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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The earliest stage of hydrocarbon generation occurs during diagenesis. 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. where hydrocarbon movement ceases and accumulation occurs. called metagenesis. Although the transformation process is very complex. Formation of biogenic methane has been recognized for a long time. Most of this organic matter is transformed during diagenesis info very large molecules. kerogen begins to decompose into smaller. and are called bitumen . During this second transformation phase. it is known that organic debris derived from plants and algae is best preserved in fine-grained sediments deposited in the absence of oxygen. As temperature rises.Organic Facies . These changes lead to a gradual cessation of microbial activity. more mobile molecules. As burial depth increases. however. are chemically distinct from each other. Many of the chemical compounds present in sediments are in fact derived from bacteria. oil and gas molecules can be expelled from the source rock into more permeable carrier beds or conduits. the largest of which are called kerogen. convert some of the organic debris to biogenic methane. Low-temperature chemical and biological reactions (called diagenesis) that occur during transport to and early burial in the depositional environment modify this organic matter.Introduction FORMATI0N OF 0IL AND GAS Proponents of the organic origin of oil and gas have given us a general picture of how organic matter derived from dead plants is converted to hydrocarbons. . In the late stages of catagenesis and in the final transformation stage. these are the precursors for petroleum. Certain microorganisms. These differences can have a significant effect on hydrocarbon generation. These play a key role as the precursors for oil and much natural gas. and temperature increases. In the early stages of catagenesis most of the molecules produced from kerogen are still relatively large. thermal reactions become increasingly important. and were formed as dead organic matter was converted to microbial tissues. porosity and permeability decrease. Once formed. and thus eventually bring organic diagenesis to a halt. Migration through these conduits often leads to traps. but only within the last few years have we realized that in many areas a large portion of the natura!-gas reserves are biogenic. called methanogens.5 1 . with many details still poorly understood. called catagenesis. the principal products consist of smaller gas molecules. or under different diagenetic conditions.

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

If this deeper water is enriched in nutrients.000 billion t) dispersed in fine-grained sedimentary rocks. with a preference for horizontal water movement within each density layer. accumulation of organic-rich sediments cannot occur. Nutrients dissolved in waters below the photic zone therefore go unutilized. Productivity is the logical place to begin our analysis. Peru. Although oxidative decay destroys most of the yearly production. FACTORS INFLUENCING ORGANIC RICHNESS In order for organic-rich rocks to be formed. paleoclimate.Organic Facies . Bodies of water naturally develop density stratification. light intensity. The three primary factors influencing the amount of organic matter in a sedimentary rock are productivity. Each of these categories could in turn be further subdivided. where there is local recycling of nutrients from decaying organisms and influx of fresh nutrients from terrestrial sources.7 extensive oxidation of land-plant debris in soils. Only where there is upwelling of subsurface waters can these nutrients return to the photic zone. Each factor may be dominant under different conditions.000. and dilution. preservation.000 billion t. Upwelling occurs where bulk movement of surface water away from a particular area allows deeper water to ascend to replace it. Only a small fraction of this (10. and Northwest Africa that result from the movement of surface waters away from these coasts. nutrient availability would depend on such factors as water circulation patterns. high photosynthetic productivity will occur at the site of upwelling. carbonate supply. When we consider inefficiencies in discovery and recovery. On the other hand. or about 0. however. the low TOC values could indicate that the remaining organic matter has no more nutritional value. Total Organic Carbon (TOC) values decrease monotonically through the first 300 meters of burial before levelling out at about 0.1%. Depth could interfere with microbial diagenesis when compaction reduces pore sizes and nutrient fluxes in interstitial waters. Shallowmarine environments. volcanism. one of the critical parameters governing productivity. For example. because under normal circumstances they cannot move upward into the zone of photosynthesis. and general water chemistry. watercirculation patterns are particularly important for supplying nutrients and thus controlling productivity. suggesting that either depth or organiccarbon content eventually limits diagenesis. and that the microbes have given up trying to digest it. much of the terrestrial organic material is already highly oxidized when it arrives in the sediments. temperature. Nutrient availability is. and recycling by organic decay. orogeny and erosion. There is another zone of seasonal upwelling off the Horn of Africa in the Indian Ocean as a result of . In the modern world there are zones of intense seasonal upwelling off the west coasts of California. in fact. significant amounts of organic matter must be deposited and protected from diagenetic destruction. In relatively unrestricted marine environments. a great deal of the oxidation of organic matter occurs within the sediments themselves. predators.05%) occurs in economic deposits of fossil fuels. are therefore much more productive than the open ocean. over vast amounts of geologic time the small fraction that escaped the carbon cycle has built up extremely large quantities of organic matter (20. because without adequate productivity. Namibia. PRODUCTIVITY A partial listing of the many factors influencing productivity would include nutrient availability. Although some destruction of organic material occurs during transport to the depositional environment. only one molecule out of about every one million successfully negotiates the journey from living organism to the gasoline pump.

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

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

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

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

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

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

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

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

000 atomic mass units. Although cellulose is quite resistant to decomposition under some conditions. and amino acids. and thus tends to become concentrated as other organic matter is decomposed. Lignin monomers are linked topether to form molecules having molecular weights from 3000 to 10. it is an important constituent of terrestrial organic matter. It is a polymer consisting of many repetitions and combinations of three basic aromatic subunits.16 varying structure. Amino acids are the building blocks of proteins. Lignin is an important component of wood. Because phenols are potent bactericides. however. which are aromatics having a hydroxyl group (OH) attached. Upon decomposition lignin forms phenolic compounds. but asphaltene molecules are smaller and more aromatic than most kerogens. providing much of the structural support for large land plants. Among these are lignin. They are rapidly metabolized by virtually all organisms. Many nonhydrocarbon molecules common to living organisms are also present in sediments. and thus are seldom preserved in sediments (exceptions occur in shell material and in bones. They have many characteristics in common with kerogen. where small amounts of preserved amino acids can be used to date specimens) . carbohydrates. and cellulose. the latter is the most abundant organic compound in the biosphere. sugars. Lignin and cellulose are major constituents of humic coals. Carbohydrates include starch. Like lignin.Organic Chemistry . lignin is rather resistant to degradation. most carbohydrates are attacked readily by microorganisms.

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

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

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

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

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

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

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

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

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

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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.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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Petroleum Traps . multi-interpretable (D).Make the interpretations from easy (A) to more difficult. . The logs show SP (Self Potential or Spontaneous Potential) on the left and R (Resistivity) on the right. Interpret the geological relationships shown in each by drawing a structural cross-section through the logs.45 EXERCISES EXERCISE 1: The following well logs have been hung on a structural datum.

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

47 .Petroleum Traps .

48 .Petroleum Traps .

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

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

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

This method works fairly well if the kerogen is still within the oil-generation window. it is impossible to determine which maturation path brought it to that point. Atomic H/C ratios must therefore be corrected for the effects of . Problems with living organic matter are easily avoided by physically removing tiny plant roots and other recognizable debris. which affect only the kerogen portion of the sample. Contaminants of particular notoriety are diesel fuel. it can lead to an overly optimistic assessment of the organic richness of the section. Like pyrolysis. Careful picking of lithologies and comparison with up-hole samples can often recognize caved materials. of course. It breaks down at high maturity levels. because of their friability. Caving is a particular problem for coals. Mold or other surface growth may also be present. This discovery led to the use of CPI as an indicator of maturity. and can be removed prior to beginning the analytical sequence. diesel fuel affects both kerogen and bitumen. therefore. atomic H/C ratios measure the present day status of the kerogen rather than its original chemical composition. In many cases.Source Rock Evaluation . ESTIMATION OF ORIGINAL SOURCE CAPACITY Of the three major methods of determining kerogen type. In such cases TOC values will be raised and reflectance histograms will show a large population near 0. 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.5%. and therefore should be easy to avoid. vitrinite reflectance measurements offer the best means of recognizing caving. Caving is not a problem for conventional or sidewall cores. they can usually be identified with reasonable confidence. whereas those of oils were almost always below 1. Hydrocarbon contamination is rare except in the immediate vicinity of production or where vehicles are used. however. have low CPI values even when immature. in which the input of terrestrial lipids was very limited. Without additional information. It is capable of impregnating sidewall and conventional cores as well as cuttings. TOC values will be raised and vitrinite-reflectance values lowered by the presence of adsorbed diesel. Fortunately. and lignite from lignosulfonates. Furthermore.52 values (> 1. 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. in the last decade kerogen analyses have replaced bitumen analyses as the routine procedure in source-rock evaluation. where the fluorescence that enables us to distinguish between oil-prone and non-oil-prone disappears toward the end of the oil-generation window. Well Samples . As long as kerogen particles are not completely black. Walnut hulls and other organic debris are also easy to detect microscopically. In contrast to solid additives. but it can be devastating in cuttings samples. however. of course.The main causes of contamination among samples obtained from wells are caving and adulteration by drilling-fluid additives. strongly affected by maturity. rocks deposited in pelagic environments. because all kerogens have low pyrolysis yields. fewer CPI determinations are made now. In particular. palynological analysis can usually detect the presence of lignosulfonates because of the unique pollen assemblages present in the lignite. Pyrolysis yields are. 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. Drilling-fluid additives have been a severe headache for petroleum geochemists for a long time. The exception to this rule is with amorphous material. only microscopic analysis is relatively unaffected by maturity. As a result. walnut hulls and other solid debris.2.5).

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

Because some Cenozoic land plants are richer in resins and waxes than Paleozoic plants. They have excellent potential to generate liquid hydrocarbons. A second. Those between 150 and 300 contain more Type III kerogen than Type II and therefore have marginal to fair potential for liquids. resinite. because during the Paleozoic the biota was quite different than during the Cenozoic.5% Ro.9% Ro. for most kerogens the onset of oil-generation is taken to be near 0. Conodont Alteration Index (CAI) values ranging from 1 to 5 were tied loosely to vitrinite reflectance and fixed carbon content of coals.54 values in milligrams per gram of TOC. less common application is to decide whether oil will be stable in a given reservoir. Because variations in TOC have been removed in the normalizing calculation. The normalized S2 and S3 values are called the hydrogen index and the oxygen index. Kerogens with hydrogen indices above 600 usually consist of nearly pure Type I or Type II kerogens. and the coals were of bituminous to anthracite rank. Because vitrinite reflectance is the most popular method of determining maturity. Determination of the oil-generation window in a particular section is the objective of most maturity analyses performed on possible source rocks. Some laboratories put the onset of maturity at 435° C. a unified scale for comparing them with Ro values has not been adopted. 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. this generalization has two fallacies: most of the coalfields originally studied were of Paleozoic age. either from terrestrial macerals (cutinite. some Cenozoic coals should have better potential for generating liquid hydrocarbons. Thus. Although Tmax values are determined objectively. . However.35% Ro. the hydrogen index serves as an indicator of kerogen type. Age of coals is important. Interpretation of hydrogen indices for immature kerogens is straightforward. CAI can actually measure high-grade metamorphism. 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. The ultimate limit of oil stability is not known for certain. but in most cases is probably not much above 1. but there are still some minor variations from one laboratory to another. Peak generation is reached near 0. Measured hydrogen indices must be corrected for maturity effects by using a modified van Krevelen diagram as outlined above. respectively. most other maturation parameters are related to Ro values. 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. The correlations among maturity parameters have been fairly well established. and the end of liquid-hydrocarbon generation is thought to be at about 1. because they vary with kerogen type as well as maturity. MATURITY Kerogen Parameters. others use 440°. Hydrogen indices above 150 reflect increasing amounts of lipid-rich material. exinite) or from marine algal material.Source Rock Evaluation . It is particularly difficult to generalize about TAI values because the numerical values of TAI scales have not been standardized among laboratories. Kerogens with hydrogen indices above about 300 contain substantial amounts of Type II macerals.6% Ro. and thus are considered to have good source potential for liquid hydrocarbons. Nevertheless. with CAI of 8 reached in a marble. if you are using TAI determinations determined by an analytical laboratory.

50 0. To do this intelligently we must have the ability to develop regional models of organic facies and thermal maturity. Whenever possible.35 1.Source Rock Evaluation .55 SUMMARY Any source-rock evaluation should attempt to answer three questions: What are the quantity.00 Thermal Alteration Index (TAI) 2. With increasing experience one can also learn to derive important information on thermal histories.8 3.20 1.5 2 2 2 3 4 4 5 Correlation of various kerogen-maturity parameters with vitrinite-reflectance (Ro) values .4 3. type.00 1.6 2. Interpretation of source-rock data on a basic level is quite simple. rather.40 0.8 4. therefore. unconformities and erosional events. and maturity of the organic matter present in the rocks? Satisfactory methods are available in most cases to answer all these questions.50 2. we should attempt to corroborate the measured data by other analyses. we should not rely on a single analytical technique. Vitrinite Reflectance (%Ro) 0. We should always attempt to extrapolate our measured data over as large an area as possible.00 3.0 2.80 1.0 3.3 2.00 4.0 4.0 Pyrolysis Tmax (°C) 420 430 440 450 460 465 470 480 500 500 + 500 + Conodont Alteration Index (CAI) 1 1 1 1.60 0.5 3. and organic facies.2 3. In some areas one technique may fail completely or may be only partially successful.

07 1.1 2.81 1.6 0. present-day H/C ratios to the ones that the kerogens had when they were thermally immature.72 0.5 2.15 0.2 Atomic H/C 1.5 2. quality (H /C and %Alginite + Exinite)." To do this. one must first convert the measured. however.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).65 0. The calculated immature H/C ratios are listed in the table on next page.7 2.5 0.7 2.27 1.5 2-2.0 2-2. B) H/C versus TAI for Mauve Well samples.77 0.1 3. 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 2.3 1.5 2.7 3. as shown in Figure B (derived from Figure A).86 0.0 0.0 3. Both the immature H / C ratios and the maceral analysis data need to be scaled to calculate "Total Oil. A) Calculation of the immature kerogen H/C ratio(at A) from the present-day H/C ratio and vitrinite reflectance data(at P) .7 1. presenting the kerogen quality factor as a .22 1.33 1. To use the H /C data.05 0." Two independent quality measurements have been made.75 0.5 1.7 1.6 2.66 0.5 1.6 2. and then tracing the H/C ratio back to its immature value.Source Rock Evaluation .3 0.5 2-2.98 0.9 3.2 1.38 TAI 2.2 3.8 0.56 EXERCISES Worked out example: Perform a source-rock analysis on the Mauve Well. so "Total Oil" can be plotted against "Oil Already Generated. and both should be utilized and examined for possible discrepancies. This can be done easily by plotting H/C versus TAI.41 0. and maturity (TAI). refer to the graph on next page.2 2.5 0.

In likewise manner (not illustrated here) the quality factor can be determined from maceral analysis data. the H/C ratio gives the lower quality factor.9 1.30 1.77 0.50 1.65 0. 2000.85 1. however.0 0. The most important point being made here is that these discrepanties must be taken seriously by the interpreter.35 0. it is impossible to pinpoint the error.77 0.07 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 1.90 ? ? Quality Factor Quality Factor (from H/ C) (from 1. 4000. 2300.98 0.00 0.35 1.05 1.57 function of H/C ratio of the immature kerogen in order to determine the quality factor from H/C.8 1.05 0.81 1. In each case.17 0.43 1.22 1.38 Immature H/C 1.05 1.6 1.65 0.07 1. If these attempts produced no resolution of the problem.72 0.Source Rock Evaluation .75 0.90 0.6 1. The samples at 1000.90 0.6 1. to check for analytical error. so some systematic error is likely.15 0.5 1.60 0. Kerogen quality factor as a function of H/C ratio of the immature kerogen.66 0.90 0.60 0. 1500.20 1. and 4500 meters all show differences in the quality factors calculated from the two types of data.8 ? ? * * * Indicates discrepancy between quality factors calculated from H /C and from maceral analysis. 1750. such as pyrolysis.05 0. The prudent interpreter might now ask that some of the H/C ratios be rerun.90 0. and not .4 1.5 1. and would certainly request that the slides made for maceral analysis be reviewed.2 0.70 1.27 1.41 0.9 0.7 1.86 0. Without more knowledge.35 0.60 ? ? * * * * * 1.33 1.05 0. the interpreter might then decide to try a third technique. The scaled quality factors are given for each parameter in the table on next page.22 1. It is apparent that there are serious discrepanties between the H/C and maceral analysis results for several of the samples.81 1.5 1.

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

8 0.5 3.3 1.5 2.05 0.42 0.88 0.5 2.03 0.22 0.11 0.18 0.09 0. Source-rock data tor the Turquoise Well Depth (ft) 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500 8000 8500 9000 9500 10.66 0.51 0.21 1.49 0.0 2.5 2.86 1.6 2.10 0.07 0.5-3 2. EXERCISE Source Rock 2 Perform a source-rock evaluation of the section penetrated in the Turquoise Well.00 1.0 2.2 2.1 2.91 1.71 0.41? 1.02 Atomic H/C 0.59 0.60 0.5-3 2.85 0.5 3.12 *TAI and Ro are interconverted according to the correlation table at the end of chapter 7.7 0.03 0.000 Type of Sample Cuttings Cuttings TOC 1.51 0.5-3.0 2.63 0.33? 1.51 0.02 0.02 0.09 0.44 0.17 0.07 0.06 0.01 0.91 0.49 0.60 0.5 2.06 0.55 0.25 1.52 0. 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 2.4 0.21 1.5-3 3.5 2.60 0.17 0.5 2.07 1.91 1.0-2.5 2.5 TOC = Total Organic Carbon Bit/TOC = Bitumen/Total organic carbon ? indicates a poor histogram TAI = Thermal Alteration Index Ro = Vitrinite reflectance .5-3 2. Explain how you resolved any apparent discrepancies.05 0.66 0.5 0.5 3-3.9 1.Source Rock Evaluation .6 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.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10 2-2.46 0.0 0.65 0.5 2.7 0.08 0.3 2.08 0.21 0.99 1.65 0.27 1.8 1.3 2.27 0.0 2.59 0.5 2.48 Ro 0.2 0.06 0.5-3 2.6 4.67 0.3 2.08 0.08 0.5 2.0 2.90 0.1 0.3 Bit/TOC 0.5-3 2.0-2.0-2.5 2.61 0.03 0.26? 1.0 3-3.25 0.0 2.

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

Neglecting compaction effects. it is easy to construct burial-history curves with a high level of confidence. . In the Tiger well. This geometry is a direct consequence of ignoring compaction effects. Nevertheless. which was constructed from the time stratigraphy for the Tiger well. The subsurface temperature must be specified for every depth throughout the relevant geologic past. Using the other control points from the input table. Using these present-day data and extrapolating them into the past. by 80 Ma the sediment had been buried to a depth of 900 m (point C).Predicting Thermal Maturity . burial-history curves represent our best understanding of the geological history of an area.(9-2) All of the shallower and younger horizons will have burial-history curves whose segments are parallel to those of the oldest horizon. In cases where biostratigraphic data are available and deposition has been reasonably continuous. The next step is to locate the first control point from the time-stratigraphic data on the input table. 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. representing the initial deposition of the sediment (point A) and its position today (point B). if constructed as carefully as the data permit. Today the rock is at a depth of 3700 m. a burial-history curve may represent only a rather uncertain guess. sediment has accumulated continuously but at varying rates since deposition of the oldest rock 100 million years ago (Ma). are marked on the age-depth plot. An example is shown in the following figure. Connecting the six dots completes the burial-history curve. The burial-history curve was constructed in the following way: two points. In cases where biostratigraphic data are lacking or where the sediments have had complex tectonic histories. Burial-history curves are based on the best information available to the geologist. TEMPERATURE HISTORY The next step is to provide a temperature history to accompany our burial-history curve. Suppose further that local weather records indicate a yearly average surface temperature of 19° C. Suppose. and that a corrected bottom-hole temperature of 133° C was obtained at 3800 m. 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. that the Tiger well was logged. for example. we can construct the complete figure.

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

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

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

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

A question of some concern comes from the previously mentioned fact that most of the maturity models treat all types of kerogen identically.000 Type of Sample Cuttings Cuttings TOC 1. an accurate interpretation of the ancient geothermal history may be critical.49 0.66 0.5-3. particularly where Paleozoic rocks are involved.01 0.91 1.08 0.02 Atomic H/C 0.05 0.150 ft in the Middle Miocene. however. EXERCISES EXERCISE Thermal Maturity 1 Perform a source-rock evaluation of the section penetrated in the Turquoise Well.5 2. In other cases.59 0.02 0. Despite experimental evidence indicating that different kerogens decompose to yield hydrocarbons at different levels of maturity models.65 0.5 0.06 0. we still would have to extrapolate the present somehow into the past.5-3 2. In many cases. Source-rock data tor the Turquoise Well Depth (ft) 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500 8000 8500 9000 9500 10.71 0.5 3.7 0.5-3 2.60 0.25 1.1 2.3 1.41? 1.51 0.5 3.7 0.21 1.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10 2-2.51 0.22 0.03 0.85 0. The corrected bottom-hole temperature was 270° F.07 1.5 2.88 0.17 0.52 0.5-3 2.5 2.18 0.08 0.0 3-3.9 1. Base Pleistocene 2 Ma Base Pliocene 5 Base Upper Miocene 11 Base Middle Miocene 50 Ma .21 1.3 Bit/TOC 0.99 1.27 1. 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.4 0.5 3-3.91 0. and 11. where presentday temperatures are maximum paleotemperatures. Construct a family of burial-history curves for the well and calculate the present-day TTI at total depth.5-3 2. even an inaccurate extrapolation into the past may not cause significant problems.000 ft of Upper Miocene before being abandoned at 16.8 0.86 1.5 TOC = Total Organic Carbon Bit/TOC = Bitumen/Total organic carbon ? indicates a poor histogram TAI = Thermal Alteration Index Ro = Vitrinite reflectance EXERCISE Thermal Maturity 2 The Black Well was drilled off the Louisiana Gulf Coast.2 0.48 Ro 0.90 0.Predicting Thermal Maturity .8 1. A plausible average surface temperature is 20° C.6 4.0 0.26? 1.91 1.08 0. do not utilize different kinetic parameters for the various kerogen types.00 1. however.1 0.5 2.27 0. 3500 ft of Pliocene.5-3 2.33? 1.3 2.65 0.5-3 3.66 Even if we could measure present-day subsurface temperatures with perfect accuracy.67 0.03 0. It penetrated 1000 ft of Pleistocene sediments.06 0.

Assuming a surface temperature of 10° C and a geothermal gradient of 2° F/100 ft. Corrected BHT (4200 m): Estimated surface temp.5 88. At a depth of 1500 ft. assuming a constant geothermal gradient through time. Total original thickness of the Kimmeridgian is thought to be 1500 ft. Time-stratigraphic data Temperature data Age (Ma) 0 2 38 65 80 100 Depth (m) 0 500 1200 2700 3000 4000 Present-day average surface temp.67 EXERCISE Thermal Maturity 3 Calculate present-day TTI at 3000 m in the Red Well. The following Upper Cretaceous boundaries are noted: Maestrichtian-Campanian Campanian-Santonian Santonian-Coniacian Coniacian-Turonian Turonian-Cenomanian 1807 ft 2002 ft 2360 ft 2546 ft 3017 ft The Cenomanian is 480 ft thick and overlies 1000 ft of Kimmeridgian-age shale.end Cretaceous: 15° C 141° C 25° C EXERCISE Thermal Maturity 4 The Ultraviolet Well is spudded in Paleocene sediments. It is also believed that 500 ft of Lower Cretaceous sediments were deposited before uplift and erosion began.5 base Turonian base Cenomanian base Cretaceous top Kimmeridgian base Kimmeridgian 91 Ma 97 144 150 156 Ma .Predicting Thermal Maturity . Determine when each of the strata began to generate oil. Age data top Paleocene base Paleocene base Maastrichtian base Campanian base Santonian base Coniacian 55 Ma 65 73 83 87. Total depth is reached at 6120 ft in Middle Jurassic rocks. Find when the rock at 3000 m began to generate oil (TTI = 10). draw a burial-history curve for the section penetrated and calculate maturity for the Kimmeridgian shale. Evidence from related sections indicates that the Paleocene was originally about 3000 ft thick and that no other Cenozoic sediments were ever deposited. micropaleontology indicates the rocks to be of Maestrichtian age.

rich. No unconformities are recognized within the Paleozoic. No other reservoirs are anticipated. The source rock is thought to be about 300 Ma old.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. The basin filled at a generally uniform rate from about 300 Ma to 100 Ma. Carboniferous '' '' '' '' E. The following geological summary is available to you. 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. The reservoir is sealed by a thick salt layer. Erosional removal since the Permian probably totals about 2000 ft.000 25. From 40 Ma to the present about 500m of additional burial occurred. Nearby well control indicates that a geothermal gradient of 3. 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. Your responsibility is to make a recommendation regarding the nature of hydrocarbons that might be present in die prospect. upper management has decided that gas and condensate are not economical. they are in turn overlain at 2750m by a sandstone of excellent reservoir quality. .000 18.000 13. oil-prone source rock at about 4300m depth near the prospect. The geothermal gradient was found to be 1. Time-stratigraphic data are given in the following table.000 8. At that time nearby orogenic activity caused the first traps to be formed during a gradual 1200m uplift lasting until 40 Ma.0° F/100 ft. evaluate the prospect. Highly fractured carbonates overlie the source rock. No other source rocks were noted. Carboniferous '' Ordovician '' Depth (ft) 7.500 21. "A regional study of the area suggests the probable presence of a thin." Utilizing the principles of hydrocarbon generation and preservation.68 EXERCISE Thermal Maturity 5 Analyze the timing of oil generation in the Pink Well. and the surface temperature today is about 15° C.500 27.65°C/100 m and a surface intercept of 15°C are reasonable for the area.000 23. Because of the high operations cost.000 11.Predicting Thermal Maturity .

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

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

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

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

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

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