulsion can occur is from very organic-rich rocks prior to the onset of strong hydrocarbon generation. Of course. oil-phase expulsion can take place when bitumen forms a continuous network that replaces water as the wetting agent in the source rock. and assuming that expulsion of hydrocarbons is ten times as efficient as expulsion of NSO compounds. Such a phase could only exist where the amount of gas far exceeds the amount of liquid hydrocarbons. Therefore. expulsion of oil dissolved in gas. upward. primary migration may be of poor efficiency. but a large proportion of NSO compounds and heavier hydrocarbons are left behind. hydrocarbons will be expelled in any direction that offers a lower pressure than that in the source rock. particularly in brittle carbonate and opal-chert source rocks. Finally. where they do exist. This type of expulsion is probably only operative in very rich source rocks during the main phase of oil generation. Expulsion of hydrocarbons is facilitated because water-mineral and water-water interactions no longer need be overcome. unfractured source-rock units are relatively rare. we conclude that solution in gas is a minor mechanism for oil expulsion. Fracture and joint systems. The third mechanism. Because neither case is of great general significance for petroleum formation. but the mechanism by which overpressuring is achieved is not understood. because petroleum is being forced through rocks having low matrix permeabilities. the migrating fluids will take them. In most cases hydrocarbons are generated within short distances of viable secondary-migration conduits. Primary migration is unquestionably the most difficult part of the entire migration process. depending upon the carrier-bed characteristics of the surrounding rocks.30 Once the threshold has been exceeded. requires that there be a separate gas phase. As soon as easier paths become available. Thus inefficiency of expulsion is responsible for much of the difference in composition of bitumen and petroleum that we noted earlier. or downward. also make excellent secondary-migration pathways." We can only estimate the fraction of the bitumen left in the source rock during microfractureinduced expulsion. Sand stringers within shale units can provide secondary migration conduits for hydrocarbons sourced in the shales. The organic matter expelled consists mainly of lipids that were present in the sediment during deposition and diagenesis. DISTANCE AND DIRECTION The distances traversed by hydrocarbons during primary migration are short. By comparing the average hydrocarbon compositions of bitumen and crude oil. Because the source rock is overpressured. most of the hydrocarbons are expelled. this early expulsion mechanism seems to be limited to rocks having very high original contents of lipids. Massive. Because the driving force for microfracture-induced primary migration is pressure release. therefore. we can estimate that once the expulsion threshold is reached the expulsion efficiency for bitumen is about 50%. In most cases the distances of primary migration are probably between 10 centimetres and 100 m. this approach is rather approximate. This expulsion process probably releases internal pressures in the rock. Primary migration is difficult and slow. Thus a source rock lying between two sands will expel hydrocarbons into both carrier beds. but it does give some idea of the efficiency of expulsion. expulsion can be lateral. Thus primary migration ends whenever a permeable conduit for secondary migration is reached. it would be expected only in the late stages of catagenesis or in source rocks capable of generating mainly gas. .Migration . but also an "exit tax.
the more deformation is required. If. the globule must deform to squeeze into the pore. A third force-namely. Hydrocarbons are thus capable of displacing water downward and moving upward themselves. the globule cannot enter. and becomes stuck until either the buoyant force or the capillary entry pressure changes. which is resistance to entry of the hydrocarbon globule or stringer into pore throats. Thus movement within a confined migration conduit will be updip perpendicular to structural contours whenever possible. That is. Coalescence of globules of hydrocarbons after expulsion from the source rock therefore increases their ability to move upward through water-wet rocks. If the upward force of buoyancy is large enough. if bulk water movement opposes the direction of buoyant movement. then the rate of hydrocarbon movement should be enhanced somewhat. but it is not essential and does not change our basic model. whereas capillary-entry pressure retards or stops it. secondary migration will cease until either the capillary-entry pressure is reduced or the buoyant force is increased. the force required to deform the oil globule enough to enter the pore throat. Buoyancy promotes migration. the pore throat is very tiny or if the buoyant force is small. This fact has important implications for tracing migration pathways through a thick conduit. hydrodynamic flow. When hydrocarbons cease moving.31 SECONDARY MIGRATION MECHANISM Once hydrocarbons are expelled from the source rock in a separate hydrocarbon phase into a secondary-migration conduit. Where faulting or facies changes create impassable barriers (capillary-entry pressure exceeds buoyant force). Within massive sandstone. however. we say that accumulation has occurred. the globule will squeeze into the pore throat and continue moving upward. This model is very simple. Structural contours on the top of the carrier bed will . then the rate of hydrocarbon transport will be retarded. DISTANCE AND DIRECTION Secondary migration occurs preferentially in the direction that offers the greatest buoyant advantage. can modify hydrocarbon movement. These modifications to the overall scheme are probably minor. secondary migration will occur both laterally and vertically. If the capillary-entry pressure exceeds the buoyant force. hydrocarbons entering the land from an underlying source rock will move toward the top of the sand even as they migrate laterally updip. If water is flowing in the subsurface in the same direction as hydrocarbons are moving by buoyancy. The magnitude of the buoyant force is proportional both to the density difference between water and hydrocarbon phase and to the height of the oil stringer. Whenever a pore throat narrower than the globule is encountered. subsequent movement of the hydrocarbons will be driven by buoyancy. requiring only the existence of two forces. Hydrocarbons are almost all less dense than formation waters. Retardatin of buoyant movement as an oil globule (X) is deformed to fit in to a narrow pore throat (Y). In contrast. Opposing the buoyancy is capillary-entry pressure. The upward buoyant force is partly or completely opposed by the capillary-entry pressure.Migration . migration may have to proceed at an oblique angle to structural contours. and therefore are more buoyant. The smaller the pore throat.
when migration was thought to occur mainly in water solution. large drainage areas and chances for very large accumulations. thus providing a potentially very effective system for combined vertical and lateral migration. the process of hydrocarbon accumulation was somewhat mystical. however. Long-distance migration implies. However. not only because they often juxtapose carrier beds from different stratigraphic horizons. This model greatly simplifies the problem of accumulation.Migration . Indeed. are broken up tectonically and have poor lateral continuity of carrier beds. can offer possible pathways (although sometimes rather tortuous ones) for vertical migration. The question of long-distance migration has been much discussed and disputed. at which time they suddenly became immiscible with the water and formed a separate hydrocarbon phase. they are rare for very good geological reasons: they occur in extremely stable tectonic settings where major but gentle downwarping has deposited and matured huge volumes of source rocks. because now accumulation can occur where the buoyancy-driven movement of the hydrocarbon phase is stopped or even strongly impeded. the heavy oils in the Orinoco Belt of Venezuela. all must have migrated long distances. Most basins. and has provided as carrier beds continuous blankets of sand juxtaposed with these source rocks. ACCUMULATION INTRODUCTION In the old days. leading to smaller fault-bounded accumulations and vertical migration. Lateral migration is therefore often stymied. Vertical migration across stratigraphic boundaries is more difficult. It is possible to have lateral migrations of as much as a few hundred kilometers in exceptional circumstances. Migration updip within a single stratum can accomplish a large amount of "vertical" migration rather painlessly. for example. distances of several thousand feet are not unheard of. otherwise it is impossible to account for the incredible volumes of hydrocarbons in place today. however. Various mechanisms for exsolution were proposed to explain how all this was supposed to happen. Today we believe that hydrocarbons migrate as a separate phase. as a result of both tectonic disruption and facies changes related to tectonic events. Hydrocarbons had to remain in solution until they reached the trap. Lack of long-distance migration opportunities implies that supergiant and giant accumulations are far less likely and that exploration targets will be smaller. The problem in discussing long-distance migration is that such cases are rare. including the Athabasca Tar Sands of western Canada. There is no a priori reason why secondary migration cannot be a very-long-distance phenomenon. The absence of both tectonic and stratigraphic barriers permits long-distance migration. Stacked sands in a paleodelta. but also because an active fault or the brecciated zone adjacent to a fault may itself have high permeability. Cap rocks having low . the largest hydrocarbon deposits known. Nevertheless. although it should be remembered that there are two fundamentally different types of vertical migration. because final control on migration direction will be exerted by the upper part of the bed (assuming that no laterally continuous shale breaks divide the carrier bed into two or more separate systems). Much more common. Vertical migration distances can also be considerable.32 in general be more useful than contours on its base. and the Saudi Arabian crude oils. Unconformities also can juxtapose migration conduits. Vertical migration can also occur across formations. Faults may play an important role in vertical migration. Drainage area is one of the most important factors influencing the size of hydrocarbon accumulations. by definition. are basins in which lateral migration distances do not exceed a few tens of kilometers.
KINETIC TRAPS Kinetic traps represent a fundamentally new concept in trapping mechanisms for hydrocarbons. The Elmworth Field in the Alberta Deep Basin of Canada is the prototype for kinetic gas accumulations. it remains water wet. Gas production is actually from the low-permeability sand rather than from the high-permeability sand updip and downdip. No traditional seal exists. This model requires. Thus the Elmworth Field exhibits a water-over-gas contact. of course.33 permeabilities to hydrocarbons provide barriers to migration: that is. High rates of hydrocarbon generation can actually create traps by causing tensile failure of source rocks that have become overpressured as a result of hydrocarbon generation. and vertical migration becomes important. a fractured shale that is both source and reservoir. the low-permeability sands become filled with gas. Classical traps are well understood. Seals in the traditional sense of the word may not exist.Migration . Much of the hydrocarbon storage at Antelope is apparently in silts and sands juxtaposed with the producible Bakken reservoir. rocks whose capillary-entry pressures are high enough to overcome hydrocarbon buoyancy. CLASSICAL TRAPS. The seal prevents vertical migration from the reservoir rock into overlying strata. . and will be covered separately. Because the high permeability sand updip allows gas to migrate rapidly through. that strong hydrocarbon generation and migration is going on today. Gas generated in the late stages of kerogen catagenesis in the Alberta Deep Basin is trapped in a sandstone bed having lower permeability than the overlying sand. while the structure or lithologic change prevents lateral updip migration. The low permeability sand thus creates a bottleneck to gas migration. Lateral migration is of necessity short distance. Cross section across the Rhine Graben of West Germany showing the discontinuity of strata as a result of extensional tectonism endemic to rift basins. Because gas generation is very rapid. The simple principle behind a kinetic trap is that hydrocarbons are supplied to the trap faster than they can leak away. Fracturing associated with high races of oil generation in the Green River Shale has created a supergiant accumulation at Altamont. Most hydrocarbon traps are either structural or stratigraphic. The much smaller Antelope Field produces from the Mississippian Bakken Formation. Accumulations are small because drainage areas are small.
Because intense oil generation is going on now. When the original hydrocarbon phase contains large amounts of light components. and thus get left behind as the oil globule or stringer moves upward. A second characteristic is that gas hydrates form effective seals against vertical hydrocarbon migration. the quantities of gas in such accumulations are huge. the lighter (gas) phase will be far more buoyant than the liquid phase. and would be incapable of sealing accumulations for long geologic periods. unconsolidated sediments that would have no other means of retaining the methane. EFFECTS ON OIL AND GAS COMPOSITION It has already been suggested that most of the compositional changes seen between bitumens and normal crude oils occur during expulsion (primary migration) from the source rock. there may be a chromatographic effect during secondary migration. but hydrates large enough to accommodate butane molecules are known. large accumulations have formed despite high rates of leakage. The technology necessary for producing these hydrocarbons has not yet been developed. Because hydrate zones are often hundreds of meters thick. tar-mat traps are worth discussing because they include the largest hydrocarbon accumulations known: those of the Athabasca Tar Sands and the Orinoco heavy-oil belt. The base of the gas hydrate zone forms a pronounced seismic reflector that often simulates bottom contours and cuts across bedding planes. Gas hydrates form and are stable under pressuretemperature regimes that occur at depths of a few hundred meters below the sea floor in deep water. It will therefore migrate much faster and . but it may also include some heavier hydrocarbons dissolved in the gas. these changes in temperature and pressure can cause separation of the original phase into a liquid phase and a gas phase. of course. and thus are not expelled as efficiently with the oil phase. One important feature of methane hydrates is that they are much more efficient at storing methane than is liquid pore water. GAS HYDRATES Formation of crystalline hydrates of natural gas provides an extremely efficient trapping mechanism for natural gas. TAR-MAT TRAPS Tar mats produced by biodegradation can create excellent seals. because the same conditions that created the tar mat persist in the subsurface. Formation of hydrates thus provides an important trapping mechanism. Despite the rarity of tar-mat seals. especially methane. because much of the methane trapped is biogenic and was formed in young. tar mats may provide the only possible means for retaining any hydrocarbons. Accumulations beneath tar-mat seals are generally biodegraded themselves. Phase changes occur as a result of decreases in pressure and temperature during migration. Cap-rocks in those fields are often poor. however. In cases where no other structural or stratigraphic trapping mechanism exists. The polar molecules once again interact most strongly with interstitial water and mineral surfaces. The gas phase will. At the present time the vast potential of gas-hydrate accumulations is just beginning to be recognized. contain mainly light components. and the poor producibilitv of the hydrocarbons they trap. As soon as two immiscible phases are formed. These gas hydrates consist of a rigid lattice of water molecules that form a cage within which a single molecule of gas is trapped.Migration .34 Many of the accumulations in Pliocene reservoirs in southern California are also kinetic accumulations in a slightly different sense. Once expulsion has occurred. and in zones of permafrost. but in the future gas-hydrate accumulations may be of great economic significance. Methane is by far the most commonly trapped gas molecule. The polar (NSO) compounds interact most strongly with both mineral surfaces and water molecules.
. Thus if we can determine the timing of generation. and the vertical and horizontal distances involved. depending upon stacking of reservoirs. Many light oils (often called condensates) probably have such an origin Proposed separation of petroleum components during secondary migration as a result of chromatographic effects. We have already stated that oil is expelled primarily as a liquid phase. and the timing of expulsion. We need to know when hydrocarbons moved. We already know two important facts about timing from our previous discussion: expulsion based on microfracturing cannot occur before generation. in what direction they moved. and expulsion occurs concurrently with generation to relieve generation-induced overpressuring. and how far they moved. gas is presumably expelled as a gas phase. Barriers can be created by folding. Efficiency of expulsion for hydrocarbons is apparently much higher than for NSO compounds. Proximity to effective source rocks and their permeabilities to hydrocarbons determine conduits. leading to an enrichment of hydrocarbons in the expelled liquid. In summary. "What does this mean for exploration?" From their perspective the important aspects of primary migration are the nature of the hydrocarbons expelled (oil or gas). by decreases in permeability as a result of facies changes. Unstable basins seldom have depositional or tectonic continuities necessary for longdistance lateral migration to occur. or by the presence of tars. In using our understanding of secondary migration for exploration. SIGNIFICANCE FOR EXPLORATION Explorationists who are reading about migration will surely ask. Tectonically stable basins have the best potential for long-distance migration and supergiant accumulations. Vertical-migration distances can be considerable. When separation of a single hydrocarbon phase into two phases occurs.35 will also assume the structurally high position in any reservoirs containing both phases. the barriers that modify die direction of migration and eventually stop it. by faulting. Pathways. both new phases will have compositions that differ drastically from the original phase. vertical faulting. the efficiency of expulsion. Timing of expulsion must be dealt with in a different way. Lateralmigration distances are strongly influenced by tectonic and depositional histories of basins.Migration . Efficiency of expulsion of liquids has already been estimated to be in the neighbourhood of 50% after the expulsion threshold has been reached. we want to determine the main pathways and conduite through which migration occurs. as explorationists we have very pragmatic interests in migration. Polar compounds interact more strongly with water and rock minerals and thus move more slowly than hydrocarbons. as we have seen. and the possibilities of combined vertical and lateral migration. we will also have determined the timing of expulsion. are determined by structural contours on the top of the carrier beds.
36 7 . but it is often convenient to exaggerate the vertical to show the individual beds more clearly. Faults will be marked by jumps of the contours. To complement the structure contour map. before we reached our modern understanding of the geology of petroleum. The contours are in feet below mean sea-level. The highest point of the reservoir. by displacing the water already there in the porosity. and hoping for the best. and furthermore we can map out the extent and shape of the trap with a good deal of precision-thanks mostly to modern seismic techniques. The location of a trap in the subsurface is often the first objective of an exploration program. so that the highest points on the map have the lowest values. is the spill-point: this is where oil. is mapped by contours showing depth below sealevel. If then we are to find any of it still preserved. is known as the crest of the trap. exploration used to consist largely of finding a trap. not only must the reservoir be overlain by an impervious layer forming a cap rock or seal (shales or evaporites are likely to be the most effective). Such a configuration of the reservoir is known as a trap. as the beds on one side are dropped down relative to the other.Petroleum Traps We have seen petroleum generated in and expelled from the source rock formation into an overlying or underlying reservoir. they can be mapped by means of contours drawn on the top of the reservoir formation. up towards the ground surface. one or more cross-sections may be drawn. This may be caused either by the reservoir itself dying out or by an interruption of its upwards continuity to the surface. A structure contour map resembles an ordinary topographic contour map. they should properly be drawn with the same scale for both the vertical and the horizontal. These are illustrated using a simple anticline as an example. which may refer either to its depth or to the spot under the ground where it lies.Petroleum Traps . Nowadays we can do better. If it can. it will escape to surface as a seepage. the ticks are on the downthrown sides of the faults. To give a true representation. we need a few definitions. Any oil getting there will be unable to migrate further and so it starts to accumulate. The lowest point. but there must also be some sort of blockage to prevent further migration. (a) A simple hypothetical anticline. Note that we commonly highlight petroleum accumulations by shading or colouring the reservoir formations where they contain oil or gas. which may give a misleading impression of `lakes' of petroleum under the ground! Structure contour maps. if more continues to migrate up into the trap than can be . except that the contours are in depth below sealevel.(2-18) Before we go further. (b) A representation of the Piper field in the North Sea: the heavy lines are faults cutting the top of the reservoir and causing the contours to jump. First. THE REPRESENTATION OF TRAPS Traps are commonly depicted in two ways. where it is lost. Indeed. The top of a reservoir formation. drilling a well into it.
then we may see a gas-water contact. will occur as a gas cap above a gas-oil contact. Hydrodynamic traps. The vertical height of the oil (or gas) between the crest of the trap and the water contact is the oil. 2. there are various types of . When referring to a single well. they are embraced by the familiar terms oilfield or gasfield. so that we can recognize a generally horizontal oil-water contact. STRUCTURAL TRAPS The best known type of trap is the anticline: on reaching the crest. i. Similarly gas. However. If there is no oil. formed partly by structural and partly by stratigraphic effects.Petroleum Traps . These have to be discounted and the bits that remain as useful reservoir in a well section may be lumped together as the net reservoir with a net pay. or in their layering. but not entirely due to either. They are normally classified under four headings (2-21): 1. using a cross-section of a simple anticline as example (2-19). however. Now we can start to consider the types of trap whose discovery may await us. where the trap has been produced by deformation of the beds after they were deposited. which have porosities and permeabilities too low for them to contribute oil to production. A single accumulation of oil or gas is called a pool. Combination traps. which are rare and are mentioned mainly for completeness. separates out on top within the pore-spaces of the reservoir.e. being lighter still. 4. petroleum migrating up along a reservoir can go no further and it accumulates there as a pool. Oil being lighter than water. Where there is more than one such pool in the same or overlapping areas. Structural. the only structural effect being a tilt to allow the oil to migrate through the reservoir. in which the trap is formed by changes in the nature of the rocks themselves.37 accommodated. that most reservoir formations include some tight intervals. Just a couple more terms. The vertical height between the spill-point and the crest is referred to as the closure.(or gas-) column. and the same term is used loosely to refer to the area of the trap above the level of the spill-point. Some terms used to define a trap. will spill out (under) and migrate on. The trap is due to water flowing through the reservoir and holding the oil in places where it would not otherwise be trapped. Let us remember. the informal term pay is often used. 3. Stratigraphic. perhaps if more than one reservoir is present. either by folding or faulting.
and we may be able to continue exploration down to depths where we have to stop for other reasons. This can only happen if there is an apparent thickening of some beds over the crest of the fold. depending on the nature and strength of the rock layers being folded. but an understanding of the shape and size of a prospect is clearly critical to programming an exploration well. a well would have to be located off-crest at surface. noting the differences in shape and prospectivity that we have to try to interpret. and we may no longer be able to see where the bottle is. To test the crest at depth. The similar anticline.Petroleum Traps . with one flank steeper than the other. we have to know its depth to know where best to locate the well. on the other hand. In this type of structure. There is a definite limit to the depths to which we should drill. We will describe in a little detail the most important types of anticline. we can thus expect to find only smaller and smaller accumulations of petroleum down to the centre of curvature. in cross-section. many structures have forms in-between the two extremes. and the blanket bulges upwards with an anticlinal shape. the anticline is asymmetrical. Traps can also be formed against faults if a chopped-off reservoir is thrown against a shale or other impervious rock. Let us see what the implications are for exploration. Anticlines. . beyond which there may be no trap left to explore as the consequence of decoupling of layers.38 anticlines with different shapes and geometries that can affect both their prospectivity and the positions of optimum drilling locations: we have to try to understand them. (a) The dips are the same on both flanks and the crest is beneath the same locality at all depths. but we commonly have to undertake some form of geometrical construction to interpret what is happening at depth. so that the beds become intensely crushed and thrust together: we may no longer even have an anticline at all. Cross-sections of trap-forming anticlines. These conditions mean that the anticline becomes smaller and tighter at deeper levels until we reach a common `centre of curvature'. In practice. Below this point we have just too much rock to fit into the anticline. Imagine an old-fashioned stone hot-water bottle in a bed with a blanket over it: we can still see the form of the hot-water bottle. Other types of anticline can be formed without any lateral compression at all: an important one is the drape or drape-compaction structure. This is a very different kettle of fish from the concentric anticline. maintains its shape constant down to depth. we can find the trap present at all levels down to the basement. If. Cover it with a few more blankets and a duvet or two. therefore in order to drill into a reservoir near its highest point (where we would expect the oil to be). then the position of the crest will shift with increasing depth. These compressive structures pose one problem right from the start. In this case.(2-22) In the concentric fold the tops and bottoms of all the layers remain strictly parallel to each other. so that the beds maintain a constant thickness throughout. The general principles of this are straightforward. (b) The anticline is asymmetrical and the crest shifts with increasing depth. This leads us into the next problem. Seismic may help. Compressive structures have a range of shapes between the purely concentric or parallel anticline and the similar fold.
Petroleum Traps . can be a perfect seal to any underlying accumulations. Note also that salt. where the beds are draped over the eroded stumps of an old Jurassic volcano. and several others. the beds being draped over an upfaulted block (horst) of basement rocks. does not like empty holes. Diagrammatic section through two salt plugs. Nature. This creates a rollover anticline. note that the largest oilfield in the world. if the first sediments in a basin were deposited over a hilly surface. the Middle East. much of the west coast and continental shelf of Africa. being plastic. it is not always easy to separate out the two effects. is in one such trap. but also . Extensive salt deposits and plugs with associated traps occur in many parts of the world: the southern North Sea and northern Germany. In effect the downthrown side is being pulled away from the upthrown side which would tend to create an open fissure along the fault. showing the variety of traps that may be associated with them. Note that the anticline dies out upwards towards the surface.39 A drape-compaction anticline. Ghawar in Saudi Arabia. then they will blanket the hill as an anticline. Not only may an anticline be pushed up over the plug. it is also liable to fracture the overlying and surrounding beds creating fault traps. however. In case anyone should think that this is unimportant.(2-26) A wide variety of traps can be associated with salt plugs. This occurs alongside a normal fault that is curved. those near the bottom of the sequence are going to be squeezed and compacted more on the flanks than on top of the feature as it gets buried. or over an upfaulted block or horst. The effect of salt diapirism will be initially to bulge up the overlying sediments as an anticline. it may extend up to the surface of the ground or only part way if the supply of salt is limited. the Canadian Arctic Islands. A second effect comes into play here: because there is a greater thickness of beds off the structure than over the top. Another is the Forties field in the North Sea. and finally a residual bulge may be left between two nearby plugs: a turtle or turtle-back structure. higher beds will gradually mute and suppress the structure until it is no longer present at shallow levels. so that it is steep near the surface and flattens with depth. the Gulf Coast of the USA. and the beds on the downthrown side above the curving fault collapse to fill the gap. All of these possible traps may contain hydrocarbons. and then to burst through them in the form of a salt plug or salt wall. The last type of anticline that we should be aware of is the roll-over anticline. which contains more than four times as much oil as the whole of the North Sea put together. Note a characteristic of these anticlines: not only do they `grow' with depth. a salt pillow or a salt dome. bending downwards into the hole. This compaction enhances the anticline formed by the drape.(2-25) Similarly. and hence the combined name. it may bend up and seal off the strata it cuts through.
at deeper levels the crest will shift away from the position of the fault at surface. Occasionally indeed. Tertiary. The proviso is that we also have lateral closure: this may be provided by further faulting. . although there are many problems in trying to locate them in the subsurface. or have acted in the past. whether or not the reservoir is completely or only partially offset. Fault traps We indicated above that a trap may be formed where a dipping reservoir is cut off up-dip by a fault. thus causing sand against sand to permit migration and sand against shale to be sealing. The reader may care to think through the various situations sketched as bits of cross-sections in the following figure in which the faults themselves are non-sealing. UK. the position of the crest is displaced with depth and that accumulations in successive reservoirs will not underlie the same surface position. Lower Cretaceous. whether the fault is normal or reverse. Upper Cretaceous. We know that sometimes. Cross-section through the Wytch Farm oilfield. it seems that one and the same fault may act. (2-28) We do not propose to discuss fault traps in detail. L. (2-27) These roll-over structures are particularly important where the `stretching' is caused by a very thick pile of sediments at the edge of a continent gently slipping. Again. Triassic. or by opposing dips. southern England. Lower Jurassic. Note that. Middle Jurassic. Tr. It adds further uncertainties to our predictions of the subsurface occurrence of oil and gas. will depend on the dip of the reservoir as compared with that of the fault. to locate an exploration well in the right place. and how big it is. Kim+P. in both cases. and naturally we have some ideas on the subject. Much of the oil under the Niger and Mississippi Deltas is in such roll-over anticlines. we have to know whereabouts in the succession our prospective reservoir lies. therefore. and its depth.40 they are asymmetrical. a fault can provide a seal. and in understanding them. The large Wytch Farm oilfield of southern England offers a splendid example. Whether or not there is a trap. as at Wytch Farm. Roll-over anticlines: (A) a simple roll-over into a normal fault. Upper Jurassic. we still do not fully understand what the difference is due to. (B) a roll-over complicated by subsidiary faulting near the crest. these predated the deposition of the Upper Cretaceous. down towards the deep ocean. T. All very puzzling! Although attempts have been made to investigate the problem in Nigeria and elsewhere. trapped against faults to the south. BS+MJ+O. and it will depend on the amount of displacement on the fault. or slumping as a sort of land-slide.. It also depends on whether the fault itself is sealing or non-sealing. W. The oil is in two reservoirs. setting it against something impermeable. The sealing capacity of faults is a major difficulty confronting us. but we also know that sometimes faults are pathways for migrating petroleum and non-sealing at all. in both ways.Petroleum Traps .
gneisses) under an unconformity serve as reservoirs in China and North Africa. First. strongly weathered basement rock (granites. possibly through a submarine canyon. A coral reef overwhelmed by muds. however. and on the amount of displacement of the reservoir. claystone. A lot of oil has been found in recent years in this sort of trap in the North Sea. a hill on the old land surface may be formed of permeable rock. if drowned by shales. for example. A sand deposited in a river channel will be confined by the banks and.(2-29) STRATIGRAPHIC TRAPS Petroleum may be trapped where the reservoir itself is cut off up-dip. becoming younger as time goes on. we have an isolated trapping situation. will spread out as a fan over the ocean floor. say. In fact. fan sands provide one of the prime present-day exploration . and leave the reader to speculate on other possibilities. but are generally classified as stratigraphic traps. no structural control is needed. to provide a trap when later covered with. if terminated updip as not infrequently happens. Consider the sea gradually encroaching over the land as sea level rises. but nevertheless known. is the biggest in the USA outside Alaska. Unconformity traps can also be found above the break. to a large extent reflecting the restricted environments in which the reservoir rocks were deposited. on the direction of dip of the beds relative to the fault plane. We would be left with a sandstone reservoir dying out above the unconformity. the porosity could be preserved beneath the unconformity. A flood of sand washed off the shallow continental shelf into the deeper ocean. depending on whether the fault is normal or reverse. More esoterically. thus preventing further migration. The variety in size and shape of such traps is enormous. provides the classic case: the East Texas field. may serve as an isolated stratigraphic trap.41 Six trapping and two non-trapping configurations against a fault. until perhaps the supply of sand runs out. It would be pointless to list all of the possible types of stratigraphic trap that can exist. Non-unconformity traps are even more diverse. they differ somewhat in principle from the others. In this manner. the beach sands will spread progressively over the land surface.Petroleum Traps . some of them very important. We mention just three examples. It is presumed that petroleum cannot escape up the fault plane. let us note that a number of traps. are formed by unconformities. cut across by erosion and later covered above the unconformity by impermeable sediments. so we will mention a few to convey the general idea. A dipping reservoir. its edges will provide an example of a reservoir dying out laterally.
although such prospects are not easy to locate and may require a lot of sophisticated seismic. where the reservoirs overlie overpressured shales. Again the range of possibilities is almost infinite. This combination trap is partly structural (the anticline) and partly stratigraphic (beneath the unconformity). occur in traps formed by a combination of structural and stratigraphic circumstances.42 targets. The difference is believed to be due to clay being smeared into the fault plane. and where an oil-water contact is continuous across a fault. as the fault moved. As the more easily found structural traps are running out in much of the world. An investigation into the sealing qualities of faults affecting roll-over anticlines in the Niger Delta. neither completely controls the trap. where there is enough of it in the section. has most of its oil and gas trapped in a Carboniferous to Jurassic sequence which includes more than one reservoir. elsewhere it appears to form a trap.(2-31) The oil in the Argyll and many other fields in the North Sea is trapped in tilted and faulted Permian to Jurassic reservoirs. there always seems to be something new as a challenge. the biggest field in the USA. which was tilted west and eroded before deposition of the overlying beds now dipping east. The oil in these fields can only have migrated there after the traps were sealed by the higher sequences. and truncated by erosion. The oil is held in the reservoirs by younger shales overlying the erosion surface (Fig.(230) COMBINATION TRAPS A number of fields. Where a reservoir is full to spillpoint against a fault. some of them large. or the oil would have been lost.). This vital factor. these beds were folded into a faulted east-west anticline. The reservoir beds were folded into an anticline. Both the faulting and the unconformity control the traps. which were eroded and unconformably overlain by Cretaceous shales. A couple of examples may give the idea.Petroleum Traps . The Prudhoe Bay field in northern Alaska. tilted westwards. possibly even before it . A block representation of the trap at the Prudhoe Bay field in northern Alaska. We may note here one most important consideration. it is presumed that the fault is non-sealing. that the trap must be shown to have been there before the oil migrated.
geologically speaking. as we do not want to waste the money drilling wells that would miss the oil altogether. is that in most parts of the world the larger anticlines have now been drilled. is held against an unevenness of its upper surface by water flowing in the opposite direction. Depending on the balance of forces acting on the oil. This may be one of the reasons why oil accumulations trapped hydrodynamically are rare. essentially anticlinal. It is therefore always important to get a handle on the hydrodynamic regime in a reservoir for both exploration and oilfield development purposes.(2-32) THE RELATIVE IMPORTANCE OF TRAPS A review of 200 giant oilfields (those containing 500 million barrels or more) emphasize the importance of structural. are not all that rare. What our efforts are increasingly directed towards. or aquifer. Furthermore. are the more obscure and generally smaller prospects. The trouble. entering a reservoir formation. traps in both number and size. of course.Petroleum Traps . perhaps from rain. a regime of water flow cannot normally be expected to remain constant for long. This is what has been described as a hydrodynamic trap. Note that the oil-water contact is tilted down in the direction of water flow. it may find itself caught against an unevenness of the reservoir surface where there is no conventional trap at all. . Oil. only for as long as the water keeps coming: dry up the supply of water. In this sort of situation. indicating the former presence of an oil accumulation now lost. The oil-water contact in such a hydrodynamic trap is normally tilted in the direction of water flow. The timing of trap formation versus oil migration has not always worked out favorably. in say ordinary anticlinal traps. and the oil will be free to move again. There is no structural or stratigraphic closure. is yet another aspect of the petroleum geology that we have to assess in proposing exploration drilling. It is totally dependent on the flow of water and is effective. We would recognize this from residual traces of oil in a water-bearing reservoir. HYDRODYNAMIC TRAPS Imagine surface water. they are known in a number of parts of the world. attempting to escape to surface up a reservoir. therefore. we would have to be careful where we locate and drill our oil production wells.43 was generated. up in the hills and percolating downwards towards a spring. Such tilted contacts. cases are known where flowing water has apparently been able totally to flush oil out of an anticlinal trap. from our present-day point of view. Oil has found its way into the reservoir and is battling to migrate upwards to the surface against the flow of water. The number of structural field of this size may partly reflect the fact that structural traps are easier to find than the others. but the oil reserves they contain show clearly that generally they are also bigger. A hydrodynamic trap.
.Petroleum Traps .Make the interpretations from easy (A) to more difficult.45 EXERCISES EXERCISE 1: The following well logs have been hung on a structural datum. multi-interpretable (D). The logs show SP (Self Potential or Spontaneous Potential) on the left and R (Resistivity) on the right. Interpret the geological relationships shown in each by drawing a structural cross-section through the logs.
Oriskany production is from a small anticline on the upthrown side of the fault. Use this information to construct a northeastsouthwest structural cross section from the Richards well to the Dibble well.46 EXERCISE PetroleumTraps 2 The Wyckoff Gas Field. located in Steuben County.Y. The Onondaga forms a thick biohermal reef over part of the field. Elevations and marked logs are provided for 6 wells in the Wyckoff Field. A deep-seated downto-the-southwest fault extends upward along the southwest flank of the reef. produces from Onondaga Limestone and/or Oriskany Sandstone. showing the interval from top of Onondaga to bottom of Oriskany. Only the porous core facies is productive in the reef section (see map on next page). Wyckoff Reef Gas Field WellElevation CORNELL DIBBLE GUILD CHASE BANKS RICHARDS 2257' 2098' 2037' 2206' 2182' 2066' . N..Petroleum Traps .
47 .Petroleum Traps .
48 .Petroleum Traps .
we cannot measure G directly for a sample that has already begun to generate hydrocarbons. where G and Go are identical. It follows from these definitions that a particular stratum could be an effective source rock in one place. in which case virtually all the initial . a possible source rock in a nearby unstudied region.e. Go. Go can only be measured directly for immature source rocks. or is it because the rock is "burned out" (i.Source-Rock Evaluation DEFINITION OF SOURCE ROCK Much of modern petroleum geochemistry depends upon accurate assessment of the hydrocarbonsource capabilities of sedimentary rocks. However. is it because the rock never had a high initial source capacity. and might have no source potential at all in a fourth area where important facies changes had resulted in a drastically lower content of organic matter. PRINCIPLES OF SOURCE-ROCK EVALUATION QUANTITY OF ORGANIC MATERIAL The amount of organic material present in sedimentary rocks is almost always measured as the total-organic carbon (TOC) content. Possible source rock: any sedimentary rock whose source potential has not yet been evaluated. The term "effective source rock" obviously encompasses a wide range of generative histories from earliest maturity to overmaturity. the Phosphoria Formation of Wyoming and Idaho belongs to each of these classifications in different areas. is most meaningful if we can compare it to the rock's original source capacity. overmature. For example. it is also necessary to know what level of thermal maturity is represented by that particular G value. The quantity actually measured in the laboratory is always G. we actually measure its remaining (or untapped) source capacity at the present day.Source Rock Evaluation . but which may have generated and expelled hydrocarbons. Potential source rock: any immature sedimentary rock known to be capable of generating and expelling hydrocarbons if its level of thermal maturity were higher. the following distinctions can be made: Effective source rock: any sedimentary rock that has already generated and expelled hydrocarbons. The difference between Go and G represents the hydrocarbons already generated in the effective source rock. Analysis normally requires about one gram of rock. the remaining source capacity and not the original capacity (Go). if G is very low. a potential source rock in a less-mature area. much smaller amounts can be analyzed. For example. This simple. When we analyze a rock sample in the laboratory. quick. but if the rocks contain abundant organic matter. Although the term source rock is frequently used generically to describe fine-grained sedimentary rocks. instead it must be estimated by measuring G for a similar sample that is still immature.49 8 .. This quantity. that usage is a bit too broad and loose. MATURITY OF ORGANIC MATERIAL Knowing a rock's remaining source capacity G solves only one part of the puzzle. and inexpensive analysis serves as the first and most important screening technique in source-rock analysis. For better communication. which we can call G.
50 hydrocarbon-source capacity has already been used up)? The exploration implications of these two scenarios are. where the o indicates that the measurements were made with the plug immersed in oil. whenever possible. or TAI). Thermal Alteration Index (TAI). The fraction of the incident beam that is reflected coherently is measured and recorded and stored automatically on a computer. The ideal histogram of reflectance values is therefore rather rare. Despite its weaknesses. of course. There are many problems with vitrinite reflectance as applied to kerogens. far more common in shales than in coals. vitrinite reflectance. its maturity is not related to that of the rock in which it is found. The most commonly used maturity parameters today are spore color (Thermal Alteration Index. and pyrolysis temperature. Because what is present is often reworked. Reflectance values are normally plotted versus depth in a well. Vitrinite-reflectance measurements begin by isolating the kerogen with HCl and HF. and none can be applied in all cases. Results are reported as Ro values.Source Rock Evaluation . In all cases it is worthwhile to supplement vitrinite with other measures of maturity. paucity of first-cycle vitrinite renders vitrinite-reflectance measurements essentially worthless. in some cases it is essential. in obtaining more than one maturity parameter. In other rocks. vitrinite reflectance is the most popular technique today for estimating kerogen maturity. unless surrounding samples help us determine the indigenous vitrinite population. If enough vitrinite particles can be found. leading to frequent difficulties in establishing which vitrinite population is indigenous. even for experienced workers. If a log scale is used for the reflectance. Reworked vitrinite is. in fact. At the end of the analysis a histogram of the collected data is printed. the microscopist shines light on an individual vitrinite particle. All the techniques discussed are useful and probably reasonably accurate if the analytical work is carefully done. TAI measurements are carried out on bisaccate pollen grains whenever possible. and then embedding the kerogen particles in an epoxy plug. very different. In many areas it is easy to use and valuable. misidentification of macerals can cause problems. between 50 and 100 measurements will be taken. . Other macerals or solidified bitumens can often be misidentified as vitrinite. A few of these parameters will briefly be discussed. the reflectance value of vitrinite increases. more common are histograms showing few vitrinite particles or multiple modes as a result of first-cycle vitrinite contaminated with reworked vitrinite or caving of less-mature material from up-hole. If no pollen can be found. from amorphous kerogen. After the plug is polished. The method is based on the fact that with increasing thermal stress. along with a statistical analysis of the data. All the methods have strengths and weaknesses. The darkening of kerogen particles with increasing thermal maturity can be used as an indicator of maturity. with lower confidence. Because each maceral type increases in reflectance in a slightly different way as thermal stress increases. Vitrinite-reflectance techniques were developed for measuring the rank of coals. In order to minimize differences in color caused by changes in the type or thickness of the kerogen particles. TAI values are estimated. A substantial number of techniques for measuring or estimating kerogen maturity have been developed over the years. In many rocks vitrinite is rare or absent. however. Such histograms are quite often difficult or impossible to interpret. TAI measurements are made on the same slides prepared for microscopic kerogen-type analysis. Less commonly used are fluorescence and conodont color (CAI). Vitrinite reflectance (Ro). The feeling of most workers today is that there is no single maturity indicator that tells the whole story unerringly all the rime. The key to using maturity parameters effectively lies in evaluating the measured data carefully (and sometimes with skepticism) and. in which the vitrinite maceral is usually very common. the plot is a straight line.
Although conodonts are composed of carbonate apatite. Conodont Alteration Index (CAI). with the help of color charts can be carried out by inexperienced personnel. Carbon Preference Index (CPI). where most of the interest is. When palynomorphs are absent. CAI is only an indirect indicator of hydrocarbon maturity. and thus are of no value in many areas. Although TAI determinations are subjective. TAI values estimated from amorphous material are always suspect and should be corroborated by other analyses. and thus helps expand the range over which maturities can be measured. A careful worker can reproduce earlier work with excellent precision. Conodonts are isolated.51 Each laboratory has reference slides so that microscopists can continually compare the color determinations they are now making with those they and their colleagues made in the past. TAI measurements are therefore often quite accurate and correlate very well with results from other techniques. One advantage of CAI over other maturity parameters is that because conodonts existed as early as the Cambrian. TAI values must be estimated from amorphous debris. where pollen and vitrinite are often absent. leading to an inaccurate assessment of kerogen maturity. Colors of the specimens thus obtained are determined under a binocular microscope and compared with standards. One disadvantage of CAI measurements is that CAI values can be dramatically increased in the presence of hot brines. CAI is inexpensive and easy to measure and. Finally. by removing the mineral matrix with acetic or formic acid. Furthermore. or most commonly.Source Rock Evaluation . because the organic metamorphism displayed by conodonts is not related to hydrocarbon generation or destruction. Early investigations showed that immature rocks often had high CPI . lack of proper standardization. the CAI scale is most sensitive at levels of maturity much higher than can be measured by TAI. Thirdly. The chief problems arise with inexperienced workers. Other disadvantages overlap with some of the advantages. which can vary greatly in its chemical and physical properties. Conodonts are not very sensitive indicators of maturity within the oil generation window. conodonts are plentiful in carbonate rocks. most commonly from fossiliferous carbonates. thus defusing to a large degree the criticism that TAI is too subjective to be valid. Finally. use of careful standards and the same type of palynomorph in each analysis greatly aid reproducibility. the absence of spores and pollen in the samples. they offer a means of measuring maturity in rocks that do not contain pollen grains or vitrinite. Conodonts do not occur in rocks younger than the Triassic. changes in conodont color are apparently due to carbonization of inclusions of small amounts of organic matter during catagenesis and metagenesis. The first maturity indicator applied to sediments was the Carbon Preference Index. The technique is simple and quick and can be done even by inexperienced workers.
As a result. This discovery led to the use of CPI as an indicator of maturity. in the last decade kerogen analyses have replaced bitumen analyses as the routine procedure in source-rock evaluation. rocks deposited in pelagic environments. they can usually be identified with reasonable confidence. Furthermore. walnut hulls and other solid debris. Pyrolysis yields are. Hydrocarbon contamination is rare except in the immediate vicinity of production or where vehicles are used. because of their friability. and therefore should be easy to avoid. in which the input of terrestrial lipids was very limited. Like pyrolysis. Problems with living organic matter are easily avoided by physically removing tiny plant roots and other recognizable debris. This method works fairly well if the kerogen is still within the oil-generation window. of course. Later it was realized that the decrease in CPI with increasing maturity depends upon the type of organic matter originally present as well as on maturity. atomic H/C ratios measure the present day status of the kerogen rather than its original chemical composition. Caving is not a problem for conventional or sidewall cores. It breaks down at high maturity levels. The exception to this rule is with amorphous material. Fortunately. vitrinite reflectance measurements offer the best means of recognizing caving. palynological analysis can usually detect the presence of lignosulfonates because of the unique pollen assemblages present in the lignite. Drilling-fluid additives have been a severe headache for petroleum geochemists for a long time. and lignite from lignosulfonates. It is capable of impregnating sidewall and conventional cores as well as cuttings. In contrast to solid additives. Walnut hulls and other organic debris are also easy to detect microscopically. Well Samples .The main causes of contamination among samples obtained from wells are caving and adulteration by drilling-fluid additives. have low CPI values even when immature. As long as kerogen particles are not completely black. Contaminants of particular notoriety are diesel fuel. CONTAMINATION AND WEATHERING Surface Samples -The types of contamination most frequently encountered in surface samples are caused by living organic matter or by spills of oil. In particular. In such cases TOC values will be raised and reflectance histograms will show a large population near 0. Atomic H/C ratios must therefore be corrected for the effects of . because all kerogens have low pyrolysis yields. only microscopic analysis is relatively unaffected by maturity. however. therefore.5%. and can be removed prior to beginning the analytical sequence. Careful picking of lithologies and comparison with up-hole samples can often recognize caved materials.52 values (> 1. In many cases. where the fluorescence that enables us to distinguish between oil-prone and non-oil-prone disappears toward the end of the oil-generation window. but it can be devastating in cuttings samples. Without additional information.Source Rock Evaluation .5). The most common method for taking maturity effects into account in evaluating pyrolysis data is to use a modified van Krevelen diagram to backcalculate the original hydrogen index. it can lead to an overly optimistic assessment of the organic richness of the section. diesel fuel affects both kerogen and bitumen. strongly affected by maturity. TOC values will be raised and vitrinite-reflectance values lowered by the presence of adsorbed diesel. of course. which affect only the kerogen portion of the sample. however.2. Caving is a particular problem for coals. it is impossible to determine which maturation path brought it to that point. fewer CPI determinations are made now. ESTIMATION OF ORIGINAL SOURCE CAPACITY Of the three major methods of determining kerogen type. Mold or other surface growth may also be present. whereas those of oils were almost always below 1.
cutinite.53 maturation by using a van Krevelen diagram. because the kerogens they contain are woody or highly oxidized. claiming.5% TOC are considered to have negligible hydrocarbon-source potential. gas-generative. In some rocks TOC values between 1% and 2% are associated with depositional environments intermediate between oxidizing and reducing. Pyrolysis results are normally reported in two ways. and S3) are expressed in milligrams of hydrocarbon or carbon dioxide per gram of rock sample. TYPE OF ORGANIC MATTER Microscopic kerogen-type analysis describes the proportions of the various macerals present in a sample. They will not function as highly effective source rocks. that at least some Australian inertinites can generate significant amounts of oil. and inert. Those rocks containing less than 0.0%). however. where preservation of lipid-rich organic matter with source potential for oil can occur. fluorescing amorphous kerogen. As such these quantities are a measure of the total capacity of a rock to release or generate hydrocarbons or carbon dioxide. etc. Kerogens in rocks containing less than 1% TOC are generally oxidized. Smyth (1983). The amount of hydrocarbons generated in such rocks is so small that expulsion simply cannot occur. Many rocks with high TOC values. and which are definitely worthy of further consideration (TOC > 1. has dissented from this pessimistic view. Rocks containing more than 1% TOC often have substantial source potential. INTERPRETATION OF SOURCE-ROCK DATA QUANTITY OF ORGANIC MATERIAL Almost all measurements of the amount of organic matter present in a rock are expressed as TOC values in weight percent of the dry rock.5%). exinite. Rocks containing between 0. but they may expel small quantities of hydrocarbons and thus should not be discounted completely.0%).5% and 1. which ones might be of slight interest (TOC between 0. resinite.5% and 1. A rock containing 3% TOC is likely to have much more than six times as much source capacity as a rock containing 0. Gas-generative kerogen is mainly vitrinite. Nevertheless. on the basis of deductive reasoning. Raw data (S1. In interpreting these observations we normally divide these macerals into oil-generative. and thus of limited source potential. These immature H/C ratios can then be used to calculate Go.0% TOC are marginal. yielding .5% TOC. because the type of kerogen preserved in rich rocks is often more oil-prone than in lean rocks. the kerogen in such lean rocks is almost always highly oxidized and thus of low source potential. Interpretation of TOC values therefore does not simply focus on the quantity of organic matter present. These raw data are then normalized for the organic-carbon content of the sample. the actual volume percent occupied by the organic material is about twice the TOC percentage. The oil-generative macerals are those of Type I and Type II kerogens: alginite. Because the density of organic matter is about one-half that of clays and carbonates. We therefore use TOC values as screens to indicate which rocks are of no interest to us (TOC < 0. have little oil-source potential. however. We must still determine whether the kerogen present is in fact of good hydrocarbon-source quality.Source Rock Evaluation . TOC values above 2% often indicate highly reducing environments with excellent source potential. S2. Furthermore. Inertinite is considered by most workers to have no hydrocarbon-source capacity. the direct evidence for such a statement is rather meager. Thus high TOC values are a necessary but not sufficient criterion for good source rocks.
the hydrogen index serves as an indicator of kerogen type. The normalized S2 and S3 values are called the hydrogen index and the oxygen index.35% Ro. some Cenozoic coals should have better potential for generating liquid hydrocarbons. resinite. exinite) or from marine algal material. Some laboratories put the onset of maturity at 435° C. because during the Paleozoic the biota was quite different than during the Cenozoic. most other maturation parameters are related to Ro values. Because vitrinite reflectance is the most popular method of determining maturity. for most kerogens the onset of oil-generation is taken to be near 0. Nevertheless.54 values in milligrams per gram of TOC. Thus. with CAI of 8 reached in a marble. MATURITY Kerogen Parameters. but there are still some minor variations from one laboratory to another. A second. CAI can actually measure high-grade metamorphism. respectively. Age of coals is important. Although Tmax values are determined objectively. a unified scale for comparing them with Ro values has not been adopted. Measured hydrogen indices must be corrected for maturity effects by using a modified van Krevelen diagram as outlined above. Those between 150 and 300 contain more Type III kerogen than Type II and therefore have marginal to fair potential for liquids. make sure that you have a copy of their equivalency between TAI and Ro. Hydrogen indices above 150 reflect increasing amounts of lipid-rich material. Peak generation is reached near 0. but in most cases is probably not much above 1.5% Ro. . because they vary with kerogen type as well as maturity. It is particularly difficult to generalize about TAI values because the numerical values of TAI scales have not been standardized among laboratories.6% Ro. The limits of the oil generation window vary considerably depending upon the type of organic matter being transformed. this generalization has two fallacies: most of the coalfields originally studied were of Paleozoic age. Kerogens with hydrogen indices above 600 usually consist of nearly pure Type I or Type II kerogens. They have excellent potential to generate liquid hydrocarbons. Conodont Alteration Index (CAI) values ranging from 1 to 5 were tied loosely to vitrinite reflectance and fixed carbon content of coals. less common application is to decide whether oil will be stable in a given reservoir.Source Rock Evaluation . However. COALS AS SOURCE ROCKS Coals have been traditionally discounted as effective source rocks for oil accumulations because of the lack of geographic correlation between oil fields and coal deposits. and the coals were of bituminous to anthracite rank. either from terrestrial macerals (cutinite. Hydrogen indices below about 150 mg HC/g TOC indicate the absence of significant amounts of oil generative lipid materials and confirm the kerogen as mainly Type III or Type IV.9% Ro. Determination of the oil-generation window in a particular section is the objective of most maturity analyses performed on possible source rocks. Because some Cenozoic land plants are richer in resins and waxes than Paleozoic plants. and thus are considered to have good source potential for liquid hydrocarbons. The ultimate limit of oil stability is not known for certain. Kerogens with hydrogen indices above about 300 contain substantial amounts of Type II macerals. and the end of liquid-hydrocarbon generation is thought to be at about 1. others use 440°. Interpretation of hydrogen indices for immature kerogens is straightforward. Because variations in TOC have been removed in the normalizing calculation. The correlations among maturity parameters have been fairly well established. if you are using TAI determinations determined by an analytical laboratory.
unconformities and erosional events.5 2 2 2 3 4 4 5 Correlation of various kerogen-maturity parameters with vitrinite-reflectance (Ro) values .00 3.0 Pyrolysis Tmax (°C) 420 430 440 450 460 465 470 480 500 500 + 500 + Conodont Alteration Index (CAI) 1 1 1 1. Interpretation of source-rock data on a basic level is quite simple.35 1.2 3.Source Rock Evaluation .3 2. therefore.60 0.00 4.5 3. Vitrinite Reflectance (%Ro) 0.55 SUMMARY Any source-rock evaluation should attempt to answer three questions: What are the quantity.00 1. Whenever possible. rather. In some areas one technique may fail completely or may be only partially successful.80 1.8 4.8 3.00 Thermal Alteration Index (TAI) 2. We should always attempt to extrapolate our measured data over as large an area as possible.6 2.20 1. type. and maturity of the organic matter present in the rocks? Satisfactory methods are available in most cases to answer all these questions.0 2.0 4. and organic facies. With increasing experience one can also learn to derive important information on thermal histories.0 3. To do this intelligently we must have the ability to develop regional models of organic facies and thermal maturity.50 0. we should not rely on a single analytical technique. we should attempt to corroborate the measured data by other analyses.40 0.50 2.4 3.
41 0. however.72 0. and maturity (TAI). and then tracing the H/C ratio back to its immature value.2 1.5 1.0 2-2.56 EXERCISES Worked out example: Perform a source-rock analysis on the Mauve Well.38 TAI 2.2 Atomic H/C 1.6 2. present-day H/C ratios to the ones that the kerogens had when they were thermally immature. so "Total Oil" can be plotted against "Oil Already Generated." To do this.1 3.98 0.5 2.1 2. Both the immature H / C ratios and the maceral analysis data need to be scaled to calculate "Total Oil.07 1. refer to the graph on next page.5 2.7 3.2 2.65 0.27 1.86 0.6 0.5 2-2.5 2.6 2.81 1.75 0.6 2.Source Rock Evaluation .7 2.8 % Alginite + Exinite 75 80 80 75 80 90 85 75 70 50 45 60 45 40 ? ? Core Cuttings Data are available on quantity (%Corg).7 2." Two independent quality measurements have been made. The calculated immature H/C ratios are listed in the table on next page.22 1.5 0.05 0.7 1. and both should be utilized and examined for possible discrepancies.0 3.15 0.5 2-2.5 0.0 0. presenting the kerogen quality factor as a .7 1. To use the H /C data.9 3.77 0.5 1.33 1. Source-rock data for the Mauve Well Depth (m) 1000 1200 1500 1750 2000 2300 2700 3000 3500 3600 3800 4000 4500 4600 4800 5000 Type of Sample Sidewall Cores %Corg 0.66 0. as shown in Figure B (derived from Figure A).3 1. This can be done easily by plotting H/C versus TAI. one must first convert the measured. B) H/C versus TAI for Mauve Well samples. quality (H /C and %Alginite + Exinite).3 0. A) Calculation of the immature kerogen H/C ratio(at A) from the present-day H/C ratio and vitrinite reflectance data(at P) .8 0.2 3.
If these attempts produced no resolution of the problem. and would certainly request that the slides made for maceral analysis be reviewed.35 0. In likewise manner (not illustrated here) the quality factor can be determined from maceral analysis data.4 1.00 0.75 0. such as pyrolysis. The prudent interpreter might now ask that some of the H/C ratios be rerun.15 0.85 1.05 1. Kerogen quality factor as a function of H/C ratio of the immature kerogen. and 4500 meters all show differences in the quality factors calculated from the two types of data.05 1.60 0.05 0.8 ? ? * * * Indicates discrepancy between quality factors calculated from H /C and from maceral analysis.90 0. It is apparent that there are serious discrepanties between the H/C and maceral analysis results for several of the samples.9 0.90 ? ? Quality Factor Quality Factor (from H/ C) (from 1. to check for analytical error. Scaled Quality Data tor Mauve Well Samples Depth (m) macerals) 1000 1200 1500 1750 2000 2300 2700 3000 3500 3600 3800 4000 4500 4600 4800 5000 Measured H/C 1.66 0.8 1.90 0. the interpreter might then decide to try a third technique.6 1.86 0.98 0.72 0.27 1.07 1.5 1.81 1.50 1.Source Rock Evaluation . 2300. and not .77 0.05 0.22 1.20 1.7 1.65 0.22 1. it is impossible to pinpoint the error.17 0.9 1.57 function of H/C ratio of the immature kerogen in order to determine the quality factor from H/C.60 ? ? * * * * * 1. 2000.05 0. In each case.6 1. The most important point being made here is that these discrepanties must be taken seriously by the interpreter.35 0. however.07 1.33 1.5 1. 1500.60 0. Without more knowledge.6 1. the H/C ratio gives the lower quality factor. The samples at 1000. so some systematic error is likely.43 1.30 1. 4000.5 1.0 0.35 1.81 1.90 0.65 0. The scaled quality factors are given for each parameter in the table on next page.77 0.41 0.2 0. 1750.70 1.38 Immature H/C 1.90 0.
and the H/C ratios are not helpful because the maceral types cannot be ascertained from such low H/C values. The relative organic richness of the blackened samples below 4600 meters makes them interesting for further investigation. therefore.58 be overlooked or swept under the rug. a more thermally mature version of the rocks lying between 2700 and 3000 meters in the Mauve Well could already have generated very large quantities of oil. More samples between 3000 and 3500 meters should be obtained to define better the zone of high "Total Oil" values. The only sample where the discrepancy is significant is that from 2000 meters. "Total Oil" and "Oil Already Generated" profiles tor the Mauve Well. . "Total Oil" and "Oil Already Generated" profiles are plotted in above figure. because sourcerock potential is not good for most of the section.Source Rock Evaluation . about the oil-source history of the section below 4600 meters. In fact. Most of the discrepanties among the different quality factors turn out to be unimportant. Finally. The rest of the section shows a good correspondente between the two parameters. no maceral analysis was possible here. These two kerogens are highly mature and quite black. "Total Oil" values are generally unexciting. Future exploratory activity could include an attempt to find such a section. It may be necessary occasionally to offer two alternative interpretations without choosing between them. "Oil Already Generated" values indicate that only the section lying below 4500 meters is likely to have generated anything approaching a commercially attractive amount of oil. Let us take this last approach to this problem. except for the two deepest samples. although the section between 2000 and 3500 meters shows fairly good potential. One can say little.
2 0.3 2.12 *TAI and Ro are interconverted according to the correlation table at the end of chapter 7.0 2.08 0.25 0.8 1.06 0.3 2.48 Ro 0.3 2.3 1.Source Rock Evaluation .5-3 2.07 0.5 3-3.5 2.91 1.66 0.51 0.0 2.08 0.1 0.7 0.02 0.7 0.27 1.03 0.5 2.07 0.5-3 3.60 0.67 0.0-2.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10 2-2.6 2.0 0.3 Bit/TOC 0.88 0.06 0.1 2.0 2.5 2.0 2.21 1.5-3.65 0.09 0.00 1.5-3 2.61 0.46 0.6 0.17 0.08 0.49 0.51 0.5-3 2.0-2. Thermal-maturity data for the Blue Well Depth (ft) TAI Ro Bitumen/TOC 1000 1200 1500 2000 2300 2600 3000 3200 3400 3700 4000 4200 4800 5000 5200 5400 5700 6000 2.99 1.2 2.55 0.33? 1.27 0.26? 1. Explain how you resolved any apparent discrepancies.8 0.21 0.08 0.91 0.03 0.5 2.90 0.41? 1.52 0.18 0.02 Atomic H/C 0.21 1.71 0.5-3 2.85 0.01 0.5 3.5 3.60 0.17 0.59 0.59 0.10 0.5 2.5 2.9 1.5 TOC = Total Organic Carbon Bit/TOC = Bitumen/Total organic carbon ? indicates a poor histogram TAI = Thermal Alteration Index Ro = Vitrinite reflectance .5 2.22 0.5 0.000 Type of Sample Cuttings Cuttings TOC 1.05 0.0-2.49 0.42 0.05 0.6 4.44 0.91 1.11 0.0 2.51 0.07 1.86 1.06 0.5 2.0 2.5 2.65 0.09 0.5 2.03 0.0 3-3.5 2.5-3 2.59 EXERCISE Source Rock 1 Combine the data from the Blue Well to give a coherent picture of thermal maturity in the section drilled. EXERCISE Source Rock 2 Perform a source-rock evaluation of the section penetrated in the Turquoise Well.63 0.60 0. Source-rock data tor the Turquoise Well Depth (ft) 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500 8000 8500 9000 9500 10.25 1.4 0.66 0.02 0.
and migration with timing of structure development or trap formation. The common thread running through all these models is the assumption that oil generation depends upon both the temperature to which the kerogen has been heated and the duration of the heating. We need data that will enable us to construct a time stratigraphy for the location of interest and to specify its temperature history. indeed. we still have no clue as to when oil generation occurred. in frontier basins there may not be a single well within tens or hundreds of kilometers. Lopatin in the Soviet Union described a simple method by which the effects of both time and temperature could be taken into account in calculating the thermal maturity of organic material in sediments. These two factors are interchangeable: a high temperature acting over a short time can have the same effect on maturation as a low temperature acting over a longer period. expulsion. In most cases.Predicting Thermal Maturity INTRODUCTION Measured maturity values for possible source rocks are invaluable because they tell us much about the present status of hydrocarbon generation at the sample location. CONSTRUCTION OF THE GEOLOGICAL MODEL One of the advantages of Lopatin's method is that the required input data are very simple and easy to obtain. estimates can be made. If no well data are available. Furthermore. Lopatin's method allows one to predict both where and when hydrocarbons have been generated and at what depth liquids will be cracked to gas. however. especially if the seismic reflectors can be tied to well data. If no subsurface data are available. Part of this problem is a consequence of the limitations we face in attempting to obtain reliable maturity measurements. In order to circumvent these difficulties. for it is in keeping with the predictions of chemical-kinetic theory. In 1971. It has even been suggested that maturity models are more accurate than measured data for determining the extent of petroleum generation. He developed a "Time-Temperature Index" of maturity (TTI) to quantify his method. In some areas there are no well samples available. Nevertheless.60 9 .Predicting Thermal Maturity . measured maturity data are of limited value in exploration. early efforts to take both time and temperature into account in studying the process of hydrocarbon generation were only partially successful because of the mathematical difficulties inherent in allowing both time and temperature to vary independently. If our measurements indicate that a rock has already passed through the oil-generation window. maturity measurements can only tell us about present-day maturity levels. Even in maturely explored basins the samples available for analysis often do not give a representative picture of maturity in the basin. methods have been developed for calculating maturity levels where measurements are not available. . a time stratigraphy can sometimes be constructed using seismic data. These considerations are important when we want to compare timing of generation. nor do we know at what depth or temperature it occurred. however. perhaps from thicknesses of exposed sections nearby. Time-stratigraphic data are usually available as formation tops and ages obtained by routine biostratigraphic analysis of well cuttings. This assumption is a logical and defensible one. In this chapter you will learn how to carry out maturity calculations using Lopatin's method and how to use Lopatin's method in exploration.
The subsurface temperature must be specified for every depth throughout the relevant geologic past. . Suppose. and that a corrected bottom-hole temperature of 133° C was obtained at 3800 m. are marked on the age-depth plot. burial-history curves represent our best understanding of the geological history of an area.Predicting Thermal Maturity . it is easy to construct burial-history curves with a high level of confidence. Using these present-day data and extrapolating them into the past.61 BURIAL-HISTORY CURVES Implementation of Lopatin's method begins with the construction of a burial-history curve for the oldest rock layer of interest. Neglecting compaction effects. a burial-history curve may represent only a rather uncertain guess. The next step is to locate the first control point from the time-stratigraphic data on the input table. by 80 Ma the sediment had been buried to a depth of 900 m (point C). we can construct the complete figure. TEMPERATURE HISTORY The next step is to provide a temperature history to accompany our burial-history curve. representing the initial deposition of the sediment (point A) and its position today (point B). The burial-history curve was constructed in the following way: two points. that the Tiger well was logged. if constructed as carefully as the data permit.(9-2) All of the shallower and younger horizons will have burial-history curves whose segments are parallel to those of the oldest horizon. In cases where biostratigraphic data are lacking or where the sediments have had complex tectonic histories. In cases where biostratigraphic data are available and deposition has been reasonably continuous. Suppose further that local weather records indicate a yearly average surface temperature of 19° C. Using the other control points from the input table. The simplest way to do this is to compute the present-day geothermal gradient and assume that both the gradient and surface temperature have remained constant throughout the rock's history. An example is shown in the following figure. sediment has accumulated continuously but at varying rates since deposition of the oldest rock 100 million years ago (Ma). which was constructed from the time stratigraphy for the Tiger well. for example. Burial-history curves are based on the best information available to the geologist. Today the rock is at a depth of 3700 m. This geometry is a direct consequence of ignoring compaction effects. In the Tiger well. Connecting the six dots completes the burial-history curve. Nevertheless. we can construct the temperature grid with equally spaced isotherms parallel to the earth's surface.
but the geothermal gradient varies in response to heating or cooling events. Whenever erosional removal occurs. There is no theoretical limit to the complexity that can be introduced into our temperature histories. Causes for such events could include global warming and cooling or local climatic variations resulting from continental drift or elevation changes. burial-history curves for both hanging wall and footwall can be represented on a single diagram. Given adequate data or an appropriate model on which to base complex temperature reconstructions. the movement of hot rocks from the bottom of the overthrusted slab over cool rocks at the top of the underthrusted slab will affect . Erosion is indicated in a burial-history curve by an upward movement of the curve. If thrusting is rapid compared to the rate of thermal equilibration between thrust sheets. The effects of thrusting on thermal maturity are not well understood. we can change surface temperatures through time without altering the geothermal gradient. however. In other cases the surface temperature remains constant. In most cases. the resultant thinning of the section must be represented in the entire family of burial-history curves.62 Where measured bottom-hole temperatures are not available. For example (9-7). As an example: lowering the geothermal gradient by rapid sediment accumulation results in subsurface temperatures that are anomalously low compared to the "normal" ones that dominated previously. temperature profiles will be based largely on guesswork. the burial-history curve again begins to trend downward. we are limited only by our own creativity. More complicated temperature histories account for changes in thermal conductivities caused by variations in lithology. however. If deposition resumes later. maps of regional geothermal gradients can be useful in estimating the gradient at a particular location. There are numerous other variations that can be employed in creating temperature grids. SPECIAL CONSIDERATIONS ABOUT BURIAL-HISTORY CURVES The most common complicating factor in constructing burial-history curves is erosional removal. If part of the section is missing as a result of faulting.Predicting Thermal Maturity . If. two separate diagrams should be used for the sake of clarity. The individual segments of each of the burial-history curves in a family will remain parallel. In many poorly explored areas. the data necessary for highly sophisticated temperature reconstructions are simply not available. Faulting can be dealt with by considering the hanging wall and footwall as separate units having distinct burial histories. some part of the section is repeated as a result of thrusting.
(9-12) CALCULATION OF MATURITY Once the burial-history curves and temperature grids have been constructed. In order to carry out maturity calculations conveniently. Because the rate of maturation was assumed to increase by a factor of two for every 10° C rise in temperature. increases exponentially with increasing temperature. Lopatin chose the 100°-110° C interval as his base and assigned to it an index value n = 0. more work is required before we will understand fully how thrusting influences hydrocarbon generation and destruction.400 cal/mol will approximately double with every 10° C increase in reaction temperature. These dots define the time and temperature intervals that we shall use in our calculations. Loss of 1000 m of section by erosion during an uplift event lasting from 70 Ma to 60 Ma. decreases by 1000 m. However. we must paste them together. Testing of his model and the successful application of Lopatin's method in numerous published examples have confirmed the general validity of this assumption.63 organic maturation by causing important perturbations in subsurface temperatures. Multiplying the time factor for any temperature interval by the appropriate temperature-factor for that interval gives a product called the Time-Temperature Index of maturity (TTI). expressed in millions of years. The temperature factor. Temperature intervals are defined by successive isotherms spaced 10° C apart.Predicting Thermal Maturity . spent by the rock in each temperature interval. respectively. but the distance between the two lines which bracket the erosion. in contrast. A Time interval is the length of time that the rock has spent in a particular temperature interval. Studies in the Overthrust Belt of Wyoming indicate that a slow-equilibration model is superior to a simple model invoking rapid thermal equilibration. Now we can carry out the maturity calculations. Chemical reaction-rate theory states that the rate of a reaction occurring at 90° C (a reasonable average for oil generation) and having a pseudoactivation energy of 16. for any temperature interval the temperature factor (?) was given by: ? = 2n The temperature-factor thus reflects the exponential dependence of maturity on temperature. Total maturity is calculated by summing the incremental maturity added in each succeeding temperature interval. we need to define both a time factor and a temperature factor for each temperature interval. Lopatin defined each time factor simply as the length of time. This intervalTTI value represents the maturity acquired by the rock in that temperature interval during the time . Lopatin (1971) assumed that the rate of maturation followed this doubling rule. Index values increase or decrease regularly at higher or lower temperatures intervals. Intersections of the burial-history curve with each isotherm are marked with dots. Individual burial-history curves remain parallel.
On the other hand. In the adjoining table interval-TTI values and total-TTI values up to the present day are calculated. it can never go backward because interval-TTI values are never negative. Four of the many paths by which an 80-Ma-old rock could have reached a present burial depth of 3000 m is indicated in the figure (9-21). baking will continue. no matter how much or how rapidly we cool it down. Figure C shows rapid burial during the first 20 Ma. by 10 Ma of uplift and erosion. where the time factors and yfactors for each temperature interval are shown on the burial-history curve. . In A the rock was buried at a constant rate for its entire 80-my history. FACTORS AFFECTING THERMAL MATURITY Because maturity is affected by both baking time and baking temperature. as the oven cools down. A good analogy can be drawn between oil generation and baking. we simply sum all the interval-TTI values for the rock. In B burial was very slow during the first 70 Ma of the rock's existence. maturity continues to increase (albeit at a slower rate) because y is always greater than zero. the cake will bake slowly at first but will bake faster and faster as the temperature rises. even if a rock cools down. If we turn off the oven but leave the cake inside. the specific burial history of a rock can strongly affect its maturity.(9-20) It is also possible to determine the total-TTI value at any time in the past simply by stopping the calculation at that time. In D 40 Ma of rapid burial to a depth of 4000 m was followed by a hiatus lasting 30 Ma and. Maturity always increases. Furthermore. followed by a nonerosional depositional hiatus for the last 50 Ma. although at increasingly slower rates.Predicting Thermal Maturity . we cannot "unburn" it. The first step in calculating TTI is illustrated in the following figure. TTI values differ appreciably among these four scenarios. If we put a cake in a cold oven and turn the oven on. if we forget about the cake when the oven is hot and let it burn.64 given. finally. but quite rapid in the last 10 my. To obtain total maturity.
The sensitivity of maturity to temperature is clearly indicated by the exponential dependence of maturity on temperature predicted by the Arrhenius equation. In actuality.65 A) Initial proposed burialhistory model for Well #1. First. Km = Lance-Meeteetse formations. the dependence of maturity on time is linear. we usually have excellent control on rock ages through micropaleontology. in contrast. showing the evolution of the oilgeneration window through time. Present-day subsurface temperatures are difficult to measure accurately. Only in cases where micropaleontological dating was not or could not be carried out. our uncertainties about the true values of subsurface temperatures are much greater than about time. Tu = undifferentiated Tertiary. Wyoming. is the single most important cause of uncertainty and error in maturity calculations. . Secondly. so even a rather large error in baking time will not produce a catastrophic change in maturity. Kc = Cody-Frontier formations. B) Revised burial-history model for Well #1 based on the poor correlation with measured maturity data. Family of burial-history curves for a well in the Big Horn Basin. Tfu = Fort Union Formation. Temperature. might we anticipate possible problems with time. and can be even better in Cenozoic rocks. Age calls are often made within a million years. Various methods have been developed for this purpose. but there is no guarantee of their accuracy in any particular case. The hiatus has been reinterpreted as an erosional unconformity (9-23) POTENTIAL PROBLEMS WITH MATURITY CALCULATIONS The most obvious errors in maturity calculations will come from inaccuracies in time and temperature data. time data are seldom a problem. Most logged temperatures are too low and require correction.(9-29) Furthermore.Predicting Thermal Maturity . The model includes an extensive nonerosional depositional hiatus.
00 1.5-3 2.59 0.5 3.7 0. The corrected bottom-hole temperature was 270° F. EXERCISES EXERCISE Thermal Maturity 1 Perform a source-rock evaluation of the section penetrated in the Turquoise Well.5 2.5-3 2.08 0.08 0. Construct a family of burial-history curves for the well and calculate the present-day TTI at total depth.150 ft in the Middle Miocene.52 0.000 ft of Upper Miocene before being abandoned at 16.000 Type of Sample Cuttings Cuttings TOC 1.5 0.91 1. do not utilize different kinetic parameters for the various kerogen types.18 0.41? 1.07 1.5 TOC = Total Organic Carbon Bit/TOC = Bitumen/Total organic carbon ? indicates a poor histogram TAI = Thermal Alteration Index Ro = Vitrinite reflectance EXERCISE Thermal Maturity 2 The Black Well was drilled off the Louisiana Gulf Coast.1 2.5 2.49 0.67 0. A plausible average surface temperature is 20° C.4 0. Despite experimental evidence indicating that different kerogens decompose to yield hydrocarbons at different levels of maturity models. particularly where Paleozoic rocks are involved.91 1. It penetrated 1000 ft of Pleistocene sediments.27 0. In other cases.86 1.91 0.25 1.26? 1.6 4.06 0.51 0.2 0.8 1.9 1.66 0.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10 2-2.22 0.21 1.0 3-3.99 1.5 3.60 0.17 0. Source-rock data tor the Turquoise Well Depth (ft) 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500 8000 8500 9000 9500 10.3 Bit/TOC 0.48 Ro 0.21 1. however. we still would have to extrapolate the present somehow into the past.02 0.01 0.27 1.5-3 2. and 11.85 0.5 2.5-3 2.1 0. In such cases we should be very careful about using predicted maturities unless we have some independent confirmation of the validity of our model from a comparison with measured maturity data. Base Pleistocene 2 Ma Base Pliocene 5 Base Upper Miocene 11 Base Middle Miocene 50 Ma .06 0.0 0.71 0. where presentday temperatures are maximum paleotemperatures.65 0.7 0.5-3.3 1. however.5 2.88 0. In many cases.05 0.03 0.03 0. A question of some concern comes from the previously mentioned fact that most of the maturity models treat all types of kerogen identically.Predicting Thermal Maturity .5-3 3.8 0.66 Even if we could measure present-day subsurface temperatures with perfect accuracy.5-3 2.90 0. even an inaccurate extrapolation into the past may not cause significant problems.3 2.02 Atomic H/C 0.51 0.65 0.08 0.33? 1. 3500 ft of Pliocene. an accurate interpretation of the ancient geothermal history may be critical.5 3-3.
Assuming a surface temperature of 10° C and a geothermal gradient of 2° F/100 ft. assuming a constant geothermal gradient through time. It is also believed that 500 ft of Lower Cretaceous sediments were deposited before uplift and erosion began. draw a burial-history curve for the section penetrated and calculate maturity for the Kimmeridgian shale. Total depth is reached at 6120 ft in Middle Jurassic rocks. micropaleontology indicates the rocks to be of Maestrichtian age.5 88. Evidence from related sections indicates that the Paleocene was originally about 3000 ft thick and that no other Cenozoic sediments were ever deposited.5 base Turonian base Cenomanian base Cretaceous top Kimmeridgian base Kimmeridgian 91 Ma 97 144 150 156 Ma . Age data top Paleocene base Paleocene base Maastrichtian base Campanian base Santonian base Coniacian 55 Ma 65 73 83 87. Corrected BHT (4200 m): Estimated surface temp. Find when the rock at 3000 m began to generate oil (TTI = 10). Determine when each of the strata began to generate oil.67 EXERCISE Thermal Maturity 3 Calculate present-day TTI at 3000 m in the Red Well. Total original thickness of the Kimmeridgian is thought to be 1500 ft. Time-stratigraphic data Temperature data Age (Ma) 0 2 38 65 80 100 Depth (m) 0 500 1200 2700 3000 4000 Present-day average surface temp. At a depth of 1500 ft.Predicting Thermal Maturity . The following Upper Cretaceous boundaries are noted: Maestrichtian-Campanian Campanian-Santonian Santonian-Coniacian Coniacian-Turonian Turonian-Cenomanian 1807 ft 2002 ft 2360 ft 2546 ft 3017 ft The Cenomanian is 480 ft thick and overlies 1000 ft of Kimmeridgian-age shale.end Cretaceous: 15° C 141° C 25° C EXERCISE Thermal Maturity 4 The Ultraviolet Well is spudded in Paleocene sediments.
The geothermal gradient was found to be 1.500 EXERCISE Thermal Maturity 6 You have been asked to evaluate an undrilled prospect in a remote area that is available in an expensive farm-in deal. Time-stratigraphic data are given in the following table.000 13. No other source rocks were noted. Highly fractured carbonates overlie the source rock. Erosional removal since the Permian probably totals about 2000 ft.000 18.500 21.0° F/100 ft. Nearby well control indicates that a geothermal gradient of 3. "A regional study of the area suggests the probable presence of a thin. and the surface temperature today is about 15° C. The reservoir is sealed by a thick salt layer." Utilizing the principles of hydrocarbon generation and preservation. Because of the high operations cost. No other reservoirs are anticipated. Your responsibility is to make a recommendation regarding the nature of hydrocarbons that might be present in die prospect. From 40 Ma to the present about 500m of additional burial occurred.65°C/100 m and a surface intercept of 15°C are reasonable for the area. they are in turn overlain at 2750m by a sandstone of excellent reservoir quality.000 11. At that time nearby orogenic activity caused the first traps to be formed during a gradual 1200m uplift lasting until 40 Ma.000 8. No unconformities are recognized within the Paleozoic. evaluate the prospect.Predicting Thermal Maturity .000 25. Carboniferous '' Ordovician '' Depth (ft) 7. oil-prone source rock at about 4300m depth near the prospect. The source rock is thought to be about 300 Ma old. The basin filled at a generally uniform rate from about 300 Ma to 100 Ma. rich. Top of Permian Virgil Missouri Des Moines Atoka Morrow Mississippian Kinderhook Sylvan Arbuckle Age (Ma) 230 280 288 296 304 309 320 340 425 470 Period Permian 0 L.68 EXERCISE Thermal Maturity 5 Analyze the timing of oil generation in the Pink Well. upper management has decided that gas and condensate are not economical.000 23.500 27. Carboniferous '' '' '' '' E. The traps at the prospect location formed slightly prior to the beginning of erosional removal in the basin and have retained integrity to the present. The following geological summary is available to you. .
half a mile or whatever. just what these changes amount to. and tertiary reserves using more exotic techniques. of the following terms: OIL IN PLACE This is the total volume of oil. we have to remember that we are dealing with a resource and that we are very concerned with the quantities involved. they might designate as `probable'. The stock tank is. This section is included to give an idea of what is involved. Some might use the term to refer to the amount of recoverable oil that is believed to lie within a given radius. located at surface near the well-head.Quantitative Assessment . it is desirable to be able to express our degree of confidence in it.69 10 . And yet oil companies need to know what to expect. Because anyway there is uncertainty about this amount. measured in barrels or other units that is present in an accumulation under the ground. unless we can be more specific about how we are going to produce them. before we started to take any of it out. and hence the STOOIP refers to the oil in place in the reservoir but corrected to the volume it would occupy under surface pressure and temperature. Proven reserves: Here we start to enter a minefield! Different companies have different definitions of what is proven. and therefore without any dissolved gas of significance. It usually refers to what was there originally. and oil may be produced directly into it. What they think is beyond that in the accumulation. RESERVES Perhaps the following explanations will give you some idea of what we are up against when we come to consider quantities of the resource on which a good deal of our civilization depends. Increasingly these days. of a well. We will refer to oil. We cannot regard these quantities as `reserves'. let us again emphasize that we are dealing all the time with uncertainties. is liable to change between our information points. that the proportion of the oil in place that we can recover will depend on the economics: how much money are we prepared to spend on getting it out of the ground. So. Similarly. Recoverable reserves: The volume of oil that can actually be produced to surface from an accumulation. Note. Now we must see how we can apply our knowledge of the geology to assessing the amounts of petroleum that we have found. since we are never able to recover all of the oil that is down there in the reservoir. companies tend to use `proven' for those reserves that are believed to be present with an 85 or maybe 90 per cent degree of .Quantitative Assessment So far we have been talking in rather generalized terms. or hope to find. We have to try to understand. our wells. even within oil companies. This may be done via a standard deviation or by a statistical probability (see below). in the case of small fields. or predict. we are involved with a greater or less degree of uncertainty about quantities. once a discovery is made. however. You may see the engineers using the term STOOIP: stock tank oil originally in place. until actually all of the oil has been produced. We may distinguish between primary reserves that can be produced without any artificial assistance other than pumping. There is no way of knowing in advance of drilling whether or not there is going to be any oil or gas at all down there under the ground. A bald figure for `recoverable reserves' is somewhat meaningless. However. How do we handle these problems? Before we get into this. secondary reserves. there is no way that we can know precisely how much we have found: the geology. methods. but the same considerations. and terms can be used equally for gas. which controls the amounts of oil in the reservoir. which can be produced using assisted or enhanced recovery techniques. First. we have to clear a good deal of misunderstanding and misuse. let alone how much.
. BV will be determined from seismic and well data. It may well be that it is best to avoid the terms `proven'. What anyway should we regard as net reservoir? A rather arbitrary porosity cut-off value is often used. in this case 50 per cent. This reflects the fact that oil under the ground in the reservoir occupies more space than it does when we get it up to the surface. We do our best from measurements on core samples and from wireline log interpretation. if we hear simply about `reserves'.Sw)] * RF * Constant FVF where: – BV is the volume of the reservoir formation within the closure of the trap above the spill-point. The shape of the trap. then this factor may be little more than a guess. it is the remaining reserves. They refer respectively to what was there and recoverable before we started producing. and just to qualify our figures by statistical probabilities: at least then people would know what is meant! Original and remaining reserves: These are fairly obvious. faulting. including the adequacy of the source rock to provide enough oil to the trap. Again we need an average value for the field. and the thickness of the reservoir govern it. if we do. like `proven'. which is the percentage of the bulk volume that actually contains the oil. the normal way of estimating how much has been found is to start with the volume of the reservoir within the closure of the trap. Usually. `probable'. – ? is the porosity. the percentage of the porosity that is occupied by the immovable water. So we multiply the bulk volume of the reservoir in the trap by those factors that represent the non-oil. Not all of a reservoir formation is going to be sufficiently porous and permeable to contribute oil to production. and the quality and strength of the cap rock. We have not only all the problems of average porosity but remember that the size of the pores comes in here as well: the finer the sand. DISCOVERED RESERVES Once a discovery of oil has been made.Quantitative Assessment . – Fill is the `fill factor'. This will be controlled by variations in the nature of the sediments that comprise the reservoir. even when we have information from a lot of wells. or rather the average porosity of the net reservoir across the entire accumulation. to cover the reserves that have only a 15 or 10 per cent chance of being present. This can be pretty subjective. It is affected by many factors. we shall see shortly. We have to discount those parts of it that are useless and just consider the net reservoir thickness. – FVF is the formation volume factor. but what happens between and beyond our well control? – Sw is the water saturation. – N/G is the net to gross ratio.70 confidence or statistical probability. We may actually be able to measure the FVF if we have a sample of oil collected under subsurface pressures from the bottom of our well. and what is still there for the taking at a given date. to refer to a degree of confidence or probability. and `possible' altogether. that are meant. We then eliminate progressively everything from this volume that is not oil. the volume of the gas cap and the water-bearing rock below the oil-water contact being discounted. it shrinks because gas bubbles out of it as its pressure is eased during production. Probable reserves: Equally dodgy! One definition was given above: the term may be used. then we can go straight to the bulk reservoir volume containing the oil. the higher will be the water saturation. What this means and how we arrive at the figure. and regional and local geological interpretation. Sometimes `possible' is also seen. Recoverable reserves = [BV * Fill * N/G * ? * (1 . If we do not know where the gas-oil and oil-water contacts are. meaning that we have to try to interpret in detail the environments that the sediments were deposited in.
somewhere within which the `true' figure must be. and again. is to multiply uncertainties by uncertainties. from minimum possible to maximum possible. Then we get a computer to pick a value for each factor at random from the range we have given. It will be clear to anyone that. even though they may be well aware that any such figures will eventually turn out to be wrong. maybe 500 or 1000 times. for this average value. . we can work out the standard deviation (the ±) which will give an idea of our confidence in our answer. What we are doing. and to try to be as honest and objective as possible. The list is put into order from the smallest to the largest. however. since it is about this that the standard deviation can be calculated. known as a Monte Carlo simulation. A constant is needed to adjust the units. we have to multiply the figure we calculate by 7758. this is commonly about 50-60 per cent.. Instead of estimating single figures for the factors that go into the reserves formula. there must be considerable uncertainty to say the least. our best estimate. and arrive at perhaps wildly different answers. and we also specify the total range. and then analysed statistically. The one that has the most answers in (= the modal class of the distribution) we can regard as the most probable value -in other words. we give as our preferred figure the average of all the answers (the mean). but biassing its pick towards our best estimate. Diagrammatic plots of the outputs from two Monte Carlo simulations.Quantitative Assessment . companies.This is because. In a sandstone reservoir. To get an answer to our sum in barrels of oil.. More commonly. we shall find that the bulk of them tend to cluster round the middle (Fig. The computer does the sum using these values. The number of answers in successive reserve ranges is plotted against the size ranges themselves. doubtful estimates by doubtful estimates.). Most commonly these days. Who is right? Whose answer should we use? Can we indeed believe any of them? Unfortunately we cannot escape from the problem. but it may be a good deal less from carbonates. Then we ask it to do the same thing again.71 – – RF is the recovery factor. It is a figure that we cannot know exactly until we have finished producing. The Americans measure reservoir volume in acre-feet: area in acres multiplied by reservoir thickness in feet. any one of which could be the real value. Note that the preferred answer that is usually used is the mean value. If we are working entirely in the metric system. the problem is tackled through a statistical technique. the proportion of the oil in the reservoir that we can actually recover and produce. in producing figures for all of these factors. then we don't have to worry. So we have a whole list of answers. If we plot out the answers on our list falling within successive size ranges (in barrels of oil). and governments must have numbers that they can use for planning purposes. until we begin to wonder whether our answer has any reality or meaning at all. So we usually have to base our estimate on prior experience elsewhere. Different geologists will certainly come up with different values for at least some of the input factors. then. and again. having regard to all of the geology. Alternatively one may plot the frequencies as percentages of the total number of answers: the statistical probabilities. for each of the factors we work out our best estimate.
and possible at.at least until we start also considering the costs and economics. Incidently. In the lower plot. This chance (probability) is known as the risk factor: it is an expression. So this type of graph has now become one of the standard key tools in exploration/development decision. if the engineers say that a field of so many million barrels is going to be needed to justify development and production costs. we can read off from the graph the chances of our field containing that much oil or more. objective. for geological reasons. We have to give not only our best estimate of how much petroleum there might be. and honest as can be in assessing exploration risk. . 50. there really is no such thing as the risk factor. We try to assess the probability that each factor will be satisfied. For example. if any one of them fails or is lacking. now gives a more complete picture of the viability of an undrilled prospect . then no oil. the curve represents the chance (probability) that the reserves are a certain size or greater. say. to give the chance of discovering certain reserves or more including the 50 per cent chance that we may find nothing at all. Indeed it does not! When we are looking at exploration of the unknown. And if all this sounds like a gambling game.the risk factor. different geologists will arrive at different figures for the probability of success. It is also used to assist management in making their exploration/development decisions. probable. but also the chance of there in fact being any oil at all. When it comes down to risk. we have to go a stage further. Most usefully. you may say.72 The output from a Monte Carlo simulation with the percentages plotted cumulatively. It is this sort of thing that helps to make the oil exploration business so competitive. the same values are discounted by a 50 per cent risk factor. but rather it is the number an individual geologist might produce to reflect his/her personal interpretation of the geology. it doesn't take any account of the fact that our exploration well may. combined with the estimate of how much. UNDISCOVERED RESERVES This is all very well. This is what is used to determine those reserves that may be called proven.Quantitative Assessment . turn out to be totally dry-lacking in hydrocarbons. management can then decide whether or not to take the gamble on developing the field at those odds. as opposed to assessing what we already know to be there. and then merely combine the probabilities to give an overall probability . The risk factor. By plotting the answers from the 100 per cent probability downwards. the 90. that is exactly what it is.). but it assumes that we have already discovered oil. It will give a graph which shows the probability that the reserves will be of a certain size or more. and 10 per cent levels of probability respectively. and ensures that all possibilities are considered. Of course we try to be as scientific. in numbers. The way it is commonly approached is to go back to the basic conditions for oil acumulation: all of the essential requirements have to be met if there is to be oil in a particular place and that. It cannot be worked out completely objectively. we can plot out the percentages of answers in successive size ranges cumulatively as we work down the list (Fig. one of the main benefits from all of this is that it forces us to think carefully about the geological requirements for oil to be present. perhaps. of our confidence that there will be at least some oil.
and the area under that bit will represent what. 3. Adding this to the original reserves will give us what is sometimes called the `ultimate reserves'-a grand total for the basin. and use the figures for the known also for the unknown ones. 4. and made available for entrapment (the `charge') can be calculated. This combines in a single estimate. the expected reserve estimates from our Monte Carlo simulation multiplied (discounted) by the risk factor (Fig. for our `best estimate'. This figure is extremely imprecise and may be not much more than a guess. Let us look at the more important ones. we can. to believe that we can do this would be the height of conceit. How now do we estimate what still remains to be discovered over a wider area or even an entire sedimentary basin? There really is no objective way of doing it-but still companies and governments want to know. sometimes in combination. go for a large but very risky prospect. ULTIMATE RESERVES So far we have been talking about a single oil accumulation or a single prospect. Should we. and we should be on our guard against believing that it is what we shall find (it most categorically is not) or otherwise trying to read too much into it. we are said to be consulting the oracles! All of the above techniques have been used. it is a pretty wild sort of plot. Use past statistics (number of barrels of oil found on average for each 100m of exploration drilling?) and extrapolate to future drilling. But we have to admit that. qualify it by a statistical probability. knowing how rich it is. the amount of oil generated. otherwise we may be doing little more than guessing. and calculate average quantities of oil per cubic mile of sediment. There are lots of uncertainties in this but the calculation would be amenable to a Monte Carlo type of simulation. expelled. however. This kind of plot can be used also for individual basins or for the whole world. We could adopt what is known as a `geochemical material balance' approach. on average. Many `experts' have scratched their heads over the estimation of undiscovered reserves. Some of these will be successful.Quantitative Assessment . 6. However. 1. Undiscovered are thus what we hope to find in a prospect area or sedimentary basin in the future. We might look at explored and known parts of the basin. however. In a similar vein the amount of oil found world-wide each year from the beginning of the century can be plotted. is a hypothetical figure. If all else fails. we have to assume that today we can identify and assess all of the prospects that ever will be found in the basin. and a number of techniques have been employed. for example. and some may be more appropriate in given circumstances than the others. Delphi was the place in ancient Greece where one went to consult the oracle about one's future. then use these figures for the unexplored parts of the basin. 2. Extrapolate this smoothing line out into the future.). and as such can be very useful in planning an exploration program. the built-in risk factor takes care of this. We could make comparisons between known and unknown basins. all of them are very dodgy . this technique may bring us into the right ball-park. This starts with the volume of mature source rock in the basin and then. 5. However. if we draw a smooth line through it to even out the peaks and the troughs.73 Lastly. merely use the average of the figures they produce. If we have a reasonable amount of information and control. but some will be dry. or underlying each square mile of surface area. unless we really have a lot of information (we never have enough!). on this tack. or would our money be better spent on drilling a smaller but safer one? The risked reserves. the two elements of size and chance of success. The obvious thing to do is to add together the risked reserves estimates of all the remaining prospects. This is known as the Delphi technique. remains to be found. let us note a number known as the risked reserves. Forcing these experts to agree a figure amongst them might refine the approach. get a number of experts to make their forecasts by whatever technique they prefer and. then the area under it represents the total volume of oil found to date.
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