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

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

nutrient availability would depend on such factors as water circulation patterns. When we consider inefficiencies in discovery and recovery. only one molecule out of about every one million successfully negotiates the journey from living organism to the gasoline pump. Total Organic Carbon (TOC) values decrease monotonically through the first 300 meters of burial before levelling out at about 0. carbonate supply. Only where there is upwelling of subsurface waters can these nutrients return to the photic zone. and Northwest Africa that result from the movement of surface waters away from these coasts. Productivity is the logical place to begin our analysis. and dilution. or about 0. The three primary factors influencing the amount of organic matter in a sedimentary rock are productivity. and that the microbes have given up trying to digest it. temperature. Peru. Bodies of water naturally develop density stratification. and recycling by organic decay. Shallowmarine environments. a great deal of the oxidation of organic matter occurs within the sediments themselves. Nutrient availability is. In relatively unrestricted marine environments. the low TOC values could indicate that the remaining organic matter has no more nutritional value. There is another zone of seasonal upwelling off the Horn of Africa in the Indian Ocean as a result of . and general water chemistry. paleoclimate. Each factor may be dominant under different conditions. in fact. light intensity.Organic Facies . In the modern world there are zones of intense seasonal upwelling off the west coasts of California. Although some destruction of organic material occurs during transport to the depositional environment. Depth could interfere with microbial diagenesis when compaction reduces pore sizes and nutrient fluxes in interstitial waters. orogeny and erosion. predators. over vast amounts of geologic time the small fraction that escaped the carbon cycle has built up extremely large quantities of organic matter (20.7 extensive oxidation of land-plant debris in soils. Namibia. one of the critical parameters governing productivity.000 billion t. FACTORS INFLUENCING ORGANIC RICHNESS In order for organic-rich rocks to be formed. PRODUCTIVITY A partial listing of the many factors influencing productivity would include nutrient availability. Nutrients dissolved in waters below the photic zone therefore go unutilized. much of the terrestrial organic material is already highly oxidized when it arrives in the sediments. however.000 billion t) dispersed in fine-grained sedimentary rocks. preservation. If this deeper water is enriched in nutrients. accumulation of organic-rich sediments cannot occur. with a preference for horizontal water movement within each density layer. are therefore much more productive than the open ocean. Although oxidative decay destroys most of the yearly production. because without adequate productivity. high photosynthetic productivity will occur at the site of upwelling.000. watercirculation patterns are particularly important for supplying nutrients and thus controlling productivity. significant amounts of organic matter must be deposited and protected from diagenetic destruction. because under normal circumstances they cannot move upward into the zone of photosynthesis. Upwelling occurs where bulk movement of surface water away from a particular area allows deeper water to ascend to replace it.05%) occurs in economic deposits of fossil fuels. where there is local recycling of nutrients from decaying organisms and influx of fresh nutrients from terrestrial sources. For example. Each of these categories could in turn be further subdivided. volcanism.1%. On the other hand. suggesting that either depth or organiccarbon content eventually limits diagenesis. Only a small fraction of this (10.

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

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

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

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

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

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

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

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

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

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

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

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

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

much as a cookie browns during baking. EFFECTS OF MATURATION ON KEROGENS Kerogen undergoes important and detectable changes during catagenesis and metagenesis. Old rocks will often generate hydrocarbons at significantly lower temperatures than young rocks. There is therefore no necessary cause-and-effect relationship . These reactions are intimately related to important changes in the chemical structure of kerogen. Kerogen particles become darker during catagenesis and metagenesis. much of the sulfur is lost in the earliest stages of catagenesis. but it also states that at any temperature above absolute zero reactions will be occurring at some definable rate. In the late stages of maturity. however. the cracking of any organic molecule requires hydrogen. Furthermore. high-sulfur oils found in a number of areas. as evidenced by low maturity. Nitrogen loss occurs primarily during late catagenesis or metagenesis. and III kerogens will therefore be very similar chemically. Types I. Nitrogen and sulfur are also lost from kerogens during catagenesis. oil. the chemical process of maturation never stops completely. There is a steady color progression yellow-goldenorange-light brown-dark brownblack as a result of polymerization and aromatization reactions. but they are not necessarily identical with hydrocarbon generation. after hydrogen loss is well advanced. 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. thus allowing us to judge the extent to which kerogen maturation has proceeded. The most important implication of these chemical changes is that the remaining hydrocarbongenerative capacity of a kerogen decreases during catagenesis and metagenesis. As we saw earlier. Because many of the light product molecules are rich in hydrogen. is to monitor hydrocarbon generation. The real reason for following kerogen catagenesis. In contrast. even if drastic decreases in temperature occur. and thus are not necessarily valid indicators of hydrocarbon generation. provided that the hydrogen content of the kerogen was known prior to the onset of catagenesis. The more hydrogen a kerogen contains. 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. Chemical reaction-rate theory requires that the rates of reactions decrease as temperature decreases. the residual kerogen gradually becomes more aromatic and hydrogen poor as catagenesis proceeds. and gas) will be discussed in a following chapter. II. For practical purposes. Although it is obvious that many measurable changes in kerogens are related to hydrocarbon generation.Kerogen . Kerogen maturation is not a reversible process-any more than baking a cake is reversible. of course. including the Miocene Monterey Formation of southern California. All kerogens become increasingly aromatic and depleted in hydrogen and oxygen during thermal maturation. The composition of the products (bitumen. the more hydrocarbons it can yield during cracking. 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. 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. simply because the longer time available compensates for lower temperatures. Some of these changes can be measured quantitatively. This complex interplay between the effects of time and temperature on maturity is discussed in a later chapter. possessing essentially no remaining hydrocarbon generative capacity. Furthermore. It is impossible to set precise and universal temperature limits for catagenesis.21 This chapter will focus on those changes in the residual kerogen that accompany catagenesis. because time also plays a role.

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

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

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

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

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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.

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

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

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

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

rocks whose capillary-entry pressures are high enough to overcome hydrocarbon buoyancy. Much of the hydrocarbon storage at Antelope is apparently in silts and sands juxtaposed with the producible Bakken reservoir. The low permeability sand thus creates a bottleneck to gas migration. 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. 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. Thus the Elmworth Field exhibits a water-over-gas contact. and vertical migration becomes important. while the structure or lithologic change prevents lateral updip migration. 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.33 permeabilities to hydrocarbons provide barriers to migration: that is. KINETIC TRAPS Kinetic traps represent a fundamentally new concept in trapping mechanisms for hydrocarbons. This model requires. CLASSICAL TRAPS. Gas production is actually from the low-permeability sand rather than from the high-permeability sand updip and downdip. Classical traps are well understood. and will be covered separately. of course. Because gas generation is very rapid. Accumulations are small because drainage areas are small. Most hydrocarbon traps are either structural or stratigraphic. Cross section across the Rhine Graben of West Germany showing the discontinuity of strata as a result of extensional tectonism endemic to rift basins. the low-permeability sands become filled with gas. The much smaller Antelope Field produces from the Mississippian Bakken Formation. a fractured shale that is both source and reservoir. The simple principle behind a kinetic trap is that hydrocarbons are supplied to the trap faster than they can leak away. Because the high permeability sand updip allows gas to migrate rapidly through. The seal prevents vertical migration from the reservoir rock into overlying strata. The Elmworth Field in the Alberta Deep Basin of Canada is the prototype for kinetic gas accumulations.Migration . No traditional seal exists. that strong hydrocarbon generation and migration is going on today. Lateral migration is of necessity short distance. . it remains water wet.

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

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

they can be mapped by means of contours drawn on the top of the reservoir formation. except that the contours are in depth below sealevel.(2-18) Before we go further. Indeed. These are illustrated using a simple anticline as an example. but there must also be some sort of blockage to prevent further migration.Petroleum Traps . the ticks are on the downthrown sides of the faults. If it can. up towards the ground surface. if more continues to migrate up into the trap than can be . but it is often convenient to exaggerate the vertical to show the individual beds more clearly. The location of a trap in the subsurface is often the first objective of an exploration program. it will escape to surface as a seepage. one or more cross-sections may be drawn. (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. THE REPRESENTATION OF TRAPS Traps are commonly depicted in two ways. To give a true representation. not only must the reservoir be overlain by an impervious layer forming a cap rock or seal (shales or evaporites are likely to be the most effective). is mapped by contours showing depth below sealevel. as the beds on one side are dropped down relative to the other. before we reached our modern understanding of the geology of petroleum. First. Faults will be marked by jumps of the contours. Note that we commonly highlight petroleum accumulations by shading or colouring the reservoir formations where they contain oil or gas. The lowest point. Nowadays we can do better. exploration used to consist largely of finding a trap. which may refer either to its depth or to the spot under the ground where it lies.36 7 . drilling a well into it. Any oil getting there will be unable to migrate further and so it starts to accumulate. The top of a reservoir formation. To complement the structure contour map. The contours are in feet below mean sea-level. by displacing the water already there in the porosity. so that the highest points on the map have the lowest values. 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. and hoping for the best. they should properly be drawn with the same scale for both the vertical and the horizontal. Such a configuration of the reservoir is known as a trap. A structure contour map resembles an ordinary topographic contour map. which may give a misleading impression of `lakes' of petroleum under the ground! Structure contour maps. If then we are to find any of it still preserved.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. is the spill-point: this is where oil. is known as the crest of the trap. (a) A simple hypothetical anticline. where it is lost. we need a few definitions. The highest point of the reservoir.

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

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

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

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

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

which were eroded and unconformably overlain by Cretaceous shales. elsewhere it appears to form a trap.(2-31) The oil in the Argyll and many other fields in the North Sea is trapped in tilted and faulted Permian to Jurassic reservoirs. some of them large.(230) COMBINATION TRAPS A number of fields.42 targets. neither completely controls the trap. although such prospects are not easy to locate and may require a lot of sophisticated seismic.Petroleum Traps .). The Prudhoe Bay field in northern Alaska. The oil in these fields can only have migrated there after the traps were sealed by the higher sequences. the biggest field in the USA. that the trap must be shown to have been there before the oil migrated. A couple of examples may give the idea. Both the faulting and the unconformity control the traps. where the reservoirs overlie overpressured shales. The reservoir beds were folded into an anticline. and where an oil-water contact is continuous across a fault. has most of its oil and gas trapped in a Carboniferous to Jurassic sequence which includes more than one reservoir. or the oil would have been lost. there always seems to be something new as a challenge. as the fault moved. An investigation into the sealing qualities of faults affecting roll-over anticlines in the Niger Delta. which was tilted west and eroded before deposition of the overlying beds now dipping east. occur in traps formed by a combination of structural and stratigraphic circumstances. A block representation of the trap at the Prudhoe Bay field in northern Alaska. it is presumed that the fault is non-sealing. tilted westwards. these beds were folded into a faulted east-west anticline. The difference is believed to be due to clay being smeared into the fault plane. Where a reservoir is full to spillpoint against a fault. Again the range of possibilities is almost infinite. As the more easily found structural traps are running out in much of the world. This vital factor. and truncated by erosion. We may note here one most important consideration. where there is enough of it in the section. possibly even before it . This combination trap is partly structural (the anticline) and partly stratigraphic (beneath the unconformity). The oil is held in the reservoirs by younger shales overlying the erosion surface (Fig.

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

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

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

47 .Petroleum Traps .

Petroleum Traps .48 .

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

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

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

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

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

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

00 4.6 2.0 Pyrolysis Tmax (°C) 420 430 440 450 460 465 470 480 500 500 + 500 + Conodont Alteration Index (CAI) 1 1 1 1. With increasing experience one can also learn to derive important information on thermal histories.50 2. To do this intelligently we must have the ability to develop regional models of organic facies and thermal maturity.3 2.5 2 2 2 3 4 4 5 Correlation of various kerogen-maturity parameters with vitrinite-reflectance (Ro) values .00 3.60 0. and organic facies. we should attempt to corroborate the measured data by other analyses. unconformities and erosional events.00 Thermal Alteration Index (TAI) 2. therefore.8 3. type. and maturity of the organic matter present in the rocks? Satisfactory methods are available in most cases to answer all these questions.2 3.0 3.35 1. rather.4 3.5 3. We should always attempt to extrapolate our measured data over as large an area as possible.00 1.0 4.0 2. Interpretation of source-rock data on a basic level is quite simple.40 0.50 0.80 1. we should not rely on a single analytical technique. Vitrinite Reflectance (%Ro) 0.55 SUMMARY Any source-rock evaluation should attempt to answer three questions: What are the quantity. In some areas one technique may fail completely or may be only partially successful. Whenever possible.8 4.Source Rock Evaluation .20 1.

05 0. The calculated immature H/C ratios are listed in the table on next page.9 3.Source Rock Evaluation .0 3.6 2. This can be done easily by plotting H/C versus TAI. Both the immature H / C ratios and the maceral analysis data need to be scaled to calculate "Total Oil. and then tracing the H/C ratio back to its immature value.66 0.5 1.8 0.7 2.3 1. quality (H /C and %Alginite + Exinite).5 2-2.65 0.7 3. one must first convert the measured. so "Total Oil" can be plotted against "Oil Already Generated.5 2.27 1. refer to the graph on next page.1 3.77 0.33 1.5 0. B) H/C versus TAI for Mauve Well samples." To do this.81 1.7 1.2 1.2 2.8 % Alginite + Exinite 75 80 80 75 80 90 85 75 70 50 45 60 45 40 ? ? Core Cuttings Data are available on quantity (%Corg). presenting the kerogen quality factor as a . and maturity (TAI).5 2.0 2-2.6 2. To use the H /C data. and both should be utilized and examined for possible discrepancies.0 0. A) Calculation of the immature kerogen H/C ratio(at A) from the present-day H/C ratio and vitrinite reflectance data(at P) .75 0.98 0.41 0.22 1.7 1.3 0.2 3.5 0. 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 0.72 0.6 0." Two independent quality measurements have been made.2 Atomic H/C 1.86 0.5 2.15 0.7 2.5 2-2. as shown in Figure B (derived from Figure A). however.07 1.6 2. present-day H/C ratios to the ones that the kerogens had when they were thermally immature.5 1.38 TAI 2.56 EXERCISES Worked out example: Perform a source-rock analysis on the Mauve Well.1 2.

70 1.90 ? ? Quality Factor Quality Factor (from H/ C) (from 1. the H/C ratio gives the lower quality factor. 1500.5 1. Without more knowledge.05 0. The most important point being made here is that these discrepanties must be taken seriously by the interpreter.72 0.35 1.81 1. The prudent interpreter might now ask that some of the H/C ratios be rerun.8 1. and 4500 meters all show differences in the quality factors calculated from the two types of data.77 0.90 0.4 1.05 0.38 Immature H/C 1.2 0. it is impossible to pinpoint the error.22 1.05 0.66 0. 1750.9 1.65 0. In each case.65 0.05 1.6 1.6 1.Source Rock Evaluation . It is apparent that there are serious discrepanties between the H/C and maceral analysis results for several of the samples.35 0.57 function of H/C ratio of the immature kerogen in order to determine the quality factor from H/C. 2300.43 1. and not .7 1.35 0.90 0.05 1.77 0.07 1.98 0.33 1. and would certainly request that the slides made for maceral analysis be reviewed.17 0.60 0.22 1.90 0. In likewise manner (not illustrated here) the quality factor can be determined from maceral analysis data.41 0.90 0.81 1.00 0. If these attempts produced no resolution of the problem.6 1. to check for analytical error.30 1. so some systematic error is likely.07 1.15 0.85 1.60 0.8 ? ? * * * Indicates discrepancy between quality factors calculated from H /C and from maceral analysis. 4000.5 1. 2000. The scaled quality factors are given for each parameter in the table on next page.86 0. The samples at 1000.27 1. however.0 0.9 0.20 1.5 1. such as pyrolysis. Kerogen quality factor as a function of H/C ratio of the immature kerogen.50 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. the interpreter might then decide to try a third technique.75 0.60 ? ? * * * * * 1.

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

00 1.51 0.8 0.9 1.08 0.59 0.5-3.3 2.5 3.18 0.5 2.3 2.41? 1.55 0.5 2.27 0.07 1.46 0.6 4.71 0.5 2.0 2.5 TOC = Total Organic Carbon Bit/TOC = Bitumen/Total organic carbon ? indicates a poor histogram TAI = Thermal Alteration Index Ro = Vitrinite reflectance .0-2.17 0.5-3 2.52 0.2 2. Explain how you resolved any apparent discrepancies.3 1.61 0.49 0.07 0.5-3 2.5-3 2.17 0.5 3-3.5-3 2.000 Type of Sample Cuttings Cuttings TOC 1.09 0.60 0.02 Atomic H/C 0.5 3.5-3 3. EXERCISE Source Rock 2 Perform a source-rock evaluation of the section penetrated in the Turquoise Well.21 0.5 2.12 *TAI and Ro are interconverted according to the correlation table at the end of chapter 7.0-2.59 0.6 0.7 0.21 1.5 0.60 0.86 1.0 2.08 0.11 0.0 2.8 1.2 0.25 0.51 0.03 0.03 0.88 0.5 2.21 1.5 2.08 0.06 0.6 2.91 0.85 0.02 0.0 2.02 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 2.07 0. Source-rock data tor the Turquoise Well Depth (ft) 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500 8000 8500 9000 9500 10.7 0.5 2.66 0.1 0.42 0.Source Rock Evaluation .25 1.08 0.5 2.60 0.0-2.03 0.4 0.09 0.22 0.5 2.66 0.1 2.3 2.91 1.10 0.5 2.91 1.67 0.0 0.0 2.05 0.06 0.27 1.90 0.99 1.5 2.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10 2-2.05 0.0 3-3.51 0.26? 1.3 Bit/TOC 0.0 2.65 0.63 0.49 0.06 0.33? 1.01 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.44 0.65 0.5-3 2.48 Ro 0.

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

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

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

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

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

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

33? 1. In other cases.5-3 2.8 1.000 ft of Upper Miocene before being abandoned at 16.Predicting Thermal Maturity .06 0.5 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.99 1. however.4 0.65 0.67 0. Despite experimental evidence indicating that different kerogens decompose to yield hydrocarbons at different levels of maturity models.27 1.2 0.60 0.1 0.25 1.3 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. and 11.51 0.03 0.48 Ro 0.07 1.5-3 2. EXERCISES EXERCISE Thermal Maturity 1 Perform a source-rock evaluation of the section penetrated in the Turquoise Well. however.49 0.51 0.150 ft in the Middle Miocene.91 0.5 3. Base Pleistocene 2 Ma Base Pliocene 5 Base Upper Miocene 11 Base Middle Miocene 50 Ma .5 2.00 1.5 2.1 2.3 Bit/TOC 0.03 0.27 0.5-3 2.71 0.5 2.02 0.5 2.6 4.0 0.05 0. an accurate interpretation of the ancient geothermal history may be critical.01 0.85 0.5-3 2.52 0. do not utilize different kinetic parameters for the various kerogen types.91 1. Source-rock data tor the Turquoise Well Depth (ft) 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500 8000 8500 9000 9500 10.7 0. we still would have to extrapolate the present somehow into the past.08 0. In many cases.5 3.21 1. The corrected bottom-hole temperature was 270° F. where presentday temperatures are maximum paleotemperatures. even an inaccurate extrapolation into the past may not cause significant problems.22 0.5-3.26? 1.0 3-3. Construct a family of burial-history curves for the well and calculate the present-day TTI at total depth.88 0.8 0.9 1. It penetrated 1000 ft of Pleistocene sediments.08 0.5-3 3. 3500 ft of Pliocene.5 0.21 1. A plausible average surface temperature is 20° C.7 0.17 0.08 0.18 0.5-3 2.06 0.65 0.59 0.66 0.86 1. particularly where Paleozoic rocks are involved.02 Atomic H/C 0.3 2.90 0.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10 2-2.41? 1.91 1. A question of some concern comes from the previously mentioned fact that most of the maturity models treat all types of kerogen identically.5 3-3.66 Even if we could measure present-day subsurface temperatures with perfect accuracy.000 Type of Sample Cuttings Cuttings TOC 1.

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

Highly fractured carbonates overlie the source rock. rich.68 EXERCISE Thermal Maturity 5 Analyze the timing of oil generation in the Pink Well. Time-stratigraphic data are given in the following table.000 23. 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.0° F/100 ft. No other source rocks were noted.65°C/100 m and a surface intercept of 15°C are reasonable for the area.000 8.Predicting Thermal Maturity . "A regional study of the area suggests the probable presence of a thin. No unconformities are recognized within the Paleozoic. Your responsibility is to make a recommendation regarding the nature of hydrocarbons that might be present in die prospect. The following geological summary is available to you. Carboniferous '' Ordovician '' Depth (ft) 7. The reservoir is sealed by a thick salt layer. The geothermal gradient was found to be 1. 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 basin filled at a generally uniform rate from about 300 Ma to 100 Ma. The source rock is thought to be about 300 Ma old. evaluate the prospect. Because of the high operations cost.500 27. No other reservoirs are anticipated. upper management has decided that gas and condensate are not economical. oil-prone source rock at about 4300m depth near the prospect. At that time nearby orogenic activity caused the first traps to be formed during a gradual 1200m uplift lasting until 40 Ma. Erosional removal since the Permian probably totals about 2000 ft. they are in turn overlain at 2750m by a sandstone of excellent reservoir quality. and the surface temperature today is about 15° C." Utilizing the principles of hydrocarbon generation and preservation.500 21.000 18.000 25. Carboniferous '' '' '' '' E. Nearby well control indicates that a geothermal gradient of 3. From 40 Ma to the present about 500m of additional burial occurred. .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.000 11.000 13.

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

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

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

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

to believe that we can do this would be the height of conceit. Use past statistics (number of barrels of oil found on average for each 100m of exploration drilling?) and extrapolate to future drilling.73 Lastly. and as such can be very useful in planning an exploration program. and some may be more appropriate in given circumstances than the others. go for a large but very risky prospect. 6. and we should be on our guard against believing that it is what we shall find (it most categorically is not) or otherwise trying to read too much into it. we can. unless we really have a lot of information (we never have enough!). is a hypothetical figure. Some of these will be successful. and the area under that bit will represent what. or would our money be better spent on drilling a smaller but safer one? The risked reserves. the amount of oil generated. knowing how rich it is. The obvious thing to do is to add together the risked reserves estimates of all the remaining prospects. expelled. for our `best estimate'. remains to be found. and a number of techniques have been employed. the built-in risk factor takes care of this. we are said to be consulting the oracles! All of the above techniques have been used.). sometimes in combination. However. We might look at explored and known parts of the basin. 5. and calculate average quantities of oil per cubic mile of sediment. If we have a reasonable amount of information and control. Many `experts' have scratched their heads over the estimation of undiscovered reserves. This combines in a single estimate. get a number of experts to make their forecasts by whatever technique they prefer and. qualify it by a statistical probability. 1. on average. the two elements of size and chance of success. merely use the average of the figures they produce. all of them are very dodgy . Undiscovered are thus what we hope to find in a prospect area or sedimentary basin in the future.Quantitative Assessment . otherwise we may be doing little more than guessing. however. How now do we estimate what still remains to be discovered over a wider area or even an entire sedimentary basin? There really is no objective way of doing it-but still companies and governments want to know. We could make comparisons between known and unknown basins. then the area under it represents the total volume of oil found to date. or underlying each square mile of surface area. and use the figures for the known also for the unknown ones. If all else fails. Extrapolate this smoothing line out into the future. 3. In a similar vein the amount of oil found world-wide each year from the beginning of the century can be plotted. This kind of plot can be used also for individual basins or for the whole world. on this tack. This figure is extremely imprecise and may be not much more than a guess. Forcing these experts to agree a figure amongst them might refine the approach. the expected reserve estimates from our Monte Carlo simulation multiplied (discounted) by the risk factor (Fig. let us note a number known as the risked reserves. we have to assume that today we can identify and assess all of the prospects that ever will be found in the basin. Adding this to the original reserves will give us what is sometimes called the `ultimate reserves'-a grand total for the basin. then use these figures for the unexplored parts of the basin. Let us look at the more important ones. Should we. However. But we have to admit that. but some will be dry. We could adopt what is known as a `geochemical material balance' approach. There are lots of uncertainties in this but the calculation would be amenable to a Monte Carlo type of simulation. for example. This starts with the volume of mature source rock in the basin and then. this technique may bring us into the right ball-park. it is a pretty wild sort of plot. however. if we draw a smooth line through it to even out the peaks and the troughs. ULTIMATE RESERVES So far we have been talking about a single oil accumulation or a single prospect. and made available for entrapment (the `charge') can be calculated. Delphi was the place in ancient Greece where one went to consult the oracle about one's future. 4. 2. This is known as the Delphi technique.