HYDROCARBONS

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.

HYDROCARBONS

CONTENTS
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

Contents

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

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Certain microorganisms.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. convert some of the organic debris to biogenic methane. or under different diagenetic conditions. These changes lead to a gradual cessation of microbial activity. called metagenesis. called catagenesis. oil and gas molecules can be expelled from the source rock into more permeable carrier beds or conduits. Although the transformation process is very complex. During this second transformation phase. and were formed as dead organic matter was converted to microbial tissues. These differences can have a significant effect on hydrocarbon generation. . Many of the chemical compounds present in sediments are in fact derived from bacteria. and temperature increases. Most of this organic matter is transformed during diagenesis info very large molecules. the largest of which are called kerogen. with many details still poorly understood. Migration through these conduits often leads to traps. these are the precursors for petroleum. kerogen begins to decompose into smaller. are chemically distinct from each other. As burial depth increases. As temperature rises. Formation of biogenic methane has been recognized for a long time. thermal reactions become increasingly important. In the early stages of catagenesis most of the molecules produced from kerogen are still relatively large. In the late stages of catagenesis and in the final transformation stage. Once formed. These play a key role as the precursors for oil and much natural gas. but only within the last few years have we realized that in many areas a large portion of the natura!-gas reserves are biogenic. where hydrocarbon movement ceases and accumulation occurs. it is known that organic debris derived from plants and algae is best preserved in fine-grained sediments deposited in the absence of oxygen. The earliest stage of hydrocarbon generation occurs during diagenesis. and thus eventually bring organic diagenesis to a halt. Low-temperature chemical and biological reactions (called diagenesis) that occur during transport to and early burial in the depositional environment modify this organic matter. called methanogens.Organic Facies .5 1 . porosity and permeability decrease. more mobile molecules. and are called bitumen . 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. the principal products consist of smaller gas molecules. however.

A large fraction.6 2 . Preservation of organic material is actually a rare event. comprises microbial tissue formed within the sediments by the bacterial transformation of plant and algal debris. however. Preservation of organic matter begins with photosynthesis. Because of .Organic Facies THE CARBON CYCLE Because oil and gas are generated from organic matter in sedimentary rocks. Oxidative decay of dead organic matter is a highly efficient process mediated largely by microorganisms. as a consequence of the much more rapid reproduction of simple aquatic organisms.Organic Facies . the yearly productivity of both groups is about equal. less than 1% of the annual photosynthetic production escapes from the carbon cycle and is preserved in sediments. Zooplankton and higher animals contribute relatively little organic matter to sediments. we need to understand how this organic matter came to be preserved in the rocks. Some of the organic material in sediments consists of fragments of plants or algae that derived their energy from the sun. Most organic carbon is returned to the atmosphere through the carbon cycle. 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. Despite the great imbalance in biomass between terrestrial plants (450 billion metric tons [t]) and aquatic phytoplankton (5 billion t).

Only a small fraction of this (10. If this deeper water is enriched in nutrients. Each of these categories could in turn be further subdivided. Total Organic Carbon (TOC) values decrease monotonically through the first 300 meters of burial before levelling out at about 0. and dilution. predators. accumulation of organic-rich sediments cannot occur. because without adequate productivity. In the modern world there are zones of intense seasonal upwelling off the west coasts of California. When we consider inefficiencies in discovery and recovery. In relatively unrestricted marine environments. preservation. light intensity. Nutrients dissolved in waters below the photic zone therefore go unutilized. and that the microbes have given up trying to digest it.000 billion t) dispersed in fine-grained sedimentary rocks. orogeny and erosion.000 billion t. Shallowmarine environments.05%) occurs in economic deposits of fossil fuels. The three primary factors influencing the amount of organic matter in a sedimentary rock are productivity.7 extensive oxidation of land-plant debris in soils. There is another zone of seasonal upwelling off the Horn of Africa in the Indian Ocean as a result of . Upwelling occurs where bulk movement of surface water away from a particular area allows deeper water to ascend to replace it.1%. the low TOC values could indicate that the remaining organic matter has no more nutritional value.000. Productivity is the logical place to begin our analysis. and general water chemistry. For example. one of the critical parameters governing productivity. Although some destruction of organic material occurs during transport to the depositional environment. and Northwest Africa that result from the movement of surface waters away from these coasts. watercirculation patterns are particularly important for supplying nutrients and thus controlling productivity. PRODUCTIVITY A partial listing of the many factors influencing productivity would include nutrient availability. On the other hand. Depth could interfere with microbial diagenesis when compaction reduces pore sizes and nutrient fluxes in interstitial waters. over vast amounts of geologic time the small fraction that escaped the carbon cycle has built up extremely large quantities of organic matter (20. or about 0. Each factor may be dominant under different conditions.Organic Facies . Only where there is upwelling of subsurface waters can these nutrients return to the photic zone. FACTORS INFLUENCING ORGANIC RICHNESS In order for organic-rich rocks to be formed. high photosynthetic productivity will occur at the site of upwelling. only one molecule out of about every one million successfully negotiates the journey from living organism to the gasoline pump. Namibia. suggesting that either depth or organiccarbon content eventually limits diagenesis. significant amounts of organic matter must be deposited and protected from diagenetic destruction. a great deal of the oxidation of organic matter occurs within the sediments themselves. Nutrient availability is. Bodies of water naturally develop density stratification. however. carbonate supply. are therefore much more productive than the open ocean. in fact. Although oxidative decay destroys most of the yearly production. Peru. where there is local recycling of nutrients from decaying organisms and influx of fresh nutrients from terrestrial sources. with a preference for horizontal water movement within each density layer. volcanism. paleoclimate. nutrient availability would depend on such factors as water circulation patterns. temperature. and recycling by organic decay. because under normal circumstances they cannot move upward into the zone of photosynthesis. much of the terrestrial organic material is already highly oxidized when it arrives in the sediments.

essentially the only viable organisms are those that we call anaerobes. and paleoclimates. These anaerobic processes are inefficient compared with aerobic diagenesis. Thus if anoxia can develop. much oxic sediment also contains large amounts of organic matter. At lower levels of dissolved oxygen. Three factors affect the preservation (or destruction) of organic matter: the concentration and nature of oxidizing agents. and we could coin the term dysoxic to describe the zone itself. paleoclimatic conditions. microorganisms that utilize materials like sulfate or nitrate ions instead of molecular oxygen as electron acceptors in their metabolic processes. The term "anoxic" literally means "having no oxygen.2 mL/L. Because most of the oxidation occurring in the water column. however. landmasses.5 milliliters (mL) per liter (L)). Such models are interesting.Organic Facies . There are. oxidizing agents are probably the most crucial factor. respectively. Processes that occur in these two zones are called aerobic and anaerobic.8 monsoonal winds that drive surface waters away from the coast." hut because of the radical change in biota that occurs at about 0. ANOXIA. All these areas exhibit high productivity when upwelling occurs. some problems associated with their application. diagenesis is restricted to anaerobic processes. All large organisms require oxygen in order to live. and all the other factors that influence upwelling loci is severely limited. soils. Secondly. Anoxic sediments are not always easy to recognize. preservation of organic matter will be much enhanced. the simplest way to limit oxidation is to limit the supply of oxygen. First.5 mL/L). the remaining individuals often become dwarfed in an effort to survive in a hostile environment. Anoxia is of tremendous importance in the preservation of organic matter in sediments. The presence of undegraded marine organic material is a strong indication of anoxia. especially in the Palaeozoic. and the sediment-accumulation rate.2-0. the type of organic matter deposited. We call the zone in which oxygen contents are high the oxic zone. many species disappear. although some species can tolerate extremely low oxygen levels (0. because some of the commonly used indicators of anoxia may be misleading. productivity is probably not as important a factor as preservation. Anoxic sediments always contain elevated TOC values (generally above 2% and always above 1% ).2 mL/L is called the anoxic zone. After all. and sediments is biological. Of these. At dissolved oxygen levels below about 0. and because most biological oxidation processes require molecular oxygen. if on the average only 1% of organic matter is preserved. There are many more organic-rich facies resulting from excellent preservation than from extremely high productivity. The term dysaerobic has been used to describe processes occurring in the transitional zone (0. and may in fact prove useful in future exploration efforts. TOC values alone must therefore be used with caution. the accuracy with which we can reconstruct continental positions. because marine organic matter is consumed preferentially by organisms. its use in practice has been expanded to include very low oxygen levels as well. because when the availability of oxygen is limited. the zone where oxygen falls below 0. PRESERVATION The principal control on organic richness is the efficiency of preservation of organic matter in sedimentary environments. However. Theoretical models have been developed to predict upwelling (and consequent productivity) in ancient seas from input data on continental configurations. Its presence in . wind and water circulation patterns. and are usually limited in scope by the availability of sulfate or nitrate.2 mL/L. especially of woody origin. increasing preservation rates is a very efficient way to increase organic richness.

STAGNANT BASINS. Color should be used mainly as a negative criterion: If a rock is not very.9 rocks therefore indicates that diagenesis was stopped prematurely. anoxia can be very local. The ultimate implications of anoxia for petroleum exploration are great. Wyoming). but limnic environments often are. The laminae prove that burrowing fauna were absent. are anoxic in some of the places where they have been penetrated. Finally. it may well have developed after burial. Truly stagnant basins are actually quite rare. Although pyrite does indeed form under anoxic conditions. anoxic sediments. Lack of communication between the layers prohibits replenishment of oxygen in the bottom layer. and warm climates are necessary to avoid overturn caused by freeze-thaw cycles. most likely by absence of oxygen. Therefore. are not rich in organic carbon. 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. Consumption of oxygen results from decay of dead organisms that have sunk from the photic zone above. particularly in understanding lacustrine beds. where photosynthesis and turbulence can no longer contribute oxygen to the water. and both the waters in the bottom layer and the underlying sediments will become anoxic. Furthermore. leading to the eventual development of a pycnocline (density interface) which prevents interchange between the two layers. and if the climate is subtropical or tropical. If an isolated body of water is deep enough. 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. very dark. The cooler. Lakes of the Rift Valley of East Africa are excellent modern analogs receiving much attention from both researchers and explorationists at the present time. Nevada). however. Depths in excess of 200 m are required to prevent mixing during storms. OXYGEN-MINIMUM LAYER (OML). Conversely. in fact. and strata from several basins in China. it is instructive to consider complete stagnation. It therefore behoves us to understand the conditions under which anoxia develops. and its presence indicates that the anaerobic reduction of sulfate ion did occur. and therefore that dissolved-oxygen levels were below 0. the Elko Formation (Eocene/Oligocene. they often owe their dark color to finely divided pyrite or to particular chert phases. The supply of fresh oxygen is therefore limited to horizontal . All anoxic sediments will be very dark gray or black when deposited. slow circulation or turnover of the water column occurs almost everywhere. denser waters remain at the bottom. Lakes in failed rifts can also contain organic-rich. The presence of pyrite itself can also be deceptive. it has been estimated. that most of the world's oil was generated from source beds deposited under anoxic conditions. Marine basins are seldom isolated enough to fit well into the stagnant-basin model. no more oxygen can enter.Organic Facies . Many black rocks. The oxygen minimum layer usually begins immediately below the photic zone. it cannot represent an anoxic facies. the presence of bioturbation indicates that the bottom waters were not anoxic. This oxygen minimum develops when the rate of consumption of oxygen within that layer exceeds the rate of influx of oxygen to it. Color is not a reliable indicator. Lake deposits associated with continental rifting. there is no guarantee that anoxia was present at the sea floor. anoxic sediments show preserved depositional laminae on a millimeter or submillimeter scale. especially during the Triassic along the margins of the developing Atlantic Ocean. Nevertheless.2 mL/L. Among the ancient lake beds thought to have been deposited in permanently stratified waters are the well-known Green River Shale (middle Eocene. once the original oxygen has been consumed in oxidizing organic matter. then permanent density stratification will arise as a result of temperature differences within the water column. although stunted burrows can be used as evidence of dysoxia.

Evaporitic environments combine the opportunity for abundant growth of algae with ideal conditions for preservation. but it is too slow to disturb the anoxia which develops in the bottom layer. Large amounts of organic material are preserved in coal swamps as a result of the combined effects of poor water circulation. Anoxia . in areas of poor circulation. Where the sill is shallow. Coal Swamps. as a result of diminished oxygen demand. The result is often deposition of organic-rich laminae within evaporites. those environments can also incorporate the features of an oxygen-minimum-layer model. the oxygen they can contribute is limited. mid-Cretaceous. and diminished bacterial activity. Shallowly silled basins often yield evaporites. Nutrients are concentrated by evaporation. the shallowness of the swamps prevents the waters themselves from becoming anoxic. In either case. Below the OML oxygen levels again increase. if the basin is deep enough. Intensely developed OMLs occur in areas of high productivity and. which could be excellent hydrocarbon source rocks. because these horizontally moving waters also lie within the oxygen minimum layer. Circulation is often restricted by the presence of a sill. the point of connection between the restricted area and the open-marine environment. the waters entering or leaving the basin are near surface. 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. In an evaporitic environment (Karabogaz in the Caspian Sea) there is a net flow of water into the basin. permanent density stratification will develop. Although an oxygen-minimum layer exists virtually everywhere in the ocean. High productivity reduces oxygen levels. sediments will be deposited under low-oxygen conditions. when a major transgression had greatly increased the continental shelf area. Shallow Silling. RESTRICTED CIRCULATION. Any organic matter arriving in those sediments will have an excellent chance to escape oxidation. In contrast. Wherever an intensely developed OML intersects the sediment-water interface. since most organic matter was destroyed within the overlying OML. In actuality there is a lazy turnover of the bottom waters. It has been proposed that at certain times in the past (e. Late Devonian) the world oceans were severely depleted in dissolved oxygen. 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. an upward expansion of the OML led to a tremendous increase in the surface area covered by anoxic bottom waters.. and high hydrogen-sulfide concentrations create conditions poisonous to predators.g. including paleoclimate and water circulation.Organic Facies . It is not coincidental that these were times of deposition of large amounts of organic-rich rocks in many parts of the world. During those times the OML expanded both upward and downward because of poor supply of oxygen to subsurface waters. to a lesser extent. In times like the mid-Cretaceous. because of their connection with the open-marine realm. whereas in a fluvially dominated system (Black Sea) the net flow of surface water is out over the sill. However. high influxes of organic matter. Although circulation in coal swamps is generally sluggish. and grazers and predatory organism are eliminated by the high salinities.10 movement of oxygen-bearing waters. This depletion was probably the result of the complex interplay of several factors. There are other ancient and modern examples of organic-rich rocks deposited under anoxic or near-anoxic conditions associated with OMLs. Late jurassic. with the bottom layer almost isolated from the open-marine waters. its intensity varies greatly. Coal swamps can develop under a variety of conditions in both marine and non-marine environments. foreset beds within the same system are leaner in organic matter because they are deposited above the OML. Furthermore. or as lateral facies equivalente thereof. Settings in which circulation is restricted are much more common than stagnant basins.

. because extensive decomposition occurs during its fall to the ocean floor. Oxic Settings. Coals also accumulate very rapidly and. It may also contain very resistent organic debris derived from erosion of ancient rocks. and therefore wi11 contain primarily oxidized organic matter. cellulosic. much of the organic material that does reach the bottom in deep waters arrives in relatively large fecal pellets. The extremely high accumulation rates for biogenic carbonates and siliceous sediments in zones of high productivity promote preservation of the associated algal protoplasm. at very high accumulation rate dilution may become a more important factor than increased preservation. the phenolic components present in lignin-derived terrestrial material are toxic to many micro-organism. very slow sedimentation rates. thus preventing extensive diagenesis of such material. In fact. and other oxidative processes.Organic Facies . Coals are important source rocks for gas accumulations. Near-shore oxidizing facies sometimes have high TOC values. lignitic. and low productivity in the overlying pelagic realm. Dilution does not reduce the total amount of organic matter preserved. renders it of little nutritional value. with their high concentrations of organic matter. biogenic inorganic sediment. and more favorable for gas than for oil. because its chemical components are digestible and provide precisely the nutrients required by scavengers and predators. RAPID SEDIMENTATION AND BURIAL. Rapid settling of organic debris through the water column is also important. Phenolic bactericides derived from lignin hinder bacterial decay in the water and throughout the sediment column. Most depositional settings not specifically catalogued above will be more or less well oxygenated. their virtual absence in much terrestrial organic material. DILUTION Although high sediment-accumulation rates enhance preservation of organic matter. all of which are chemically quite distinct from each other. Any extensive organic diagenesis is therefore likely to eliminate algal organic matter first.11 develops within the sediments rather than in the water column. but it does spread that organic material through a larger volume of rock. Lack of sulfate in non-marine swamps further prevents anaerobic microbial destruction of the organic matter. and may include woody. or organic material. Nitrogen and phosphorus are in particular demand. which settle several orders of magnitude faster than individual phytoplankton. especially in structural (woody) material. The net result is a reduction in TOC values. Rapid sedimentation and burial con also enhance preservation. as a result of more rapid removal of organic material from the zone of microbial diagenesis. That material which remains is dominantly of terrestrial origin. The hydrocarbon-source potential of all of these oxidizing facies is low. Rapid deposition of inorganic detritus is common in turbidites and in prodelta shales. Furthermore. but their supposedly low potential for generating oil is to be reconsidered. TOC values increase as sediment-accumulation rates increase. TYPE OF ORGANIC MATTER. but the organic material is almost invariably woody. provide an ideal means of maintaining low-oxygen conditions. cuticular. Abyssal sediments are notoriously low in organic carbon as the result of the combined effects of high oxygen levels in abyssal waters. Organic matter of algal (phytoplanktonic) origin is consumed more readily by organisms than are other types of organic material. forest fires. Rapid burial is accomplished by a high influx of inorganic detritus. or resinous material.

Some of the commonly applied criteria are apt to be misleading. a strongly developed oxygen-minimum layer. Anoxic events in the past were probably not as large in scale or as long lasting as some workers have suggested. in contrast. dilution is far less marked. Direct control of the anoxia was thus probably local. and rapid burial.and atmospheric-circulation patterns. such events were often interrupted for long periods before anoxia was reinduced. Productivity can be predicted by locating ancient sites of marine upwellings. however. Consequently. in contrast. As in the modern oceans. as a result of high productivity or sluggish circulation. anoxia in bottom waters is a phenomenon whose effects we should learn to recognize in ancient rocks. including stagnancy or near-stagnancy. such models are not yet of much practical value for the distant past. in which the organic and inorganic materials arrive together. . we should always strive to place the organic rich rocks in the larger context of basin evolution through time and space. however. Our ability to make accurate predictions is limited. SUMMARY There are three principal factors that affect the amount of organic matter in sedimentary rocks: primary photosynthetic productivity.12 Dilution effects depend upon rock lithology. The most reliable criteria for bottom-water anoxia are the preservation of fine depositional laminae. effectiveness of preservation. Biogenic sediments. Models that integrate the concepts of organic richness with depositional cycles and facies analysis will be valuable tools for understanding hydrocarbon systems in basins. Because of its role in creating rocks with excellent hydrocarbon-source potential. Of these. lack of knowledge of seawater chemistry and nutrient availability at those times. If the rapidly accumulating sediment is mainly clastic. Preservation is best accomplished where oxygen is excluded from bottom waters. however. To derive maximum value from our analyses. and the presence of high TOC values coupled with the occurrence of undegraded marine organic matter. anoxic sediments were deposited discontinuously through time and space. It is often very difficult to separate the influences of these various factors in a particular depositional environment. It is important to be able to distinguish local anoxia or anoxia developed deep within sediments from anoxia induced by anoxic bottom waters.Organic Facies . Rapid accumulation of sediment shortens the residence time of organic matter in the zone of diagenesis and thus promotes preservation. and a very imperfect understanding of oceanic. Facies changes from carbonates to shales may create large dilution effects that can be wrongly interpreted as indicating changes in oxygen levels. dilution effects may lead to lower TOC values in spite of enhanced preservation rates. are not as strongly affected by dilution. by uncertainties about exact continental positions and configurations in the past. Although certain periods undeniably contain more than their share of anoxic rocks. Shales. and dilution by inorganic material. In biogenic sediments or coals. where sediment-accumulation rates are directly proportional to organic-carbon-accumulation rates. preservation is generally the most important. show strong dilution effects when accumulation rates are very high. There are a number of mechanisms by which oxygen depletion may be fostered and maintained.

NAMES AND STRUCTURES HYDROCARBONS In chemical terms a hydrocarbon is a compound containing only the elements carbon and hydrogen. The chemical reactions of interest to us are very few and are discussed only briefly. 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. two bonds. The structures of methane and ethane are thus represented by CH4 and CH3CH3 respectively. and organic geochemistry the study of organic compounds present in geological environments. three bonds. Examples of hydrocarbons are methane. All compounds containing carbon atoms. oxygen. Writing the detailed structure of a simple molecule like methane is no problem. the explicit inclusion of every atom and every bond becomes extremely tedious. This unique property of carbon is responsible for the existence of literally millions of different organic compounds. We can make other logical simplifications for longer carbon chains. every carbon atom forms four bonds. are termed organic. ethane. and metal carbides. One common convention is to represent all the hydrogen atoms attached to a given carbon atom by a single H. In this chapter we restrict the usage of the term hydrocarbon to the standard chemical one. elsewhere in this text usage will vary. using a subscript on the H to denote the total number of hydrogens around that atom.Organic Chemistry . whose structures are shown below. Organic chemistry is thus the study of carboncontaining compounds. This usage is historical and does not imply that all such compounds are necessarily derived from living organisms. and other elements. Similarly. If one wants to draw large molecules. as it does in the real world. The following representations of n-pentane are equivalent: CH3CH2CH2CH2CH3 or CH3(CH2)3CH3. and nitrogen. hydrogen always forms one bond. trace metals. .Organic Chemistry INTRODUCTION Anyone who uses petroleum geochemistry must be familiar with basic chemical terminology. creating long chains and ring structures.13 3 . oxygen and sulfer. carbonates. especially if one has to do it only occasionally. except carbon dioxide. 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. in which one must also learn all the reactions of many classes of compounds. and indeed in every carbon compound (except a few highly unstable ones created only in laboratories). and cyclohexane. however. In each of these compounds. sulfur. Several different types of shorthand have therefore developed to facilitate drawing organic molecules. Carbon atoms like to form bonds with each other. This objective is very different trom that of a normal course in organic chemistry.

as in "alkane. Note that the name of each compound ends in -ane. That is. Many unsaturated compounds have carbon-carbon double . In the case of 2methylhexane (C7H16) the basic structure is hexane. are able to combine with additional hydrogen. For example. in contrast. Among the most important branched hydrocarbons in organic geochemistry are the isoprenoids. but the prefixes denoting the number of carbon atoms in the other alkanes are derived from Greek numbers. ethyl and propyl). Branching can occur. We have also seen that carbon atoms can be arranged in rings. Regular isoprenoids consist of a straight chain of carbon atoms with a methyl branch on every fourth carbon. 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. giving rise to a vast number of possible structures. no more hydrogen can be incorporated into the molecule without breaking it apart. these molecules are called n-alkanes or nparains. The simplest series of hydrocarbons has linear structures. These cyclic compounds (called naphthenes) are named by counting the number of carbon atoms in the ring and attaching the prefix cyclo. simple inspection shows how mant' hydrogen atoms each carbon atom must have. the names of the other nine simplest n-alkanes are given in the following table. and carbon-carbon bonds are shown as lines connecting those points. because they are saturated with respect to hydrogen." The first four names are irregular. a CH3 (methyl) group is attached to the second carbon atom. Each carbon atom is represented by a point. n-pentane and cyclohexane are represented by the line structures shown below. The term methyl. Another important group of hydrocarbons is the unsaturates. which. We have ahready encountered n-pentane. which we used earlier.14 An even quicker shorthand that uses no letters at all has evolved. Hydrogen atoms and bonds to hydrogen atoms are not shown at all. and indicates that there is no branching in the carbon chain. Other adjectival forms are made by dropping the -ane ending and adding yl (for example. Because we know that each carbon atom forms four bonds and each hydrogen atom forms one bond.Organic Chemistry . 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. The letter n stands for normal. All the compounds mentioned above are called saturated hydrocarbons or saturates. The zigzag configuration illustrated for n-pentane is adopted to show clearly each carbon atom.

In fact. they are free to move throughout the cyclic system instead of being held between two particular carbon atoms.15 bonds. that is. Aromatics possess a system of alternating single and double bonds within a cyclic structure. They are named in a similar manner to the alkanes. these compounds are called alkenes. these compounds are quite different trom the majority of the organic molecules found in living organisms. the compounds in which they occur are called heterocompounds. It is this delocalization of electrons which makes aromatic compounds very stable. propene (C3H6). sulfur. or other elements. In the laboratory they are readily converted to alkanes by the addition of hydrogen in the presence of a catalyst. Polycyclic aromatic hydrocarbons having fused ring structures are quite common. because the most common heteroatoms are nitrogen. highly aromatic materials of . bitumen. Many common NSO compounds are not directly related to biogenic precursors. and kerogen are called heteroatoms. they do not add hydrogen easily. but they actually have completely different chemical properties from alkenes and are unusually stable. except that the ending -ene indicates the presence of a double bond. and cyclohexene (C6H10). Many of the heterocompounds present in organisms are converted to hydrocarbons during diagenesis and catagenesis. including hydrogenafion. they do not long persist in geologic environments. NONHYDROCARBONS Atoms other than hydrogen and carbon that occur in petroleum. some complex hydrocarbons that are found in fossil organic material can be related directly to individual biological precursors. sulfur. Fossil organic matter often contains a vide variety of heterocompounds. The circle indicates that the electrons in the double bonds are delocalized.Organic Chemistry . and oxygen. Examples are ethene (C2H4) . which is an almost-endless sheet of aromatic rings. A variety of reactions. converts alkenes to alkanes and cyclic compounds during diagenesis. Although they are unsaturated. the majority contain oxygen. Their stability permits aromatics to be important constituents of oils and sediments. Aromatics form an extremely important class of unsaturated hydrocarbons. nitrogen. the structures of which are shown below. phosphorus. By hydrogenation ethene thus reacts to form ethane. At first glance aromatics appear to be nothing more than cyclic alkenes containing several double bonds. which are large. Heterocompounds are also called NSO compounds. Some aromatic molecules are very large. The hydrocarbons we discussed so far are relatively simple molecules. Because alkenes are highly reactive. The hydrocarbons present in petroleum are mostly the end products of extensive degradation of biogenic molecules. A simplified notation for drawing these molecules permits us to represent the double-bond system by a circle within the ring. of which some are biogenic and others are formed during diagenesis. Most biological molecules are larger and more complex than the simple hydrocarbons. Among the most important NSO compounds are the asphaltenes. Although they are very important constituents of petroleum. The extreme case is graphite.

Lignin monomers are linked topether to form molecules having molecular weights from 3000 to 10.000 atomic mass units. carbohydrates. Carbohydrates include starch. Because phenols are potent bactericides. and amino acids. the latter is the most abundant organic compound in the biosphere. sugars. and thus tends to become concentrated as other organic matter is decomposed. They have many characteristics in common with kerogen. and cellulose. Many nonhydrocarbon molecules common to living organisms are also present in sediments. Like lignin. however. providing much of the structural support for large land plants.16 varying structure. Lignin and cellulose are major constituents of humic coals. it is an important constituent of terrestrial organic matter.Organic Chemistry . 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) . Upon decomposition lignin forms phenolic compounds. which are aromatics having a hydroxyl group (OH) attached. It is a polymer consisting of many repetitions and combinations of three basic aromatic subunits. and thus are seldom preserved in sediments (exceptions occur in shell material and in bones. Although cellulose is quite resistant to decomposition under some conditions. They are rapidly metabolized by virtually all organisms. most carbohydrates are attacked readily by microorganisms. Lignin is an important component of wood. lignin is rather resistant to degradation. but asphaltene molecules are smaller and more aromatic than most kerogens.

and sediments. having very high molecular weights. and how much oil or gas can be expected. Algal (boghead) coals are formed in environments where the source phytoplankton lack both calcareous and siliceous skeletal components. Coals are a subcategory of kerogen.Kerogen INTRODUCTION Kerogen is normally defined as that portion of the organic matter present in sedimentary rocks that is insoluble in ordinary organic solvents. The residual kerogens also undergo important changes. which have molecular weights of several thousand or more. Kerogen composition is also affected by thermal maturation processes (catagenesis and metagenesis) that alter the original kerogen. for example) are partially or completely dismantled. as well as the nature of the organic matter from which it was formed. humic acids. soils. which are reflected in their chemical and physical properties. large molecules that have no regular or biologically defined structure. Large organic biopolymers of highly regular structure (proteins and carbohydrates.Kerogen . Lack of solubility is a direct result of the large size of kerogen molecules. The soluble portion. when the chemical and biological destruction and transformation of organic tissues begin. oil. The smallest of these geopolymers are usually called fulvic acids. the geopolymers become larger. Humic coals are best thought of as kerogens formed mainly from landplant material without codeposition of much mineral matter. and less regular in structure. KEROGEN FORMATION The process of kerogen formation actually begins during senescence of organisms. will be discussed in a following chapter. have more mineral matter than algal coals. Today it is used to describe the insoluble organic material in both coals and oil shales. called bitumen. in contrast. 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. The detailed chemistry of kerogen formation need not concern us greatly. carbon dioxide. and the individual component parts are either destroyed or used to construct new geopolymers. with some of the inorganic matrix often being contributed by the algae themselves. and still larger ones. During the course of diagenesis in the water column. Each kerogen molecule is unique. These geopolymers are the precursors for kerogen but are not yet true kerogens. A basic understanding of how kerogen is formed and transformed in the subsurface is therefore important in understanding how and where hydrocarbons are generated. 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. Subsurface heating causes chemical reactions that break off small fragments of the kerogen as oil or gas molecules. Coals and oil shales should therefore be viewed merely as sedimentary rocks containing special types of kerogens in very high concentrations. more complex. and ammonia from the original geopolymers. whether these hydrocarbons are mainly oil or gas. because it has patchwork structures formed by the random combination of many small molecular fragments. as well as dispersed organic matter in sedimentary rocks. Oil shales. strongly influence the ability of the kerogen to generate oil and gas. If anaerobic sulfate . Diagenesis results mainly in loss of water. 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. humins. Diagenetic and catagenetic histories of a kerogen. develop after tens or hundreds of meters of burial. True kerogens. slightly larger ones. and natural gas.17 4 . The term kerogen was originally coined to describe the organic matter in oil shales that yielded oil upon retorting.

One way that we can begin is by classifying kerogens into a few general types. Geopolymers are more or less immune to bacterial degradation. Kerogens formed under reducing conditions will be composed of fragments of many kinds of biogenic molecules. it would not be of great and direct significance to exploration geologists. Kerogen formation competes with the destruction of organic matter by oxidative processes. KEROGEN COMPOSITION Because each kerogen molecule is unique. better organic preservation. and if the sediments are depleted in heavy-metal ions (which is often the case in nonclastic sediments but is seldom true in shales). the macerals that they are composed of. in contrast. Carboncarbon double bonds. About a decade ago workers at the French Petroleum Institute developed a useful scheme for describing kerogens that is still the standard today. is developing a general method of describing gross kerogen composition and relating it to hydrocarbon-generative capacity. and their organic precursors Transformation of organic material in sediments and sedimentary rocks. and III) and have studied the chemical characteristics and the nature of the organisms from which all types of kerogens were derived. large amounts of sulfur may become incorporated into the kerogen structure. In a low-oxygen (reducing) environment. it is somewhat fruitless to attempt a detailed discussion of the chemical composition of kerogens. 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. . therefore. They identified three main types of kerogen (called Types I. The four types of kerogen. and ultimately of much greater practical value.18 reduction is occurring in the sediments. Even if such a description were possible. the subdued level of bacterial activity allows more time for the formation of geopolymers and. in contrast. II. What is within our reach. Most organic oxidation in sedimentary environments is microbially mediated. In an oxidizing environment many of the small biogenic molecules will be attacked by bacteria before they can form geopolymers. because the bacterial enzyme systems do not know how to attack them. which are highly reactive. Microorganisms prefer to attack small molecules that are biogenic. Subsequent investigations have identified Type IV kerogen as well. Those kerogens formed under oxidizing conditions. The amount of sulfur contributed by the original organic matter itself is very small. are converted into saturated or cyclic structures.Kerogen .

in contrast. in contrast. . unless they have small inclusions of Type II material. Utah. Type IV kerogens contain mainly reworked organic debris and highly oxidized material of various origins. Cellulose and lignin are major contributors. from Wyoming. They are generally considered to have essentially no hydrocarbon-source potential. of middle Eocene age.19 Type I kerogen is quite rare because it is derived principally from lacustrine algae. Most Type II kerogens are found in marine sediments deposited under reducing conditions. and fossil resin. and carbohydrates. successively. phenols. Type III kerogens are composed of terrestrial organic material that is lacking in fatty or waxy components. catagenesis. Type II (liptinitic) kerogens are also high in hydrogen. Type II kerogens arise from several very different sources. Type I kerogens have high generative capacities for liquid hydrocarbons. have the lowest hydrogen contents. have lower hydrogen contents because they contain extensive aromatic systems. are normally considered to generate mainly gas. Type III kerogens have much lower hydrocarbon-generative capacities than do Type II kerogens and. Type III kerogens have high oxygen contents because they are formed from lignin. They also include contributions from bacterial-cell lipids. cellulose. which mainly contain polycyclic aromatic systems. despite their very disparate origins. and Colorado. Type III (humic) kerogens. and metagenesis. 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. leaf waxes. The various Type II kerogens are grouped together. Type IV kerogens are highly oxidized and therefore contain large amounts of oxygen. Occurrences of Type I kerogens are limited to anoxic lakes and to a few unusual marine environments. Type IV kerogens. because they all have great capacities to generate liquid hydrocarbons. Type I (algal) kerogens have the highest hydrogen contents because they have few rings or aromatic structures. Van Krevelen diagram showing maturation pathways for Types 1 to IV kerogens as traced by changes in atomic HIC and OIC ratios. In the immature state. pollen and spores. The shaded areas approximately represent diagenesis.Kerogen . Heteroatom contents of kerogens also vary with kerogen type. Hydrogen contents of immature kerogens (expressed as atomic H/C ratios) correlate with kerogen type. Type I and Type II kerogens. contain far less oxygen because they were formed from oxygen-poor lipid materials. The best-known example is the Green River Shale. including marine algae.

which occurs after catagenesis. 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." Metagenesis begins long before true rock metamorphism. interrelated. nonclastic sediments). they are to kerogen what minerals are to a rock. In this text we shall use the terms somewhat interchangeably. By convention the term catagenesis usually refers to the stages of kerogen decomposition during which oil and wet gas are produced. in contrast. a term taken trom coal petrology. called catagenesis and metagenesis.Kerogen . The different types of kerogen particles are called macerals. forcing us to make assumptions about the source organisms. break off small molecules and leave behind a more resistant kerogen residue. Most high-nitrogen kerogens were therefore deposited under anoxic conditions where diagenesis was severely limited. is derived mainly from sulfate that was reduced by anaerobic bacteria. wherever possible. proving the origin of the particle. but they really represent different aspects of the same process. Thermal decomposition reactions. they represent fundamentally different perspectives. Catagenesis refers to transformations of kerogen molecules. In principle. The kerogen in a given sedimentary rock includes many individual particles that are often derived from a variety of sources. The biggest problem comes in identifying Type III kerogen. most terrestrially influenced kerogens are low in nitrogen. The correspondence is not perfect. Although the terms catagenesis and oil generation are often used synonymously. In others the original fabric has disappeared completely. 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. marine. . however. Despite its name. but it also continues through the metamorphic stage. The small molecules eventually become petroleum and natural gas. Nitrogen is derived mainly from proteinaceous material. they are not precisely equivalent. in some cases. High-sulfur kerogens (and coals) are almost always associated with marine deposition. which is destroyed rapidly during diagenesis. It is possible to make a reasonably good correlation between kerogen type based on chemical characteristics and kerogen type based on visual appearance. especially when we are discussing both aspects simultaneously. A list of the most common macerals and their precursors is given in the table presented earlier in this chapter. Kerogen sulfur. called maturation. Thus few kerogens consist of a single maceral type. In many cases the original cellular structure is still recognizable. metagenesis is not equivalent to "metamorphism. whereas hydrocarbon generation focuses on the production of hydrocarbon molecules. Kerogen types are defined by the morphologies of the kerogen particles. Microscopic organic analysis has reached a fairly high level of refinement and is often capable of assessing kerogen type with good accuracy. KEROGEN MATURATION INTRODUCTION Very important changes. because there is not a perfect biological separation of the various types of living organic matter.20 Sulfur and nitrogen contents of kerogens are also variable and. Catagenesis and hydrocarbon generation occur concurrently. however. represents drygas generation. Sulfur is only incorporated into kerogens in large quantities where sulfate reduction is extensive and where Fe +2 ions are absent (organic-rich. because fresh waters are usually low in sulfate. the materials from which a maceral was derived. anoxic. Many high-sulfur kerogens are also high in nitrogen. Macerals are essentially organic minerals. Because lignins and carbohydrates contain little nitrogen. Metagenesis. occur when a kerogen is subjected to high temperatures over long periods of time. Maceral names were developed by coal petrologists to describe.

Kerogen . It is impossible to set precise and universal temperature limits for catagenesis. it is also true that other changes in kerogen properties have little or nothing to do with it. 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 real reason for following kerogen catagenesis. the rates of catagenesis are generally not important at temperatures below about 70° C. the chemical process of maturation never stops completely. much as a cookie browns during baking. Although it is obvious that many measurable changes in kerogens are related to hydrocarbon generation. The composition of the products (bitumen. however. There is therefore no necessary cause-and-effect relationship . is to monitor hydrocarbon generation. after hydrogen loss is well advanced. the residual kerogen gradually becomes more aromatic and hydrogen poor as catagenesis proceeds. There is a steady color progression yellow-goldenorange-light brown-dark brownblack as a result of polymerization and aromatization reactions. The most important implication of these chemical changes is that the remaining hydrocarbongenerative capacity of a kerogen decreases during catagenesis and metagenesis. In contrast. Nitrogen and sulfur are also lost from kerogens during catagenesis. including the Miocene Monterey Formation of southern California. These reactions are intimately related to important changes in the chemical structure of kerogen. oil. the more hydrocarbons it can yield during cracking. the cracking of any organic molecule requires hydrogen. Kerogen particles become darker during catagenesis and metagenesis. In the late stages of maturity. Furthermore. high-sulfur oils found in a number of areas. much of the sulfur is lost in the earliest stages of catagenesis. of course. For practical purposes. All kerogens become increasingly aromatic and depleted in hydrogen and oxygen during thermal maturation. The more hydrogen a kerogen contains. Old rocks will often generate hydrocarbons at significantly lower temperatures than young rocks. 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. possessing essentially no remaining hydrocarbon generative capacity. and gas) will be discussed in a following chapter. Kerogen maturation is not a reversible process-any more than baking a cake is reversible. Types I. This complex interplay between the effects of time and temperature on maturity is discussed in a later chapter. thus allowing us to judge the extent to which kerogen maturation has proceeded. but it also states that at any temperature above absolute zero reactions will be occurring at some definable rate. As we saw earlier. Nitrogen loss occurs primarily during late catagenesis or metagenesis. and thus are not necessarily valid indicators of hydrocarbon generation. EFFECTS OF MATURATION ON KEROGENS Kerogen undergoes important and detectable changes during catagenesis and metagenesis. provided that the hydrogen content of the kerogen was known prior to the onset of catagenesis. but they are not necessarily identical with hydrocarbon generation. Furthermore. simply because the longer time available compensates for lower temperatures. Some of these changes can be measured quantitatively. II. 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. even if drastic decreases in temperature occur. and III kerogens will therefore be very similar chemically. because time also plays a role. as evidenced by low maturity.21 This chapter will focus on those changes in the residual kerogen that accompany catagenesis. Because many of the light product molecules are rich in hydrogen. Chemical reaction-rate theory requires that the rates of reactions decrease as temperature decreases.

and because vitrinite particles also occur in kerogens. while others are small heterocompounds. is that some of the bitumen is expelled from the source rock or cracked to gas. Some properties of kerogen change very little during catagenesis. contain large numbers of unpaired electrons. These structural reorganizations bring about changes in physical properties of kerogens. Some of these are hydrocarbons. These small compounds are much more mobile than the kerogen molecules and are the direct precursors of oil and gas. For example. Kerogens often fluoresce when irradiated. there would be a large and continuous build-up of bitumen in the rock as a result of catagenetic decomposition of kerogen. during metagenesis the chief product is methane. Free-radical concentrations can be measured by electron-spin resonance. The difference between the two curves represents bitumen expelled from the rock or cracked to light hydrocarbons.22 between kerogen darkening and hydrocarbon generation. 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. somewhat beyond the oil-generation window. and which can be used to gauge the extent of molecular reorganization. resulting in lower bitumen contents in the source. The more random a kerogen's structure. small molecules are broken off the kerogen matrix. A general name tor these molecules is bitumen. The intensity and wavelength of the fluorescente are functions of kerogen maturity. HYDROCARBON GENERATION As kerogen catagenesis occurs. What actually occurs. which are unpaired electrons not yet involved in chemical honds. and the less it will be reflected. the technique.Kerogen . is the ability of kerogen particles to reflect incident light coherently. however. carbon-isotopic compositions of kerogens are affected little by maturation. Kerogens. Both curves are highly . has been widely and successfully applied in assessing kerogen maturity. As kerogen matures and becomes more aromatic. called vitrinite reflectance. because the flat aromatic sheets can stack neatly. Bitumen generation occurs mainly during catagenesis. its structure becomes more ordered. The concentration of free radicals in a given kerogen has been found to increase with increasing maturity. Cracking often produces free radicals. especially highly aromatic ones. Plot of bitumen generation as a function of maturity (dashed fine) compared to bitumen remaining in rock (solid line). One property that is strongly affected. If neither expulsion from the source rock nor cracking of bitumen occurred. the visual appearance of kerogen also does not change during catagenesis: kerogen types are generally recognizable until the particles become black and opaque. Except for darkening. the more an incident light beam will be scattered. and no guarantee that a particular kerogen color always heralds the onset of oil generation. Because coal rank is merely a measure of coal maturity.

this result is hardly surprising. Several methods exist for estimating the extent to which hydrocarbon generation has occurred in a given kerogen. those rocks that generate few hydrocarbons may not expel them until they have been cracked to gas. In very lean rocks expulsion may occur so late that cracking of the generated bitumen is competitive with expulsion. We shall consider the latter briefly here. 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. Rich rocks will become overpressured earlier than lean ones and thus will also expel hydrocarbons earlier. Many workers now believe that microfracturing of source rocks is very important tor hydrocarbon expulsion. Resinite consists of polymerized terpanes (ten-carbon isoprenoids) that can decompose easily by reversing the polymerization process. Candidates for early expulsion would be very organic rich rocks and those containing resinite or high-sulfur kerogens.Kerogen . Microfracturing is related to overpressuring. . Conversely. Kerogens formed from resinite will generate condensates or light oils quite early. Other kerogens usually follow a more traditional model. we cannot always define the limits of hydrocarbon generation with great confidence. Source rocks that generate large amounts of hydrocarbons early are likely to expel those hydrocarbons early. In such cases the expelled products will be mainly gas. Effective generation of hydrocarbons requires that the generated products be expelled from the source-rock matrix and migrated to a trap. high-sulfur oils at low levels of maturity. Kerogens formed from lipid-rich organic material are likely to generate liquid hydrocarbons. as measured by parameters such as vitrinite reflectance. SUMMARY Kerogen begins to form during early diagenesis. The chemical composition of a kerogen controls the timing of hydrocarbon generation and the type of products obtained. residual kerogen as well as small molecules that are the direct precursors for petroleum and natural gas. because natural variations among samples cause much scatter in experimental data.23 idealized. whereas those kerogens that contain few lipids will generate mainly gas. although we know that oil generation does occur during the phase we call catagenesis. Thus. however. High-sulfur kerogens generate heavy. hydrogen-poor. including rock physics and organic-geochemical considerations. It has become apparent in recent years that not all kerogens generate hydrocarbons at the same catagenetic levels. which in turn is partly attributed to hydrocarbon generation itself. when large geopolymers are created from biological molecules. Given the significant chemical differences among the various types of kerogens. but none of these measurements is closely linked to the actual process of hydrocarbon generation. Sulfur-rich kerogens decompose easily because carbon-sulfur hbonds are weaker than any bonds in sulfur-poor kerogens. Numerous methods exist for tracing the history of a kerogen and determining its original chemical and physical characteristics. Catagenesis of kerogen produces a more aromatic. Timing and efficiency of expulsion depend on a number of factors. The chemical composition and morphology of kerogen macerals depend both on the type of original organic matter and on diagenetic transformations.

The influence of the lithologies of source and reservoir rocks on these compositional changes is poorly understood. Some of these are present in relatively large quantities. highly aromatic asphaltene molecules that are often rich in heteroatoms. One fraction consists mainly of saturated hydrocarbons. Much of this variety is related to source-rock facies and the composition of the kerogens that generated the bitumens. Saturated hydrocarbons are the most thoroughly studied of the components of petroleum and bitumen because they are the easiest to work with analytically. The lighter of these fractions. many unanswered questions remain about the processes that transform bitumen into petroleum. and cyclics. There is no doubt that they are related. and how much is due to physical separation of chemical compounds having very different properties. Petroleum. triterpanes. Such correlations can be particularly useful in establishing genetic relationships among samples. particularly those derived from diterpanes. Heavier aromatic and naphthenoaromatic hydrocarbons. Asphaltenes tend to aggregate into stacks because of their planarity. we first separate a crude oil or a bitumen into several fractions having distinct properties. A second fraction consists of aromatic hydrocarbons and some light sulfur-containing compounds. Bitumen and petroleum compositions can also be used as tools in correlating samples with each other. 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. In order to investigate the individual compounds present. The final fraction contains very large. and resins. Light aromatic hydrocarbons. Few of these heterocompounds have been studied carefully. We also do not know how much of the change involves chemical reactions. However. but we are not certain whether they occur mainly within the source rock or during migration through the reservoir rock. and steranes. The large sizes of asphaltene units render . but these compounds are lost from bitumens during evaporation of the solvent used in extracting the bitumen from the rock. n-alkanes.000. and form complexes with molecular weights of perhaps 50. Maturity also exerts control over bitumen and petroleum composition. are more commonly studied. like benzene and toluene. In order to understand bitumen and petroleum compositions and to use them for exploration. bitumen is almost universally accepted as the direct precursor for petroleum. Most of the NSO compounds appear in the remaining two fractions. contains a wide variety of small and medium-sized molecules with one or more heteroatoms. and Natural Gas INTRODUCTION Petroleum obtained from reservoir rocks and bitumen extracted from fine-grained rocks have many similarities. while others are only trace contributors. Reservoir transformations in some cases greatly affect oil composition and properties. This chapter will compare and contrast bitumen and petroleum compositions and examine the factors responsible for the observed differences. Both bitumens and petroleums exhibit a wide range of compositions. branched hydrocarbons (including isoprenoids). and Natural Gas - 5 . variously called polars.24 Bitumen. Each of the fractions contains certain types of chemical compounds. NSOs.Bitumen. Major compositional changes occur in going from bitumen to petroleum. however. Petroleum. but they also exhibit many important differences. indeed. COMPOUNDS PRESENT IN BITUMEN AND PETROLEUM GENERAL CLASSES OF COMPOUNDS Both bitumen and petroleum contain a very large number of different chemical compounds. have been studied in petroleums.

or of the diagenetic conditions under which the organic matter was buried. and by their catagenetic formation from long-chain compounds such as fatty acids and alcohols. the lower-carbon homologs are given more weight in the calculation.25 them insoluble in light solvents. 25. especially 23. If odd-carbon homologs predominate. asphaltene molecules have not been studied in detail. however. The most useful biomarkers serve as indicators of the organisms from which the bitumen or petroleum was derived. the CPI is 1. The distributions are quite sharp. because the concentration of n-alkanes often decreases with increasing carbon number.Bitumen. the CPI is greater than 1. receive contributions of n-alkanes from both terrestrial and marine sources. of course. and Natural Gas .0. 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). CPI values can therefore . or CPI. Petroleum.or even-carbon homologs is evident. In most cases. Sediments are also known that exhibit a strong preference for n-alkanes having an even number of carbon atoms. Because of their molecular complexity and heterogeneity. which are derived from biogenic precursor molecules. but their sources are simply no longer recognizable due to diagenetic and catagenetic transformations. Their high concentration in bitumens and oils is best explained by their existence in plant and algal lipids. marine algae produce n-alkanes that have a maximum in their distribution at C-17 or C22. SPECIFIC COMPOUNDS Biomarkers. They are. In a few cases specific precursor organisms or molecules can be identified. The average of two ranges is taken to minimize bias produced by the generally decreasing n-alkane concentrations with increasing number of carbon atoms. These n-alkanes are believed to be formed by hydrogenation (reduction) of longchain fatty acids and alcohols having even numbers of carbon atoms. 27. For the most part n-alkanes present in terrestrial plants have odd numbers of carbon atoms. Many of the compounds and classes of compounds that we find in crude oils and bitumens are called biomarkers. or members of the n-alkane series. Many sediments. and no preference for either odd. Their n-alkane distributions reflect this mix. such as pentane or propane. These compounds. are essentially molecular fossils. Carbon Preference Index. In contrast. Other compounds. although we know for certain that the biomarker molecule is biogenic. however. and 31 atoms. whereas in other instances we may be able to limit the possible precursors to only a few species.0.and even-carbon members is equal. even-carbon homologs predominate as strongly as do the oddcarbon homologs among the n-alkanes. where input of terrestrial n-alkanes is minimal and diagenetic conditions are highly reducing. depending upon the species present. Another important indication of the origin of n-alkanes is the distribution of individual homologs. 29. an abbreviation for biological markers. (Among the acids and alcohols present in living organisms. we are unable to use it as an "index fossil" for specific organisms. 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. of biological origin. Asphaltenes can thus be removed from oils or bitumens in the laboratory or refinery by adding a light hydrocarbon. If the number of odd. FACTORS AFFECTING COMPOSITION OF BITUMEN AND PETROLEUM SOURCE AND DIAGENESIS Biomarkers n-Alkanes were among the first biomarkers to be studied extensively.) Even-carbon preferences occur principally in evaporitic and carbonate sediments. However.

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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.

RESERVOIR TRANSFORMATIONS
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
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.

SUMMARY
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.

In order to understand the complex sequence of events that we call migration. Traps are the means by which migration is stopped and accumulation occurs. There appear to be three distinct ways in which oilphase expulsion can occur. and overpressuring commences anew. Furthermore. . Its importance is probably limited to the edges of thick units or to thin source beds. particularly along lines of weakness such as bedding planes. where pre-existing light hydrocarbons bleed out of the rocks prior to the onset of significant generation and expulsion. An important implication of the microfracturing model is that expulsion cannot take place until the strength of the source rock has been exceeded. where they can be preserved over long periods of time.Migration . the microfractures heal.29 6 . but those that have been discounted will not be discussed here. but will describe the most widely held views on the dominant mechanisms of primary and secondary migration and accumulation. and solution in gas. 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. This chapter wi11 not go into the physics and chemistry of migration in detail. Once the internal pressure has returned to normal. PRIMARY MIGRATION MECHANISMS Many theories about primary migration (expulsion) have been popular at various times. Diffusion has been shown to be active on at least a minor scale and over short distances in carefully studied cores. Diffusion would therefore have to be coupled with a powerful concentrating force to yield accumulations of appreciable size. By far the most popular mechanism invoked today to explain primary migration is expulsion of hydrocarbons in a hydrophobic (oily) phase. whereas accumulation of hydrocarbons requires concentration. Many cycles of pressure buildup. Secondary migration is the movement of oil and gas within this carrier bed. it involves expulsion of hydrocarbons from their fine-grained. Today there are only three mechanisms of primary migration that are given serious consideration by most petroleum geochemists: diffusion. and pressure release can be repeated. One occurs most commonly as a result of microfracturing induced by overpressuring during hydrocarbon generation. When the internal pressures exceed the strength of the rock. microfracturing occurs. oil-phase expulsion. Based on empirical evidence.Migration DEFINITIONS Migration is the movement of oil and gas within the subsurface. During intense hydrocarbon generation. Each of these steps is quite distinct from the others. we must look at each of these steps separately. Momper's value has been widely accepted as a reasonable average. microfracturing. The main problem with diffusion as an important mechanism of migration is that diffusion is by definition a dispersive force. Accumulation is the concentration of migrated hydrocarbons in a relatively immobile configuration. Laminated source rocks may therefore expel hydrocarbons with greater efficiency than massive rocks. Although the exact threshold value must vary considerably as a function of rock lithology and other factors. any contribution by diffusion will be overwhelmed by that from other expulsion mechanisms. expulsion. it is probably most effective in immature rocks. Primary migration is the first phase of the migration process. The hydrocarbons within the pores then become isolated again because of the impermeability of the waterwet source rocks to hydrocarbons.

expulsion can be lateral. this approach is rather approximate. Because the source rock is overpressured. A second way in which oil-phase expulsion can occur is from very organic-rich rocks prior to the onset of strong hydrocarbon generation. depending upon the carrier-bed characteristics of the surrounding rocks. Therefore. Thus inefficiency of expulsion is responsible for much of the difference in composition of bitumen and petroleum that we noted earlier. This expulsion process probably releases internal pressures in the rock. Finally." We can only estimate the fraction of the bitumen left in the source rock during microfractureinduced expulsion. Because neither case is of great general significance for petroleum formation. Primary migration is unquestionably the most difficult part of the entire migration process. Expulsion of hydrocarbons is facilitated because water-mineral and water-water interactions no longer need be overcome. Primary migration is difficult and slow. hydrocarbons will be expelled in any direction that offers a lower pressure than that in the source rock. where they do exist. most of the hydrocarbons are expelled. Thus primary migration ends whenever a permeable conduit for secondary migration is reached. this early expulsion mechanism seems to be limited to rocks having very high original contents of lipids. Of course. This type of expulsion is probably only operative in very rich source rocks during the main phase of oil generation. the migrating fluids will take them. we conclude that solution in gas is a minor mechanism for oil expulsion. By comparing the average hydrocarbon compositions of bitumen and crude oil. requires that there be a separate gas phase. DISTANCE AND DIRECTION The distances traversed by hydrocarbons during primary migration are short. particularly in brittle carbonate and opal-chert source rocks. expulsion of oil dissolved in gas. but a large proportion of NSO compounds and heavier hydrocarbons are left behind. but it does give some idea of the efficiency of expulsion. As soon as easier paths become available. Sand stringers within shale units can provide secondary migration conduits for hydrocarbons sourced in the shales. but also an "exit tax. also make excellent secondary-migration pathways. . oil-phase expulsion can take place when bitumen forms a continuous network that replaces water as the wetting agent in the source rock. The organic matter expelled consists mainly of lipids that were present in the sediment during deposition and diagenesis. because petroleum is being forced through rocks having low matrix permeabilities. it would be expected only in the late stages of catagenesis or in source rocks capable of generating mainly gas. In most cases hydrocarbons are generated within short distances of viable secondary-migration conduits. Fracture and joint systems. Thus a source rock lying between two sands will expel hydrocarbons into both carrier beds. Massive.Migration . Because the driving force for microfracture-induced primary migration is pressure release. and assuming that expulsion of hydrocarbons is ten times as efficient as expulsion of NSO compounds. we can estimate that once the expulsion threshold is reached the expulsion efficiency for bitumen is about 50%. The third mechanism. In most cases the distances of primary migration are probably between 10 centimetres and 100 m. or downward. but the mechanism by which overpressuring is achieved is not understood. therefore. unfractured source-rock units are relatively rare. Such a phase could only exist where the amount of gas far exceeds the amount of liquid hydrocarbons. primary migration may be of poor efficiency. upward.30 Once the threshold has been exceeded. Therefore the threshold must represent not only a hurdle to be cleared by the bitumen before it can leave the source rock.

Whenever a pore throat narrower than the globule is encountered. the globule will squeeze into the pore throat and continue moving upward. Hydrocarbons are thus capable of displacing water downward and moving upward themselves. Within massive sandstone. This fact has important implications for tracing migration pathways through a thick conduit. and becomes stuck until either the buoyant force or the capillary entry pressure changes. however. These modifications to the overall scheme are probably minor. and therefore are more buoyant. Thus movement within a confined migration conduit will be updip perpendicular to structural contours whenever possible. 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. hydrodynamic flow. If the capillary-entry pressure exceeds the buoyant force.31 SECONDARY MIGRATION MECHANISM Once hydrocarbons are expelled from the source rock in a separate hydrocarbon phase into a secondary-migration conduit. The smaller the pore throat. hydrocarbons entering the land from an underlying source rock will move toward the top of the sand even as they migrate laterally updip. The upward buoyant force is partly or completely opposed by the capillary-entry pressure. If water is flowing in the subsurface in the same direction as hydrocarbons are moving by buoyancy. which is resistance to entry of the hydrocarbon globule or stringer into pore throats. but it is not essential and does not change our basic model. we say that accumulation has occurred. Coalescence of globules of hydrocarbons after expulsion from the source rock therefore increases their ability to move upward through water-wet rocks. the more deformation is required. then the rate of hydrocarbon movement should be enhanced somewhat. the globule cannot enter. A third force-namely. In contrast.Migration . DISTANCE AND DIRECTION Secondary migration occurs preferentially in the direction that offers the greatest buoyant advantage. the globule must deform to squeeze into the pore. Structural contours on the top of the carrier bed will . the force required to deform the oil globule enough to enter the pore throat. then the rate of hydrocarbon transport will be retarded. When hydrocarbons cease moving. can modify hydrocarbon movement. migration may have to proceed at an oblique angle to structural contours. If. Retardatin of buoyant movement as an oil globule (X) is deformed to fit in to a narrow pore throat (Y). Hydrocarbons are almost all less dense than formation waters. subsequent movement of the hydrocarbons will be driven by buoyancy. That is. the pore throat is very tiny or if the buoyant force is small. Where faulting or facies changes create impassable barriers (capillary-entry pressure exceeds buoyant force). secondary migration will cease until either the capillary-entry pressure is reduced or the buoyant force is increased. This model is very simple. if bulk water movement opposes the direction of buoyant movement. If the upward force of buoyancy is large enough. secondary migration will occur both laterally and vertically. Buoyancy promotes migration. whereas capillary-entry pressure retards or stops it. Opposing the buoyancy is capillary-entry pressure. requiring only the existence of two forces.

The absence of both tectonic and stratigraphic barriers permits long-distance migration. Lateral migration is therefore often stymied. and the Saudi Arabian crude oils. Various mechanisms for exsolution were proposed to explain how all this was supposed to happen. ACCUMULATION INTRODUCTION In the old days. Cap rocks having low . Migration updip within a single stratum can accomplish a large amount of "vertical" migration rather painlessly. otherwise it is impossible to account for the incredible volumes of hydrocarbons in place today. Vertical migration can also occur across formations. for example. Vertical migration distances can also be considerable. because now accumulation can occur where the buoyancy-driven movement of the hydrocarbon phase is stopped or even strongly impeded. the process of hydrocarbon accumulation was somewhat mystical.32 in general be more useful than contours on its base. Nevertheless. Lack of long-distance migration opportunities implies that supergiant and giant accumulations are far less likely and that exploration targets will be smaller. are basins in which lateral migration distances do not exceed a few tens of kilometers. when migration was thought to occur mainly in water solution. at which time they suddenly became immiscible with the water and formed a separate hydrocarbon phase. as a result of both tectonic disruption and facies changes related to tectonic events. all must have migrated long distances.Migration . large drainage areas and chances for very large accumulations. are broken up tectonically and have poor lateral continuity of carrier beds. However. Faults may play an important role in vertical migration. Most basins. Unconformities also can juxtapose migration conduits. Much more common. including the Athabasca Tar Sands of western Canada. Drainage area is one of the most important factors influencing the size of hydrocarbon accumulations. thus providing a potentially very effective system for combined vertical and lateral migration. however. Long-distance migration implies. although it should be remembered that there are two fundamentally different types of vertical migration. leading to smaller fault-bounded accumulations and 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). Vertical migration across stratigraphic boundaries is more difficult. however. can offer possible pathways (although sometimes rather tortuous ones) for vertical migration. by definition. Hydrocarbons had to remain in solution until they reached the trap. The problem in discussing long-distance migration is that such cases are rare. distances of several thousand feet are not unheard of. The question of long-distance migration has been much discussed and disputed. Today we believe that hydrocarbons migrate as a separate phase. the heavy oils in the Orinoco Belt of Venezuela. Stacked sands in a paleodelta. It is possible to have lateral migrations of as much as a few hundred kilometers in exceptional circumstances. Indeed. 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. not only because they often juxtapose carrier beds from different stratigraphic horizons. There is no a priori reason why secondary migration cannot be a very-long-distance phenomenon. and has provided as carrier beds continuous blankets of sand juxtaposed with these source rocks. This model greatly simplifies the problem of accumulation. but also because an active fault or the brecciated zone adjacent to a fault may itself have high permeability. the largest hydrocarbon deposits known.

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. Much of the hydrocarbon storage at Antelope is apparently in silts and sands juxtaposed with the producible Bakken reservoir. Gas production is actually from the low-permeability sand rather than from the high-permeability sand updip and downdip.33 permeabilities to hydrocarbons provide barriers to migration: that is. Cross section across the Rhine Graben of West Germany showing the discontinuity of strata as a result of extensional tectonism endemic to rift basins. The low permeability sand thus creates a bottleneck to gas migration. No traditional seal exists. Fracturing associated with high races of oil generation in the Green River Shale has created a supergiant accumulation at Altamont. and vertical migration becomes important. 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. Classical traps are well understood. that strong hydrocarbon generation and migration is going on today. The simple principle behind a kinetic trap is that hydrocarbons are supplied to the trap faster than they can leak away.Migration . while the structure or lithologic change prevents lateral updip migration. KINETIC TRAPS Kinetic traps represent a fundamentally new concept in trapping mechanisms for hydrocarbons. Accumulations are small because drainage areas are small. of course. The much smaller Antelope Field produces from the Mississippian Bakken Formation. . This model requires. a fractured shale that is both source and reservoir. Thus the Elmworth Field exhibits a water-over-gas contact. the low-permeability sands become filled with gas. The seal prevents vertical migration from the reservoir rock into overlying strata. Because gas generation is very rapid. Seals in the traditional sense of the word may not exist. Because the high permeability sand updip allows gas to migrate rapidly through. rocks whose capillary-entry pressures are high enough to overcome hydrocarbon buoyancy. and will be covered separately. it remains water wet. Most hydrocarbon traps are either structural or stratigraphic. Lateral migration is of necessity short distance. The Elmworth Field in the Alberta Deep Basin of Canada is the prototype for kinetic gas accumulations. CLASSICAL TRAPS.

Formation of hydrates thus provides an important trapping mechanism. TAR-MAT TRAPS Tar mats produced by biodegradation can create excellent seals. Because hydrate zones are often hundreds of meters thick. One important feature of methane hydrates is that they are much more efficient at storing methane than is liquid pore water. Despite the rarity of tar-mat seals. these changes in temperature and pressure can cause separation of the original phase into a liquid phase and a gas phase. These gas hydrates consist of a rigid lattice of water molecules that form a cage within which a single molecule of gas is trapped. contain mainly light components. and the poor producibilitv of the hydrocarbons they trap. but hydrates large enough to accommodate butane molecules are known. When the original hydrocarbon phase contains large amounts of light components. and in zones of permafrost. The gas phase will. because much of the methane trapped is biogenic and was formed in young. Methane is by far the most commonly trapped gas molecule. and thus get left behind as the oil globule or stringer moves upward. 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. especially methane. and thus are not expelled as efficiently with the oil phase. A second characteristic is that gas hydrates form effective seals against vertical hydrocarbon migration.34 Many of the accumulations in Pliocene reservoirs in southern California are also kinetic accumulations in a slightly different sense.Migration . Once expulsion has occurred. The technology necessary for producing these hydrocarbons has not yet been developed. unconsolidated sediments that would have no other means of retaining the methane. 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. tar mats may provide the only possible means for retaining any hydrocarbons. because the same conditions that created the tar mat persist in the subsurface. but in the future gas-hydrate accumulations may be of great economic significance. In cases where no other structural or stratigraphic trapping mechanism exists. GAS HYDRATES Formation of crystalline hydrates of natural gas provides an extremely efficient trapping mechanism for natural gas. however. The polar molecules once again interact most strongly with interstitial water and mineral surfaces. The polar (NSO) compounds interact most strongly with both mineral surfaces and water molecules. the quantities of gas in such accumulations are huge. It will therefore migrate much faster and . Phase changes occur as a result of decreases in pressure and temperature during migration. there may be a chromatographic effect during secondary migration. large accumulations have formed despite high rates of leakage. the lighter (gas) phase will be far more buoyant than the liquid phase. of course. and would be incapable of sealing accumulations for long geologic periods. Accumulations beneath tar-mat seals are generally biodegraded themselves. As soon as two immiscible phases are formed. but it may also include some heavier hydrocarbons dissolved in the gas. 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. At the present time the vast potential of gas-hydrate accumulations is just beginning to be recognized. Cap-rocks in those fields are often poor. The base of the gas hydrate zone forms a pronounced seismic reflector that often simulates bottom contours and cuts across bedding planes. Because intense oil generation is going on now.

vertical faulting. and the possibilities of combined vertical and lateral migration. we want to determine the main pathways and conduite through which migration occurs. SIGNIFICANCE FOR EXPLORATION Explorationists who are reading about migration will surely ask. by faulting. In using our understanding of secondary migration for exploration. we will also have determined the timing of expulsion. . Timing of expulsion must be dealt with in a different way. Vertical-migration distances can be considerable. "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. and the vertical and horizontal distances involved. Barriers can be created by folding. and expulsion occurs concurrently with generation to relieve generation-induced overpressuring. Proximity to effective source rocks and their permeabilities to hydrocarbons determine conduits. Pathways. Lateralmigration distances are strongly influenced by tectonic and depositional histories of basins. depending upon stacking of reservoirs.Migration . in what direction they moved. and the timing of expulsion. When separation of a single hydrocarbon phase into two phases occurs. We already know two important facts about timing from our previous discussion: expulsion based on microfracturing cannot occur before generation. 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. both new phases will have compositions that differ drastically from the original phase. gas is presumably expelled as a gas phase. Thus if we can determine the timing of generation. Tectonically stable basins have the best potential for long-distance migration and supergiant accumulations. In summary. leading to an enrichment of hydrocarbons in the expelled liquid. Efficiency of expulsion for hydrocarbons is apparently much higher than for NSO compounds. Efficiency of expulsion of liquids has already been estimated to be in the neighbourhood of 50% after the expulsion threshold has been reached. are determined by structural contours on the top of the carrier beds. We have already stated that oil is expelled primarily as a liquid phase. We need to know when hydrocarbons moved.35 will also assume the structurally high position in any reservoirs containing both phases. and how far they moved. the efficiency of expulsion. 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. or by the presence of tars. the barriers that modify die direction of migration and eventually stop it. as we have seen.

which may give a misleading impression of `lakes' of petroleum under the ground! Structure contour maps. The location of a trap in the subsurface is often the first objective of an exploration program. 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.Petroleum Traps We have seen petroleum generated in and expelled from the source rock formation into an overlying or underlying reservoir. This may be caused either by the reservoir itself dying out or by an interruption of its upwards continuity to the surface. The highest point of the reservoir. exploration used to consist largely of finding a trap. Nowadays we can do better. is known as the crest of the trap. they should properly be drawn with the same scale for both the vertical and the horizontal. Indeed.Petroleum Traps . 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). is the spill-point: this is where oil. If then we are to find any of it still preserved. The contours are in feet below mean sea-level. To complement the structure contour map. they can be mapped by means of contours drawn on the top of the reservoir formation. (a) A simple hypothetical anticline. as the beds on one side are dropped down relative to the other. is mapped by contours showing depth below sealevel. First. the ticks are on the downthrown sides of the faults.(2-18) Before we go further. it will escape to surface as a seepage. except that the contours are in depth below sealevel. Faults will be marked by jumps of the contours. Note that we commonly highlight petroleum accumulations by shading or colouring the reservoir formations where they contain oil or gas. Any oil getting there will be unable to migrate further and so it starts to accumulate. we need a few definitions. if more continues to migrate up into the trap than can be . which may refer either to its depth or to the spot under the ground where it lies. before we reached our modern understanding of the geology of petroleum. (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.36 7 . so that the highest points on the map have the lowest values. A structure contour map resembles an ordinary topographic contour map. The lowest point. and hoping for the best. one or more cross-sections may be drawn. THE REPRESENTATION OF TRAPS Traps are commonly depicted in two ways. To give a true representation. where it is lost. but it is often convenient to exaggerate the vertical to show the individual beds more clearly. drilling a well into it. by displacing the water already there in the porosity. If it can. up towards the ground surface. but there must also be some sort of blockage to prevent further migration. Such a configuration of the reservoir is known as a trap. The top of a reservoir formation. These are illustrated using a simple anticline as an example.

2. there are various types of . Oil being lighter than water. Hydrodynamic traps. petroleum migrating up along a reservoir can go no further and it accumulates there as a pool. using a cross-section of a simple anticline as example (2-19). Where there is more than one such pool in the same or overlapping areas. so that we can recognize a generally horizontal oil-water contact. which are rare and are mentioned mainly for completeness. i. where the trap has been produced by deformation of the beds after they were deposited.(or gas-) column. 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.Petroleum Traps . or in their layering. formed partly by structural and partly by stratigraphic effects.e.37 accommodated. the only structural effect being a tilt to allow the oil to migrate through the reservoir. However. in which the trap is formed by changes in the nature of the rocks themselves. Some terms used to define a trap. Now we can start to consider the types of trap whose discovery may await us. separates out on top within the pore-spaces of the reservoir. then we may see a gas-water contact. Stratigraphic. The vertical height of the oil (or gas) between the crest of the trap and the water contact is the oil. the informal term pay is often used. Just a couple more terms. and the same term is used loosely to refer to the area of the trap above the level of the spill-point. perhaps if more than one reservoir is present. Structural. If there is no oil. The vertical height between the spill-point and the crest is referred to as the closure. STRUCTURAL TRAPS The best known type of trap is the anticline: on reaching the crest. Similarly gas. will spill out (under) and migrate on. being lighter still. which have porosities and permeabilities too low for them to contribute oil to production. will occur as a gas cap above a gas-oil contact. Combination traps. A single accumulation of oil or gas is called a pool. however. but not entirely due to either. 3. The trap is due to water flowing through the reservoir and holding the oil in places where it would not otherwise be trapped. 4. that most reservoir formations include some tight intervals. either by folding or faulting. they are embraced by the familiar terms oilfield or gasfield. They are normally classified under four headings (2-21): 1. When referring to a single well. Let us remember.

on the other hand. This leads us into the next problem. we can thus expect to find only smaller and smaller accumulations of petroleum down to the centre of curvature. If. In this case. so that the beds become intensely crushed and thrust together: we may no longer even have an anticline at all.Petroleum Traps . In practice. Compressive structures have a range of shapes between the purely concentric or parallel anticline and the similar fold. we have to know its depth to know where best to locate the well. depending on the nature and strength of the rock layers being folded. and we may no longer be able to see where the bottle is. Seismic may help. (b) The anticline is asymmetrical and the crest shifts with increasing depth.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. therefore in order to drill into a reservoir near its highest point (where we would expect the oil to be). These conditions mean that the anticline becomes smaller and tighter at deeper levels until we reach a common `centre of curvature'. There is a definite limit to the depths to which we should drill. To test the crest at depth. noting the differences in shape and prospectivity that we have to try to interpret. and we may be able to continue exploration down to depths where we have to stop for other reasons. These compressive structures pose one problem right from the start. Traps can also be formed against faults if a chopped-off reservoir is thrown against a shale or other impervious rock. the anticline is asymmetrical. many structures have forms in-between the two extremes. The general principles of this are straightforward.(2-22) In the concentric fold the tops and bottoms of all the layers remain strictly parallel to each other. then the position of the crest will shift with increasing depth. beyond which there may be no trap left to explore as the consequence of decoupling of layers. Anticlines. maintains its shape constant down to depth. This is a very different kettle of fish from the concentric anticline. in cross-section. We will describe in a little detail the most important types of anticline. Let us see what the implications are for exploration. 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. Cover it with a few more blankets and a duvet or two. Below this point we have just too much rock to fit into the anticline. . so that the beds maintain a constant thickness throughout. This can only happen if there is an apparent thickening of some beds over the crest of the fold. but an understanding of the shape and size of a prospect is clearly critical to programming an exploration well. and the blanket bulges upwards with an anticlinal shape. (a) The dips are the same on both flanks and the crest is beneath the same locality at all depths. In this type of structure. Cross-sections of trap-forming anticlines. but we commonly have to undertake some form of geometrical construction to interpret what is happening at depth. The similar anticline. a well would have to be located off-crest at surface. with one flank steeper than the other. we can find the trap present at all levels down to the basement. Other types of anticline can be formed without any lateral compression at all: an important one is the drape or drape-compaction structure.

Note also that salt. or over an upfaulted block or horst. it may bend up and seal off the strata it cuts through. it is also liable to fracture the overlying and surrounding beds creating fault traps. and hence the combined name. then they will blanket the hill as an anticline.39 A drape-compaction anticline.Petroleum Traps . This creates a rollover anticline. A second effect comes into play here: because there is a greater thickness of beds off the structure than over the top.(2-26) A wide variety of traps can be associated with salt plugs. where the beds are draped over the eroded stumps of an old Jurassic volcano. is in one such trap. the beds being draped over an upfaulted block (horst) of basement rocks. much of the west coast and continental shelf of Africa. however. it may extend up to the surface of the ground or only part way if the supply of salt is limited. does not like empty holes. and finally a residual bulge may be left between two nearby plugs: a turtle or turtle-back structure. Extensive salt deposits and plugs with associated traps occur in many parts of the world: the southern North Sea and northern Germany. This compaction enhances the anticline formed by the drape. it is not always easy to separate out the two effects. Another is the Forties field in the North Sea. In case anyone should think that this is unimportant. Diagrammatic section through two salt plugs. Note that the anticline dies out upwards towards the surface. Ghawar in Saudi Arabia. All of these possible traps may contain hydrocarbons. which contains more than four times as much oil as the whole of the North Sea put together. Nature. showing the variety of traps that may be associated with them. the Canadian Arctic Islands. bending downwards into the hole. the Gulf Coast of the USA. note that the largest oilfield in the world. the Middle East. if the first sediments in a basin were deposited over a hilly surface. This occurs alongside a normal fault that is curved. and the beds on the downthrown side above the curving fault collapse to fill the gap. Note a characteristic of these anticlines: not only do they `grow' with depth. can be a perfect seal to any underlying accumulations. In effect the downthrown side is being pulled away from the upthrown side which would tend to create an open fissure along the fault. but also .(2-25) Similarly. 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. and then to burst through them in the form of a salt plug or salt wall. a salt pillow or a salt dome. higher beds will gradually mute and suppress the structure until it is no longer present at shallow levels. Not only may an anticline be pushed up over the plug. so that it is steep near the surface and flattens with depth. being plastic. The last type of anticline that we should be aware of is the roll-over anticline. The effect of salt diapirism will be initially to bulge up the overlying sediments as an anticline. and several others.

Middle Jurassic. and how big it is. or have acted in the past. (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. Cross-section through the Wytch Farm oilfield. trapped against faults to the south. All very puzzling! Although attempts have been made to investigate the problem in Nigeria and elsewhere. Lower Jurassic. Upper Cretaceous. Fault traps We indicated above that a trap may be formed where a dipping reservoir is cut off up-dip by a fault. the position of the crest is displaced with depth and that accumulations in successive reservoirs will not underlie the same surface position. It also depends on whether the fault itself is sealing or non-sealing. but we also know that sometimes faults are pathways for migrating petroleum and non-sealing at all. at deeper levels the crest will shift away from the position of the fault at surface.. will depend on the dip of the reservoir as compared with that of the fault. although there are many problems in trying to locate them in the subsurface.40 they are asymmetrical. UK. Tertiary. and naturally we have some ideas on the subject. Whether or not there is a trap. . these predated the deposition of the Upper Cretaceous. The proviso is that we also have lateral closure: this may be provided by further faulting. Occasionally indeed. or by opposing dips. The oil is in two reservoirs. Much of the oil under the Niger and Mississippi Deltas is in such roll-over anticlines. Tr. it seems that one and the same fault may act. in both ways. in both cases. W. to locate an exploration well in the right place. and its depth.Petroleum Traps . thus causing sand against sand to permit migration and sand against shale to be sealing. whether or not the reservoir is completely or only partially offset. BS+MJ+O. down towards the deep ocean. L. Upper Jurassic. Triassic. (2-28) We do not propose to discuss fault traps in detail. The sealing capacity of faults is a major difficulty confronting us. setting it against something impermeable. therefore. as at Wytch Farm. (B) a roll-over complicated by subsidiary faulting near the crest. Roll-over anticlines: (A) a simple roll-over into a normal fault. The large Wytch Farm oilfield of southern England offers a splendid example. 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. Again. T. and in understanding them. It adds further uncertainties to our predictions of the subsurface occurrence of oil and gas. we still do not fully understand what the difference is due to. Note that. whether the fault is normal or reverse. and it will depend on the amount of displacement on the fault. we have to know whereabouts in the succession our prospective reservoir lies. We know that sometimes. southern England. Lower Cretaceous. a fault can provide a seal. or slumping as a sort of land-slide. Kim+P.

and on the amount of displacement of the reservoir. The variety in size and shape of such traps is enormous.Petroleum Traps . until perhaps the supply of sand runs out. thus preventing further migration. to a large extent reflecting the restricted environments in which the reservoir rocks were deposited. We mention just three examples. In this manner. A sand deposited in a river channel will be confined by the banks and. We would be left with a sandstone reservoir dying out above the unconformity. A flood of sand washed off the shallow continental shelf into the deeper ocean. First. and leave the reader to speculate on other possibilities. the porosity could be preserved beneath the unconformity. gneisses) under an unconformity serve as reservoirs in China and North Africa. will spread out as a fan over the ocean floor. A lot of oil has been found in recent years in this sort of trap in the North Sea. strongly weathered basement rock (granites. let us note that a number of traps. however. It is presumed that petroleum cannot escape up the fault plane. Non-unconformity traps are even more diverse. A coral reef overwhelmed by muds. to provide a trap when later covered with.(2-29) STRATIGRAPHIC TRAPS Petroleum may be trapped where the reservoir itself is cut off up-dip. It would be pointless to list all of the possible types of stratigraphic trap that can exist. cut across by erosion and later covered above the unconformity by impermeable sediments. possibly through a submarine canyon. a hill on the old land surface may be formed of permeable rock. its edges will provide an example of a reservoir dying out laterally. for example. they differ somewhat in principle from the others. may serve as an isolated stratigraphic trap. More esoterically. some of them very important. if drowned by shales. the beach sands will spread progressively over the land surface. are formed by unconformities. say. becoming younger as time goes on. but are generally classified as stratigraphic traps. A dipping reservoir. is the biggest in the USA outside Alaska. fan sands provide one of the prime present-day exploration . claystone. provides the classic case: the East Texas field. but nevertheless known. if terminated updip as not infrequently happens. Consider the sea gradually encroaching over the land as sea level rises. Unconformity traps can also be found above the break.41 Six trapping and two non-trapping configurations against a fault. we have an isolated trapping situation. no structural control is needed. on the direction of dip of the beds relative to the fault plane. so we will mention a few to convey the general idea. In fact. depending on whether the fault is normal or reverse.

(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. some of them large. The reservoir beds were folded into an anticline. or the oil would have been lost. The oil in these fields can only have migrated there after the traps were sealed by the higher sequences. possibly even before it . and where an oil-water contact is continuous across a fault. which were eroded and unconformably overlain by Cretaceous shales. as the fault moved.42 targets. neither completely controls the trap. Again the range of possibilities is almost infinite. An investigation into the sealing qualities of faults affecting roll-over anticlines in the Niger Delta. where the reservoirs overlie overpressured shales. where there is enough of it in the section. there always seems to be something new as a challenge.). the biggest field in the USA. This combination trap is partly structural (the anticline) and partly stratigraphic (beneath the unconformity). these beds were folded into a faulted east-west anticline. As the more easily found structural traps are running out in much of the world. which was tilted west and eroded before deposition of the overlying beds now dipping east. elsewhere it appears to form a trap. The difference is believed to be due to clay being smeared into the fault plane. has most of its oil and gas trapped in a Carboniferous to Jurassic sequence which includes more than one reservoir. A couple of examples may give the idea. occur in traps formed by a combination of structural and stratigraphic circumstances. A block representation of the trap at the Prudhoe Bay field in northern Alaska. and truncated by erosion. that the trap must be shown to have been there before the oil migrated. although such prospects are not easy to locate and may require a lot of sophisticated seismic. Where a reservoir is full to spillpoint against a fault.Petroleum Traps . Both the faulting and the unconformity control the traps.(230) COMBINATION TRAPS A number of fields. it is presumed that the fault is non-sealing. We may note here one most important consideration. tilted westwards. The Prudhoe Bay field in northern Alaska. This vital factor. The oil is held in the reservoirs by younger shales overlying the erosion surface (Fig.

A hydrodynamic trap. of course. This is what has been described as a hydrodynamic trap. attempting to escape to surface up a reservoir. In this sort of situation. is that in most parts of the world the larger anticlines have now been drilled.(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. geologically speaking. Such tilted contacts. essentially anticlinal. The timing of trap formation versus oil migration has not always worked out favorably. as we do not want to waste the money drilling wells that would miss the oil altogether.43 was generated. perhaps from rain. only for as long as the water keeps coming: dry up the supply of water. This may be one of the reasons why oil accumulations trapped hydrodynamically are rare. a regime of water flow cannot normally be expected to remain constant for long. Depending on the balance of forces acting on the oil. Oil. . but the oil reserves they contain show clearly that generally they are also bigger. The trouble. It is totally dependent on the flow of water and is effective. they are known in a number of parts of the world. and the oil will be free to move again. entering a reservoir formation. The number of structural field of this size may partly reflect the fact that structural traps are easier to find than the others. up in the hills and percolating downwards towards a spring. The oil-water contact in such a hydrodynamic trap is normally tilted in the direction of water flow. Oil has found its way into the reservoir and is battling to migrate upwards to the surface against the flow of water. Furthermore. 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. are the more obscure and generally smaller prospects. are not all that rare. indicating the former presence of an oil accumulation now lost. There is no structural or stratigraphic closure. or aquifer. it may find itself caught against an unevenness of the reservoir surface where there is no conventional trap at all.Petroleum Traps . We would recognize this from residual traces of oil in a water-bearing reservoir. in say ordinary anticlinal traps. It is therefore always important to get a handle on the hydrodynamic regime in a reservoir for both exploration and oilfield development purposes. is yet another aspect of the petroleum geology that we have to assess in proposing exploration drilling. Note that the oil-water contact is tilted down in the direction of water flow. we would have to be careful where we locate and drill our oil production wells. is held against an unevenness of its upper surface by water flowing in the opposite direction. traps in both number and size. therefore. What our efforts are increasingly directed towards. HYDRODYNAMIC TRAPS Imagine surface water.

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. multi-interpretable (D). The logs show SP (Self Potential or Spontaneous Potential) on the left and R (Resistivity) on the right.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. Interpret the geological relationships shown in each by drawing a structural cross-section through the logs.

Elevations and marked logs are provided for 6 wells in the Wyckoff Field.46 EXERCISE PetroleumTraps 2 The Wyckoff Gas Field.. Use this information to construct a northeastsouthwest structural cross section from the Richards well to the Dibble well. N. The Onondaga forms a thick biohermal reef over part of the field. Oriskany production is from a small anticline on the upthrown side of the fault. Wyckoff Reef Gas Field WellElevation CORNELL DIBBLE GUILD CHASE BANKS RICHARDS 2257' 2098' 2037' 2206' 2182' 2066' . located in Steuben County.Petroleum Traps . 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.Y. Only the porous core facies is productive in the reef section (see map on next page).

Petroleum Traps .47 .

48 .Petroleum Traps .

For example.Source-Rock Evaluation DEFINITION OF SOURCE ROCK Much of modern petroleum geochemistry depends upon accurate assessment of the hydrocarbonsource capabilities of sedimentary rocks.Source Rock Evaluation . This simple. Although the term source rock is frequently used generically to describe fine-grained sedimentary rocks. is most meaningful if we can compare it to the rock's original source capacity. but if the rocks contain abundant organic matter. a potential source rock in a less-mature area. a possible source rock in a nearby unstudied region. 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 difference between Go and G represents the hydrocarbons already generated in the effective source rock. it is also necessary to know what level of thermal maturity is represented by that particular G value. if G is very low. instead it must be estimated by measuring G for a similar sample that is still immature. the Phosphoria Formation of Wyoming and Idaho belongs to each of these classifications in different areas. It follows from these definitions that a particular stratum could be an effective source rock in one place. Go can only be measured directly for immature source rocks. Analysis normally requires about one gram of rock. we actually measure its remaining (or untapped) source capacity at the present day. where G and Go are identical. Go.. overmature. the following distinctions can be made: Effective source rock: any sedimentary rock that has already generated and expelled hydrocarbons. When we analyze a rock sample in the laboratory. much smaller amounts can be analyzed. and inexpensive analysis serves as the first and most important screening technique in source-rock analysis. MATURITY OF ORGANIC MATERIAL Knowing a rock's remaining source capacity G solves only one part of the puzzle. or is it because the rock is "burned out" (i. This quantity. quick. 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.49 8 . However. The term "effective source rock" obviously encompasses a wide range of generative histories from earliest maturity to overmaturity. we cannot measure G directly for a sample that has already begun to generate hydrocarbons. is it because the rock never had a high initial source capacity. For better communication. that usage is a bit too broad and loose. The quantity actually measured in the laboratory is always G. but which may have generated and expelled hydrocarbons. in which case virtually all the initial . which we can call G. 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.e. Possible source rock: any sedimentary rock whose source potential has not yet been evaluated. For example. the remaining source capacity and not the original capacity (Go).

The key to using maturity parameters effectively lies in evaluating the measured data carefully (and sometimes with skepticism) and. If a log scale is used for the reflectance. In many rocks vitrinite is rare or absent. its maturity is not related to that of the rock in which it is found. . TAI measurements are made on the same slides prepared for microscopic kerogen-type analysis. far more common in shales than in coals. and pyrolysis temperature. and then embedding the kerogen particles in an epoxy plug. A few of these parameters will briefly be discussed. The most commonly used maturity parameters today are spore color (Thermal Alteration Index. vitrinite reflectance. Vitrinite-reflectance techniques were developed for measuring the rank of coals. The feeling of most workers today is that there is no single maturity indicator that tells the whole story unerringly all the rime. TAI values are estimated. the plot is a straight line. TAI measurements are carried out on bisaccate pollen grains whenever possible. Such histograms are quite often difficult or impossible to interpret. If enough vitrinite particles can be found. If no pollen can be found. A substantial number of techniques for measuring or estimating kerogen maturity have been developed over the years. All the methods have strengths and weaknesses. of course. The darkening of kerogen particles with increasing thermal maturity can be used as an indicator of maturity. with lower confidence. between 50 and 100 measurements will be taken. Because what is present is often reworked. in fact. After the plug is polished. Results are reported as Ro values. in which the vitrinite maceral is usually very common. Despite its weaknesses. the reflectance value of vitrinite increases. whenever possible. misidentification of macerals can cause problems. The fraction of the incident beam that is reflected coherently is measured and recorded and stored automatically on a computer. Reworked vitrinite is. from amorphous kerogen. Less commonly used are fluorescence and conodont color (CAI). leading to frequent difficulties in establishing which vitrinite population is indigenous. vitrinite reflectance is the most popular technique today for estimating kerogen maturity. where the o indicates that the measurements were made with the plug immersed in oil. in some cases it is essential. and none can be applied in all cases. however. In all cases it is worthwhile to supplement vitrinite with other measures of maturity.50 hydrocarbon-source capacity has already been used up)? The exploration implications of these two scenarios are. Because each maceral type increases in reflectance in a slightly different way as thermal stress increases. in obtaining more than one maturity parameter. Other macerals or solidified bitumens can often be misidentified as vitrinite. the microscopist shines light on an individual vitrinite particle. In many areas it is easy to use and valuable. The ideal histogram of reflectance values is therefore rather rare. All the techniques discussed are useful and probably reasonably accurate if the analytical work is carefully done. unless surrounding samples help us determine the indigenous vitrinite population. 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. In other rocks. Vitrinite-reflectance measurements begin by isolating the kerogen with HCl and HF. along with a statistical analysis of the data. paucity of first-cycle vitrinite renders vitrinite-reflectance measurements essentially worthless. In order to minimize differences in color caused by changes in the type or thickness of the kerogen particles. At the end of the analysis a histogram of the collected data is printed. Vitrinite reflectance (Ro). There are many problems with vitrinite reflectance as applied to kerogens. Reflectance values are normally plotted versus depth in a well. very different.Source Rock Evaluation . even for experienced workers. The method is based on the fact that with increasing thermal stress. or TAI). Thermal Alteration Index (TAI).

Conodonts are isolated. by removing the mineral matrix with acetic or formic acid. because the organic metamorphism displayed by conodonts is not related to hydrocarbon generation or destruction. TAI values must be estimated from amorphous debris. Finally. Furthermore. The first maturity indicator applied to sediments was the Carbon Preference Index. One disadvantage of CAI measurements is that CAI values can be dramatically increased in the presence of hot brines. Other disadvantages overlap with some of the advantages. Although TAI determinations are subjective. Although conodonts are composed of carbonate apatite. Thirdly.Source Rock Evaluation . leading to an inaccurate assessment of kerogen maturity. thus defusing to a large degree the criticism that TAI is too subjective to be valid. changes in conodont color are apparently due to carbonization of inclusions of small amounts of organic matter during catagenesis and metagenesis. they offer a means of measuring maturity in rocks that do not contain pollen grains or vitrinite. the absence of spores and pollen in the samples. One advantage of CAI over other maturity parameters is that because conodonts existed as early as the Cambrian. conodonts are plentiful in carbonate rocks. TAI measurements are therefore often quite accurate and correlate very well with results from other techniques. where pollen and vitrinite are often absent. most commonly from fossiliferous carbonates. which can vary greatly in its chemical and physical properties. or most commonly. When palynomorphs are absent. Conodonts are not very sensitive indicators of maturity within the oil generation window. the CAI scale is most sensitive at levels of maturity much higher than can be measured by TAI. where most of the interest is. Finally. and thus are of no value in many areas. A careful worker can reproduce earlier work with excellent precision. Carbon Preference Index (CPI).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. CAI is inexpensive and easy to measure and. and thus helps expand the range over which maturities can be measured. The chief problems arise with inexperienced workers. lack of proper standardization. Conodont Alteration Index (CAI). Early investigations showed that immature rocks often had high CPI . CAI is only an indirect indicator of hydrocarbon maturity. with the help of color charts can be carried out by inexperienced personnel. The technique is simple and quick and can be done even by inexperienced workers. TAI values estimated from amorphous material are always suspect and should be corroborated by other analyses. use of careful standards and the same type of palynomorph in each analysis greatly aid reproducibility. Colors of the specimens thus obtained are determined under a binocular microscope and compared with standards. Conodonts do not occur in rocks younger than the Triassic.

only microscopic analysis is relatively unaffected by maturity. which affect only the kerogen portion of the sample. they can usually be identified with reasonable confidence. palynological analysis can usually detect the presence of lignosulfonates because of the unique pollen assemblages present in the lignite. Caving is not a problem for conventional or sidewall cores. In such cases TOC values will be raised and reflectance histograms will show a large population near 0. atomic H/C ratios measure the present day status of the kerogen rather than its original chemical composition. Walnut hulls and other organic debris are also easy to detect microscopically. however. but it can be devastating in cuttings samples. whereas those of oils were almost always below 1. Careful picking of lithologies and comparison with up-hole samples can often recognize caved materials. This method works fairly well if the kerogen is still within the oil-generation window.52 values (> 1. it is impossible to determine which maturation path brought it to that point. Caving is a particular problem for coals. Mold or other surface growth may also be present. and can be removed prior to beginning the analytical sequence. In many cases. 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. As a result. This discovery led to the use of CPI as an indicator of maturity. in which the input of terrestrial lipids was very limited.2. As long as kerogen particles are not completely black. fewer CPI determinations are made now. walnut hulls and other solid debris. and lignite from lignosulfonates. TOC values will be raised and vitrinite-reflectance values lowered by the presence of adsorbed diesel. Without additional information. it can lead to an overly optimistic assessment of the organic richness of the section. Pyrolysis yields are. Atomic H/C ratios must therefore be corrected for the effects of . In particular. Well Samples . Fortunately. because all kerogens have low pyrolysis yields. in the last decade kerogen analyses have replaced bitumen analyses as the routine procedure in source-rock evaluation.Source Rock Evaluation . rocks deposited in pelagic environments. diesel fuel affects both kerogen and bitumen. and therefore should be easy to avoid. Like pyrolysis. have low CPI values even when immature. It is capable of impregnating sidewall and conventional cores as well as cuttings. Problems with living organic matter are easily avoided by physically removing tiny plant roots and other recognizable debris. of course. where the fluorescence that enables us to distinguish between oil-prone and non-oil-prone disappears toward the end of the oil-generation window. Contaminants of particular notoriety are diesel fuel. Drilling-fluid additives have been a severe headache for petroleum geochemists for a long time. however. of course. It breaks down at high maturity levels. Furthermore. 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. therefore.5%. 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. The exception to this rule is with amorphous material.5). vitrinite reflectance measurements offer the best means of recognizing caving.The main causes of contamination among samples obtained from wells are caving and adulteration by drilling-fluid additives. ESTIMATION OF ORIGINAL SOURCE CAPACITY Of the three major methods of determining kerogen type. In contrast to solid additives. Hydrocarbon contamination is rare except in the immediate vicinity of production or where vehicles are used. strongly affected by maturity. because of their friability.

Thus high TOC values are a necessary but not sufficient criterion for good source rocks. the direct evidence for such a statement is rather meager. S2. where preservation of lipid-rich organic matter with source potential for oil can occur. Gas-generative kerogen is mainly vitrinite. which ones might be of slight interest (TOC between 0.0%). 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.53 maturation by using a van Krevelen diagram. Pyrolysis results are normally reported in two ways. In some rocks TOC values between 1% and 2% are associated with depositional environments intermediate between oxidizing and reducing. the kerogen in such lean rocks is almost always highly oxidized and thus of low source potential.5% TOC. A rock containing 3% TOC is likely to have much more than six times as much source capacity as a rock containing 0. We therefore use TOC values as screens to indicate which rocks are of no interest to us (TOC < 0.5% and 1. Those rocks containing less than 0.5% and 1. Inertinite is considered by most workers to have no hydrocarbon-source capacity. however. exinite. on the basis of deductive reasoning. In interpreting these observations we normally divide these macerals into oil-generative. has dissented from this pessimistic view.5% TOC are considered to have negligible hydrocarbon-source potential. however. claiming. have little oil-source potential. Smyth (1983). These immature H/C ratios can then be used to calculate Go. and S3) are expressed in milligrams of hydrocarbon or carbon dioxide per gram of rock sample. Many rocks with high TOC values. and inert. etc. They will not function as highly effective source rocks. that at least some Australian inertinites can generate significant amounts of oil. Nevertheless.0% TOC are marginal. Interpretation of TOC values therefore does not simply focus on the quantity of organic matter present. Kerogens in rocks containing less than 1% TOC are generally oxidized. TYPE OF ORGANIC MATTER Microscopic kerogen-type analysis describes the proportions of the various macerals present in a sample. because the kerogens they contain are woody or highly oxidized. The amount of hydrocarbons generated in such rocks is so small that expulsion simply cannot occur. fluorescing amorphous kerogen. Rocks containing more than 1% TOC often have substantial source potential. These raw data are then normalized for the organic-carbon content of the sample. Raw data (S1. Furthermore. The oil-generative macerals are those of Type I and Type II kerogens: alginite. resinite. but they may expel small quantities of hydrocarbons and thus should not be discounted completely. yielding . and thus of limited source potential. and which are definitely worthy of further consideration (TOC > 1.0%). because the type of kerogen preserved in rich rocks is often more oil-prone than in lean rocks. We must still determine whether the kerogen present is in fact of good hydrocarbon-source quality. As such these quantities are a measure of the total capacity of a rock to release or generate hydrocarbons or carbon dioxide.Source Rock Evaluation . TOC values above 2% often indicate highly reducing environments with excellent source potential.5%). gas-generative. the actual volume percent occupied by the organic material is about twice the TOC percentage. Rocks containing between 0. Because the density of organic matter is about one-half that of clays and carbonates. cutinite.

Interpretation of hydrogen indices for immature kerogens is straightforward. and the end of liquid-hydrocarbon generation is thought to be at about 1. A second. They have excellent potential to generate liquid hydrocarbons. this generalization has two fallacies: most of the coalfields originally studied were of Paleozoic age. However. MATURITY Kerogen Parameters. Those between 150 and 300 contain more Type III kerogen than Type II and therefore have marginal to fair potential for liquids. Nevertheless. because they vary with kerogen type as well as maturity. CAI can actually measure high-grade metamorphism. because during the Paleozoic the biota was quite different than during the Cenozoic.6% Ro. Peak generation is reached near 0. make sure that you have a copy of their equivalency between TAI and Ro. The limits of the oil generation window vary considerably depending upon the type of organic matter being transformed. some Cenozoic coals should have better potential for generating liquid hydrocarbons. Measured hydrogen indices must be corrected for maturity effects by using a modified van Krevelen diagram as outlined above.Source Rock Evaluation .9% Ro. Thus. 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.5% Ro. It is particularly difficult to generalize about TAI values because the numerical values of TAI scales have not been standardized among laboratories. The correlations among maturity parameters have been fairly well established. Because vitrinite reflectance is the most popular method of determining maturity. The ultimate limit of oil stability is not known for certain. but there are still some minor variations from one laboratory to another. Some laboratories put the onset of maturity at 435° C. Kerogens with hydrogen indices above about 300 contain substantial amounts of Type II macerals.35% Ro. and the coals were of bituminous to anthracite rank.54 values in milligrams per gram of TOC. either from terrestrial macerals (cutinite. a unified scale for comparing them with Ro values has not been adopted. . most other maturation parameters are related to Ro values. Because some Cenozoic land plants are richer in resins and waxes than Paleozoic plants. Kerogens with hydrogen indices above 600 usually consist of nearly pure Type I or Type II kerogens. respectively. Age of coals is important. and thus are considered to have good source potential for liquid hydrocarbons. but in most cases is probably not much above 1. if you are using TAI determinations determined by an analytical laboratory. Hydrogen indices above 150 reflect increasing amounts of lipid-rich material. 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. resinite. Although Tmax values are determined objectively. less common application is to decide whether oil will be stable in a given reservoir. exinite) or from marine algal material. others use 440°. with CAI of 8 reached in a marble. Because variations in TOC have been removed in the normalizing calculation. for most kerogens the onset of oil-generation is taken to be near 0. Determination of the oil-generation window in a particular section is the objective of most maturity analyses performed on possible source rocks. Conodont Alteration Index (CAI) values ranging from 1 to 5 were tied loosely to vitrinite reflectance and fixed carbon content of coals. 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.

0 Pyrolysis Tmax (°C) 420 430 440 450 460 465 470 480 500 500 + 500 + Conodont Alteration Index (CAI) 1 1 1 1. and organic facies. and maturity of the organic matter present in the rocks? Satisfactory methods are available in most cases to answer all these questions.4 3. type.0 3.60 0. Interpretation of source-rock data on a basic level is quite simple.2 3.20 1.6 2.0 4.8 4.00 3.8 3.50 2. We should always attempt to extrapolate our measured data over as large an area as possible.00 Thermal Alteration Index (TAI) 2. therefore.3 2. unconformities and erosional events. we should attempt to corroborate the measured data by other analyses. we should not rely on a single analytical technique.50 0.40 0. With increasing experience one can also learn to derive important information on thermal histories.0 2. In some areas one technique may fail completely or may be only partially successful.00 4.Source Rock Evaluation .5 2 2 2 3 4 4 5 Correlation of various kerogen-maturity parameters with vitrinite-reflectance (Ro) values .00 1. rather. Vitrinite Reflectance (%Ro) 0.80 1.55 SUMMARY Any source-rock evaluation should attempt to answer three questions: What are the quantity. To do this intelligently we must have the ability to develop regional models of organic facies and thermal maturity.5 3.35 1. Whenever possible.

2 3.41 0.6 2.66 0.5 2-2.7 2.81 1.77 0.33 1.2 Atomic H/C 1.5 2.2 2.8 0.98 0.07 1. however. so "Total Oil" can be plotted against "Oil Already Generated.75 0.7 1.6 0.5 2-2.8 % Alginite + Exinite 75 80 80 75 80 90 85 75 70 50 45 60 45 40 ? ? Core Cuttings Data are available on quantity (%Corg). one must first convert the measured.22 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 0.6 2.6 2. To use the H /C data. A) Calculation of the immature kerogen H/C ratio(at A) from the present-day H/C ratio and vitrinite reflectance data(at P) .15 0.86 0. as shown in Figure B (derived from Figure A).65 0." Two independent quality measurements have been made.5 2. and both should be utilized and examined for possible discrepancies.5 0." To do this.1 3.9 3.3 0.0 3.Source Rock Evaluation .5 2.5 1.38 TAI 2.7 2.5 0. The calculated immature H/C ratios are listed in the table on next page.27 1.0 0.1 2. This can be done easily by plotting H/C versus TAI.2 1.0 2-2. and maturity (TAI).05 0. B) H/C versus TAI for Mauve Well samples.7 1.5 1.7 3. quality (H /C and %Alginite + Exinite).3 1. presenting the kerogen quality factor as a . refer to the graph on next page. present-day H/C ratios to the ones that the kerogens had when they were thermally immature. and then tracing the H/C ratio back to its immature value.72 0.56 EXERCISES Worked out example: Perform a source-rock analysis on the Mauve Well. Both the immature H / C ratios and the maceral analysis data need to be scaled to calculate "Total Oil.

The most important point being made here is that these discrepanties must be taken seriously by the interpreter.65 0.35 1. the interpreter might then decide to try a third technique.38 Immature H/C 1.05 0.8 1.22 1.77 0.70 1.30 1.22 1.5 1.72 0. Without more knowledge.15 0.7 1.57 function of H/C ratio of the immature kerogen in order to determine the quality factor from H/C.6 1.20 1. 2300. If these attempts produced no resolution of the problem.81 1.90 0.90 0.98 0.17 0.07 1.05 0.2 0.5 1.9 0. The scaled quality factors are given for each parameter in the table on next page.77 0.07 1.90 0.60 0. to check for analytical error. however.75 0.85 1. In likewise manner (not illustrated here) the quality factor can be determined from maceral analysis data. it is impossible to pinpoint the error. 4000.6 1.5 1.0 0.35 0.60 ? ? * * * * * 1. Kerogen quality factor as a function of H/C ratio of the immature kerogen.8 ? ? * * * Indicates discrepancy between quality factors calculated from H /C and from maceral analysis. The prudent interpreter might now ask that some of the H/C ratios be rerun. and 4500 meters all show differences in the quality factors calculated from the two types of data. the H/C ratio gives the lower quality factor.05 1. and not .6 1.65 0.00 0.90 0. 1500.41 0.05 0.33 1. 1750.05 1.50 1.86 0.35 0. The samples at 1000. so some systematic error is likely.66 0.81 1.9 1.27 1.Source Rock Evaluation .4 1. 2000.43 1.60 0. and would certainly request that the slides made for maceral analysis be reviewed. It is apparent that there are serious discrepanties between the H/C and maceral analysis results for several of the samples. In each case.90 ? ? Quality Factor Quality Factor (from H/ C) (from 1. 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. such as pyrolysis.

In fact. Most of the discrepanties among the different quality factors turn out to be unimportant. It may be necessary occasionally to offer two alternative interpretations without choosing between them. These two kerogens are highly mature and quite black. although the section between 2000 and 3500 meters shows fairly good potential. about the oil-source history of the section below 4600 meters. More samples between 3000 and 3500 meters should be obtained to define better the zone of high "Total Oil" values. because sourcerock potential is not good for most of the section. Let us take this last approach to this problem. Finally. "Total Oil" and "Oil Already Generated" profiles are plotted in above figure. "Total Oil" and "Oil Already Generated" profiles tor the Mauve Well. therefore.Source Rock Evaluation . "Total Oil" values are generally unexciting. . 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. The rest of the section shows a good correspondente between the two parameters. The only sample where the discrepancy is significant is that from 2000 meters. Future exploratory activity could include an attempt to find such a section. except for the two deepest samples. and the H/C ratios are not helpful because the maceral types cannot be ascertained from such low H/C values. "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.58 be overlooked or swept under the rug. One can say little. The relative organic richness of the blackened samples below 4600 meters makes them interesting for further investigation. no maceral analysis was possible here.

05 0.5 3.17 0.46 0.0 2.90 0.0-2.5-3 3.66 0.5 3.11 0.91 1.6 2.00 1.01 0.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10 2-2.5 2.25 1.06 0.99 1.5-3 2.5 2.5 2.0 0.63 0.3 Bit/TOC 0.17 0.1 2.61 0.51 0.26? 1. 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 0.49 0.5 2.51 0.5-3 2.05 0.4 0.5 2.55 0.0-2.7 0.3 2.21 0.0 2.60 0.59 0.33? 1.5-3.08 0. Explain how you resolved any apparent discrepancies.59 0.5 2.86 1.1 0.8 0.27 0.5 2.5-3 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 2.08 0.18 0.88 0.52 0.08 0.07 1.5 2. EXERCISE Source Rock 2 Perform a source-rock evaluation of the section penetrated in the Turquoise Well.0-2.5 2.6 0.03 0.0 2.5 0.51 0.6 4.12 *TAI and Ro are interconverted according to the correlation table at the end of chapter 7.44 0.5-3 2.41? 1.8 1.09 0.02 Atomic H/C 0.02 0.5 2.3 1.08 0.2 2.3 2.5 3-3.21 1.67 0.91 1.27 1.5-3 2.65 0.09 0.60 0.42 0.21 1.03 0.2 0.07 0.22 0.10 0.Source Rock Evaluation .07 0.9 1.0 2.0 2.48 Ro 0.49 0.06 0.59 EXERCISE Source Rock 1 Combine the data from the Blue Well to give a coherent picture of thermal maturity in the section drilled.0 3-3.000 Type of Sample Cuttings Cuttings TOC 1.7 0.85 0.91 0.5 TOC = Total Organic Carbon Bit/TOC = Bitumen/Total organic carbon ? indicates a poor histogram TAI = Thermal Alteration Index Ro = Vitrinite reflectance .0 2.66 0.5 2.02 0.3 2.60 0.71 0.03 0.06 0.65 0.

in frontier basins there may not be a single well within tens or hundreds of kilometers. 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. Part of this problem is a consequence of the limitations we face in attempting to obtain reliable maturity measurements. Even in maturely explored basins the samples available for analysis often do not give a representative picture of maturity in the basin.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. 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. It has even been suggested that maturity models are more accurate than measured data for determining the extent of petroleum generation. 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. Nevertheless. 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. This assumption is a logical and defensible one. a time stratigraphy can sometimes be constructed using seismic data. In 1971. maturity measurements can only tell us about present-day maturity levels. however. methods have been developed for calculating maturity levels where measurements are not available. He developed a "Time-Temperature Index" of maturity (TTI) to quantify his method. 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. These considerations are important when we want to compare timing of generation. 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. 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. In some areas there are no well samples available. measured maturity data are of limited value in exploration. nor do we know at what depth or temperature it occurred. however. for it is in keeping with the predictions of chemical-kinetic theory.60 9 . expulsion. we still have no clue as to when oil generation occurred.Predicting Thermal Maturity . In most cases. If no well data are available. estimates can be made. and migration with timing of structure development or trap formation. We need data that will enable us to construct a time stratigraphy for the location of interest and to specify its temperature history. . If our measurements indicate that a rock has already passed through the oil-generation window. 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. indeed. Furthermore. If no subsurface data are available. In order to circumvent these difficulties. especially if the seismic reflectors can be tied to well data.

Today the rock is at a depth of 3700 m. Nevertheless. it is easy to construct burial-history curves with a high level of confidence. Using the other control points from the input table. This geometry is a direct consequence of ignoring compaction effects. Burial-history curves are based on the best information available to the geologist. sediment has accumulated continuously but at varying rates since deposition of the oldest rock 100 million years ago (Ma). for example.Predicting Thermal Maturity . In cases where biostratigraphic data are lacking or where the sediments have had complex tectonic histories. we can construct the temperature grid with equally spaced isotherms parallel to the earth's surface.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. Using these present-day data and extrapolating them into the past. The burial-history curve was constructed in the following way: two points. by 80 Ma the sediment had been buried to a depth of 900 m (point C). a burial-history curve may represent only a rather uncertain guess. are marked on the age-depth plot. and that a corrected bottom-hole temperature of 133° C was obtained at 3800 m. which was constructed from the time stratigraphy for the Tiger well. 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. Connecting the six dots completes the burial-history curve. that the Tiger well was logged. Suppose further that local weather records indicate a yearly average surface temperature of 19° C. representing the initial deposition of the sediment (point A) and its position today (point B). TEMPERATURE HISTORY The next step is to provide a temperature history to accompany our burial-history curve. we can construct the complete figure. Neglecting compaction effects. burial-history curves represent our best understanding of the geological history of an area. In the Tiger well. In cases where biostratigraphic data are available and deposition has been reasonably continuous. 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. Suppose. The next step is to locate the first control point from the time-stratigraphic data on the input table. The subsurface temperature must be specified for every depth throughout the relevant geologic past. . An example is shown in the following figure.

temperature profiles will be based largely on guesswork. but the geothermal gradient varies in response to heating or cooling events. Causes for such events could include global warming and cooling or local climatic variations resulting from continental drift or elevation changes. Erosion is indicated in a burial-history curve by an upward movement of the curve. If. the data necessary for highly sophisticated temperature reconstructions are simply not available. In most cases. burial-history curves for both hanging wall and footwall can be represented on a single diagram. 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. we are limited only by our own creativity. the movement of hot rocks from the bottom of the overthrusted slab over cool rocks at the top of the underthrusted slab will affect . In many poorly explored areas. however.Predicting Thermal Maturity . the resultant thinning of the section must be represented in the entire family of burial-history curves. In other cases the surface temperature remains constant. If deposition resumes later. we can change surface temperatures through time without altering the geothermal gradient.62 Where measured bottom-hole temperatures are not available. maps of regional geothermal gradients can be useful in estimating the gradient at a particular location. SPECIAL CONSIDERATIONS ABOUT BURIAL-HISTORY CURVES The most common complicating factor in constructing burial-history curves is erosional removal. The individual segments of each of the burial-history curves in a family will remain parallel. More complicated temperature histories account for changes in thermal conductivities caused by variations in lithology. however. If part of the section is missing as a result of faulting. There is no theoretical limit to the complexity that can be introduced into our temperature histories. Whenever erosional removal occurs. Given adequate data or an appropriate model on which to base complex temperature reconstructions. some part of the section is repeated as a result of thrusting. For example (9-7). The effects of thrusting on thermal maturity are not well understood. There are numerous other variations that can be employed in creating temperature grids. Faulting can be dealt with by considering the hanging wall and footwall as separate units having distinct burial histories. two separate diagrams should be used for the sake of clarity. If thrusting is rapid compared to the rate of thermal equilibration between thrust sheets. the burial-history curve again begins to trend downward.

Loss of 1000 m of section by erosion during an uplift event lasting from 70 Ma to 60 Ma. A Time interval is the length of time that the rock has spent in a particular temperature interval. 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. Lopatin chose the 100°-110° C interval as his base and assigned to it an index value n = 0. Testing of his model and the successful application of Lopatin's method in numerous published examples have confirmed the general validity of this assumption. spent by the rock in each temperature interval. These dots define the time and temperature intervals that we shall use in our calculations. The temperature factor. Total maturity is calculated by summing the incremental maturity added in each succeeding temperature interval.63 organic maturation by causing important perturbations in subsurface temperatures. Temperature intervals are defined by successive isotherms spaced 10° C apart. Intersections of the burial-history curve with each isotherm are marked with dots. in contrast. but the distance between the two lines which bracket the erosion.Predicting Thermal Maturity . In order to carry out maturity calculations conveniently.400 cal/mol will approximately double with every 10° C increase in reaction temperature. more work is required before we will understand fully how thrusting influences hydrocarbon generation and destruction.(9-12) CALCULATION OF MATURITY Once the burial-history curves and temperature grids have been constructed. Now we can carry out the maturity calculations. Individual burial-history curves remain parallel. However. we must paste them together. Because the rate of maturation was assumed to increase by a factor of two for every 10° C rise in temperature. expressed in millions of years. Lopatin defined each time factor simply as the length of time. decreases by 1000 m. This intervalTTI value represents the maturity acquired by the rock in that temperature interval during the time . Studies in the Overthrust Belt of Wyoming indicate that a slow-equilibration model is superior to a simple model invoking rapid thermal equilibration. for any temperature interval the temperature factor (?) was given by: ? = 2n The temperature-factor thus reflects the exponential dependence of maturity on temperature. we need to define both a time factor and a temperature factor for each temperature interval. increases exponentially with increasing temperature. respectively. Lopatin (1971) assumed that the rate of maturation followed this doubling rule. Index values increase or decrease regularly at higher or lower temperatures intervals. 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).

we simply sum all the interval-TTI values for the rock. no matter how much or how rapidly we cool it down. if we forget about the cake when the oven is hot and let it burn. even if a rock cools down. as the oven cools down. maturity continues to increase (albeit at a slower rate) because y is always greater than zero. In the adjoining table interval-TTI values and total-TTI values up to the present day are calculated. but quite rapid in the last 10 my. Figure C shows rapid burial during the first 20 Ma. although at increasingly slower rates. by 10 Ma of uplift and erosion. the specific burial history of a rock can strongly affect its maturity. On the other hand. A good analogy can be drawn between oil generation and baking. FACTORS AFFECTING THERMAL MATURITY Because maturity is affected by both baking time and baking temperature. we cannot "unburn" it. TTI values differ appreciably among these four scenarios. The first step in calculating TTI is illustrated in the following figure. followed by a nonerosional depositional hiatus for the last 50 Ma. 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). To obtain total maturity. If we turn off the oven but leave the cake inside. If we put a cake in a cold oven and turn the oven on. In D 40 Ma of rapid burial to a depth of 4000 m was followed by a hiatus lasting 30 Ma and.(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.64 given. finally. In A the rock was buried at a constant rate for its entire 80-my history. Furthermore. where the time factors and yfactors for each temperature interval are shown on the burial-history curve. In B burial was very slow during the first 70 Ma of the rock's existence. the cake will bake slowly at first but will bake faster and faster as the temperature rises. Maturity always increases.Predicting Thermal Maturity . it can never go backward because interval-TTI values are never negative. . baking will continue.

Present-day subsurface temperatures are difficult to measure accurately.(9-29) Furthermore. The model includes an extensive nonerosional depositional hiatus. time data are seldom a problem. Various methods have been developed for this purpose. Tfu = Fort Union Formation. . Most logged temperatures are too low and require correction. Kc = Cody-Frontier formations. showing the evolution of the oilgeneration window through time. Only in cases where micropaleontological dating was not or could not be carried out. the dependence of maturity on time is linear. Family of burial-history curves for a well in the Big Horn Basin. First. Secondly. Wyoming. Tu = undifferentiated Tertiary. our uncertainties about the true values of subsurface temperatures are much greater than about time. in contrast. 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. so even a rather large error in baking time will not produce a catastrophic change in maturity. is the single most important cause of uncertainty and error in maturity calculations. we usually have excellent control on rock ages through micropaleontology. might we anticipate possible problems with time. Age calls are often made within a million years. and can be even better in Cenozoic rocks. Km = Lance-Meeteetse formations. The sensitivity of maturity to temperature is clearly indicated by the exponential dependence of maturity on temperature predicted by the Arrhenius equation.65 A) Initial proposed burialhistory model for Well #1. B) Revised burial-history model for Well #1 based on the poor correlation with measured maturity data. Temperature. but there is no guarantee of their accuracy in any particular case.Predicting Thermal Maturity . In actuality.

88 0.4 0.1 2. Source-rock data tor the Turquoise Well Depth (ft) 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500 8000 8500 9000 9500 10. 3500 ft of Pliocene.6 4. however.66 Even if we could measure present-day subsurface temperatures with perfect accuracy.150 ft in the Middle Miocene. In other cases.18 0. even an inaccurate extrapolation into the past may not cause significant problems.8 0.33? 1.08 0.03 0.8 1.3 1.26? 1.5 3.5 3-3. Despite experimental evidence indicating that different kerogens decompose to yield hydrocarbons at different levels of maturity models. A question of some concern comes from the previously mentioned fact that most of the maturity models treat all types of kerogen identically.66 0.5 3.71 0. In many cases.08 0.5-3 2.00 1.03 0.02 0.7 0.5 2.06 0.5-3 2.5 2.91 1.06 0. where presentday temperatures are maximum paleotemperatures.99 1.22 0.21 1.27 1.000 Type of Sample Cuttings Cuttings TOC 1.65 0.49 0.Predicting Thermal Maturity .5 2. an accurate interpretation of the ancient geothermal history may be critical.51 0.67 0.7 0.02 Atomic H/C 0.07 1. do not utilize different kinetic parameters for the various kerogen types.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.91 1.59 0.5-3 2.21 1.1 0.2 0. particularly where Paleozoic rocks are involved.5-3 2. however.01 0.0 3-3.85 0.3 Bit/TOC 0.48 Ro 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. The corrected bottom-hole temperature was 270° F.000 ft of Upper Miocene before being abandoned at 16.08 0.25 1.5-3 3.05 0.86 1.60 0.90 0.5 2.27 0. Construct a family of burial-history curves for the well and calculate the present-day TTI at total depth.9 1.91 0.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10 2-2. A plausible average surface temperature is 20° C.3 2.5 0. we still would have to extrapolate the present somehow into the past.5-3.65 0.52 0. EXERCISES EXERCISE Thermal Maturity 1 Perform a source-rock evaluation of the section penetrated in the Turquoise Well.5-3 2.0 0. Base Pleistocene 2 Ma Base Pliocene 5 Base Upper Miocene 11 Base Middle Miocene 50 Ma .51 0. and 11.17 0.41? 1. It penetrated 1000 ft of Pleistocene sediments.

Total depth is reached at 6120 ft in Middle Jurassic rocks.Predicting Thermal Maturity .end Cretaceous: 15° C 141° C 25° C EXERCISE Thermal Maturity 4 The Ultraviolet Well is spudded in Paleocene sediments. 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. assuming a constant geothermal gradient through time. Evidence from related sections indicates that the Paleocene was originally about 3000 ft thick and that no other Cenozoic sediments were ever deposited. Find when the rock at 3000 m began to generate oil (TTI = 10).67 EXERCISE Thermal Maturity 3 Calculate present-day TTI at 3000 m in the Red Well. draw a burial-history curve for the section penetrated and calculate maturity for the Kimmeridgian shale. Age data top Paleocene base Paleocene base Maastrichtian base Campanian base Santonian base Coniacian 55 Ma 65 73 83 87. 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. micropaleontology indicates the rocks to be of Maestrichtian age.5 88. Assuming a surface temperature of 10° C and a geothermal gradient of 2° F/100 ft.5 base Turonian base Cenomanian base Cretaceous top Kimmeridgian base Kimmeridgian 91 Ma 97 144 150 156 Ma . Determine when each of the strata began to generate oil. At a depth of 1500 ft. Corrected BHT (4200 m): Estimated surface temp. It is also believed that 500 ft of Lower Cretaceous sediments were deposited before uplift and erosion began. Total original thickness of the Kimmeridgian is thought to be 1500 ft.

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. upper management has decided that gas and condensate are not economical. rich.000 23.000 8. 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 reservoir is sealed by a thick salt layer.500 21. No other source rocks were noted. Time-stratigraphic data are given in the following table. The source rock is thought to be about 300 Ma old. At that time nearby orogenic activity caused the first traps to be formed during a gradual 1200m uplift lasting until 40 Ma. they are in turn overlain at 2750m by a sandstone of excellent reservoir quality.Predicting Thermal Maturity . evaluate the prospect. "A regional study of the area suggests the probable presence of a thin.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. Erosional removal since the Permian probably totals about 2000 ft. and the surface temperature today is about 15° C. No other reservoirs are anticipated." Utilizing the principles of hydrocarbon generation and preservation. The geothermal gradient was found to be 1. Nearby well control indicates that a geothermal gradient of 3. The following geological summary is available to you. Highly fractured carbonates overlie the source rock.000 18. . From 40 Ma to the present about 500m of additional burial occurred. Because of the high operations cost.500 27. Carboniferous '' Ordovician '' Depth (ft) 7. Carboniferous '' '' '' '' E. Your responsibility is to make a recommendation regarding the nature of hydrocarbons that might be present in die prospect.000 13.65°C/100 m and a surface intercept of 15°C are reasonable for the area. The basin filled at a generally uniform rate from about 300 Ma to 100 Ma.0° F/100 ft. oil-prone source rock at about 4300m depth near the prospect.000 11. No unconformities are recognized within the Paleozoic.68 EXERCISE Thermal Maturity 5 Analyze the timing of oil generation in the Pink Well.000 25.

let us again emphasize that we are dealing all the time with uncertainties. our wells. Proven reserves: Here we start to enter a minefield! Different companies have different definitions of what is proven.Quantitative Assessment . secondary reserves.69 10 . However. 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. We will refer to oil. Similarly. And yet oil companies need to know what to expect. there is no way that we can know precisely how much we have found: the geology. Because anyway there is uncertainty about this amount. we have to remember that we are dealing with a resource and that we are very concerned with the quantities involved. What they think is beyond that in the accumulation. is liable to change between our information points. Increasingly these days. Note. it is desirable to be able to express our degree of confidence in it. We have to try to understand. Now we must see how we can apply our knowledge of the geology to assessing the amounts of petroleum that we have found. just what these changes amount to. since we are never able to recover all of the oil that is down there in the reservoir. but the same considerations. companies tend to use `proven' for those reserves that are believed to be present with an 85 or maybe 90 per cent degree of . This section is included to give an idea of what is involved. or hope to find. We cannot regard these quantities as `reserves'. we are involved with a greater or less degree of uncertainty about quantities. 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. How do we handle these problems? Before we get into this. We may distinguish between primary reserves that can be produced without any artificial assistance other than pumping. we have to clear a good deal of misunderstanding and misuse. 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. however. which can be produced using assisted or enhanced recovery techniques. in the case of small fields. before we started to take any of it out. This may be done via a standard deviation or by a statistical probability (see below). 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. even within oil companies. which controls the amounts of oil in the reservoir. of a well. once a discovery is made. A bald figure for `recoverable reserves' is somewhat meaningless. and therefore without any dissolved gas of significance. Recoverable reserves: The volume of oil that can actually be produced to surface from an accumulation. they might designate as `probable'. half a mile or whatever. measured in barrels or other units that is present in an accumulation under the ground. Some might use the term to refer to the amount of recoverable oil that is believed to lie within a given radius. and terms can be used equally for gas. of the following terms: OIL IN PLACE This is the total volume of oil. You may see the engineers using the term STOOIP: stock tank oil originally in place. or predict. unless we can be more specific about how we are going to produce them. located at surface near the well-head. and oil may be produced directly into it. The stock tank is. and tertiary reserves using more exotic techniques. It usually refers to what was there originally.Quantitative Assessment So far we have been talking in rather generalized terms. let alone how much. First. until actually all of the oil has been produced. methods. So.

If we do not know where the gas-oil and oil-water contacts are. They refer respectively to what was there and recoverable before we started producing. We have to discount those parts of it that are useless and just consider the net reservoir thickness. but what happens between and beyond our well control? – Sw is the water saturation. and `possible' altogether. 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. `probable'. or rather the average porosity of the net reservoir across the entire accumulation. – ? is the porosity. DISCOVERED RESERVES Once a discovery of oil has been made. meaning that we have to try to interpret in detail the environments that the sediments were deposited in. and the quality and strength of the cap rock. the percentage of the porosity that is occupied by the immovable water. The shape of the trap. It may well be that it is best to avoid the terms `proven'. 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. the higher will be the water saturation. This can be pretty subjective. 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. – Fill is the `fill factor'. if we do. that are meant. 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. So we multiply the bulk volume of the reservoir in the trap by those factors that represent the non-oil. and regional and local geological interpretation. including the adequacy of the source rock to provide enough oil to the trap. Not all of a reservoir formation is going to be sufficiently porous and permeable to contribute oil to production. and the thickness of the reservoir govern it. in this case 50 per cent. Recoverable reserves = [BV * Fill * N/G * ? * (1 . Probable reserves: Equally dodgy! One definition was given above: the term may be used. to refer to a degree of confidence or probability. it shrinks because gas bubbles out of it as its pressure is eased during production.70 confidence or statistical probability. Usually. We do our best from measurements on core samples and from wireline log interpretation. BV will be determined from seismic and well data. Again we need an average value for the field. we shall see shortly. the volume of the gas cap and the water-bearing rock below the oil-water contact being discounted. – N/G is the net to gross ratio. even when we have information from a lot of wells. faulting.Sw)] * RF * Constant FVF where: – BV is the volume of the reservoir formation within the closure of the trap above the spill-point. which is the percentage of the bulk volume that actually contains the oil. It is affected by many factors. then we can go straight to the bulk reservoir volume containing the oil. to cover the reserves that have only a 15 or 10 per cent chance of being present. like `proven'. it is the remaining reserves. then this factor may be little more than a guess. and what is still there for the taking at a given date. – FVF is the formation volume factor. What this means and how we arrive at the figure. What anyway should we regard as net reservoir? A rather arbitrary porosity cut-off value is often used. We then eliminate progressively everything from this volume that is not oil. . 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. Sometimes `possible' is also seen. if we hear simply about `reserves'.Quantitative Assessment . This will be controlled by variations in the nature of the sediments that comprise the reservoir.

Then we ask it to do the same thing again. companies. any one of which could be the real value. In a sandstone reservoir. since it is about this that the standard deviation can be calculated.Quantitative Assessment . and again. we shall find that the bulk of them tend to cluster round the middle (Fig. in producing figures for all of these factors. until we begin to wonder whether our answer has any reality or meaning at all. If we plot out the answers on our list falling within successive size ranges (in barrels of oil). So we usually have to base our estimate on prior experience elsewhere. there must be considerable uncertainty to say the least. It is a figure that we cannot know exactly until we have finished producing. The list is put into order from the smallest to the largest. Alternatively one may plot the frequencies as percentages of the total number of answers: the statistical probabilities. maybe 500 or 1000 times. It will be clear to anyone that. however. this is commonly about 50-60 per cent. and then analysed statistically. Who is right? Whose answer should we use? Can we indeed believe any of them? Unfortunately we cannot escape from the problem. for this average value.This is because. and governments must have numbers that they can use for planning purposes. What we are doing.71 – – RF is the recovery factor..). To get an answer to our sum in barrels of oil. and again. we can work out the standard deviation (the ±) which will give an idea of our confidence in our answer. having regard to all of the geology. from minimum possible to maximum possible. our best estimate. Note that the preferred answer that is usually used is the mean value. the problem is tackled through a statistical technique. somewhere within which the `true' figure must be. A constant is needed to adjust the units.. we have to multiply the figure we calculate by 7758. So we have a whole list of answers. The Americans measure reservoir volume in acre-feet: area in acres multiplied by reservoir thickness in feet. the proportion of the oil in the reservoir that we can actually recover and produce. then. for each of the factors we work out our best estimate. The number of answers in successive reserve ranges is plotted against the size ranges themselves. we give as our preferred figure the average of all the answers (the mean). is to multiply uncertainties by uncertainties. but biassing its pick towards our best estimate. More commonly. but it may be a good deal less from carbonates. . Diagrammatic plots of the outputs from two Monte Carlo simulations. Most commonly these days. known as a Monte Carlo simulation. Instead of estimating single figures for the factors that go into the reserves formula. and we also specify the total range. The computer does the sum using these values. and to try to be as honest and objective as possible. If we are working entirely in the metric system. Then we get a computer to pick a value for each factor at random from the range we have given. then we don't have to worry. doubtful estimates by doubtful estimates. 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. Different geologists will certainly come up with different values for at least some of the input factors. and arrive at perhaps wildly different answers. even though they may be well aware that any such figures will eventually turn out to be wrong.

When it comes down to risk. you may say. management can then decide whether or not to take the gamble on developing the field at those odds. but it assumes that we have already discovered oil. By plotting the answers from the 100 per cent probability downwards. to give the chance of discovering certain reserves or more including the 50 per cent chance that we may find nothing at all. different geologists will arrive at different figures for the probability of success. It will give a graph which shows the probability that the reserves will be of a certain size or more. This is what is used to determine those reserves that may be called proven. In the lower plot. probable.Quantitative Assessment . and possible at. but rather it is the number an individual geologist might produce to reflect his/her personal interpretation of the geology. The risk factor. now gives a more complete picture of the viability of an undrilled prospect . perhaps. Of course we try to be as scientific. that is exactly what it is. It is also used to assist management in making their exploration/development decisions. the 90. and ensures that all possibilities are considered. 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. 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. in numbers. of our confidence that there will be at least some oil. For example. and honest as can be in assessing exploration risk. Incidently. 50. Indeed it does not! When we are looking at exploration of the unknown. it doesn't take any account of the fact that our exploration well may. It cannot be worked out completely objectively. for geological reasons. as opposed to assessing what we already know to be there. and then merely combine the probabilities to give an overall probability .72 The output from a Monte Carlo simulation with the percentages plotted cumulatively. . and 10 per cent levels of probability respectively. And if all this sounds like a gambling game. We try to assess the probability that each factor will be satisfied. Most usefully. the curve represents the chance (probability) that the reserves are a certain size or greater.at least until we start also considering the costs and economics. the same values are discounted by a 50 per cent risk factor. there really is no such thing as the risk factor. objective. we have to go a stage further. we can read off from the graph the chances of our field containing that much oil or more. say. combined with the estimate of how much. but also the chance of there in fact being any oil at all. turn out to be totally dry-lacking in hydrocarbons. if any one of them fails or is lacking. We have to give not only our best estimate of how much petroleum there might be. 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. we can plot out the percentages of answers in successive size ranges cumulatively as we work down the list (Fig. It is this sort of thing that helps to make the oil exploration business so competitive. then no oil.the risk factor. This chance (probability) is known as the risk factor: it is an expression. UNDISCOVERED RESERVES This is all very well.).

and some may be more appropriate in given circumstances than the others. we have to assume that today we can identify and assess all of the prospects that ever will be found in the basin. Forcing these experts to agree a figure amongst them might refine the approach. There are lots of uncertainties in this but the calculation would be amenable to a Monte Carlo type of simulation. This combines in a single estimate. Extrapolate this smoothing line out into the future. Many `experts' have scratched their heads over the estimation of undiscovered reserves. if we draw a smooth line through it to even out the peaks and the troughs. merely use the average of the figures they produce. and use the figures for the known also for the unknown ones. In a similar vein the amount of oil found world-wide each year from the beginning of the century can be plotted. however. If all else fails. go for a large but very risky prospect. the expected reserve estimates from our Monte Carlo simulation multiplied (discounted) by the risk factor (Fig. remains to be found. expelled.73 Lastly. on average. or would our money be better spent on drilling a smaller but safer one? The risked reserves. we can. 1. for example. this technique may bring us into the right ball-park. the built-in risk factor takes care of this.Quantitative Assessment . 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. However. then use these figures for the unexplored parts of the basin. then the area under it represents the total volume of oil found to date. 2. and as such can be very useful in planning an exploration program. unless we really have a lot of information (we never have enough!). all of them are very dodgy . This starts with the volume of mature source rock in the basin and then.). If we have a reasonable amount of information and control. We could adopt what is known as a `geochemical material balance' approach. knowing how rich it is. Adding this to the original reserves will give us what is sometimes called the `ultimate reserves'-a grand total for the basin. This kind of plot can be used also for individual basins or for the whole world. otherwise we may be doing little more than guessing. sometimes in combination. But we have to admit that. Use past statistics (number of barrels of oil found on average for each 100m of exploration drilling?) and extrapolate to future drilling. however. 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. Some of these will be successful. for our `best estimate'. but some will be dry. we are said to be consulting the oracles! All of the above techniques have been used. We might look at explored and known parts of the basin. on this tack. 3. 5. 4. and the area under that bit will represent what. the amount of oil generated. ULTIMATE RESERVES So far we have been talking about a single oil accumulation or a single prospect. Delphi was the place in ancient Greece where one went to consult the oracle about one's future. and made available for entrapment (the `charge') can be calculated. the two elements of size and chance of success. and a number of techniques have been employed. 6. This figure is extremely imprecise and may be not much more than a guess. get a number of experts to make their forecasts by whatever technique they prefer and. and calculate average quantities of oil per cubic mile of sediment. Let us look at the more important ones. However. This is known as the Delphi technique. let us note a number known as the risked reserves. or underlying each square mile of surface area. it is a pretty wild sort of plot. We could make comparisons between known and unknown basins. to believe that we can do this would be the height of conceit. Undiscovered are thus what we hope to find in a prospect area or sedimentary basin in the future. qualify it by a statistical probability. The obvious thing to do is to add together the risked reserves estimates of all the remaining prospects. is a hypothetical figure. Should we.

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