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

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

significant amounts of organic matter must be deposited and protected from diagenetic destruction. are therefore much more productive than the open ocean. in fact. On the other hand. accumulation of organic-rich sediments cannot occur. In relatively unrestricted marine environments.Organic Facies . Although some destruction of organic material occurs during transport to the depositional environment.000 billion t. only one molecule out of about every one million successfully negotiates the journey from living organism to the gasoline pump. Each of these categories could in turn be further subdivided. In the modern world there are zones of intense seasonal upwelling off the west coasts of California. and general water chemistry. If this deeper water is enriched in nutrients. because under normal circumstances they cannot move upward into the zone of photosynthesis. much of the terrestrial organic material is already highly oxidized when it arrives in the sediments. predators. Only a small fraction of this (10.05%) occurs in economic deposits of fossil fuels. Shallowmarine environments. Total Organic Carbon (TOC) values decrease monotonically through the first 300 meters of burial before levelling out at about 0. Each factor may be dominant under different conditions.000. and that the microbes have given up trying to digest it. There is another zone of seasonal upwelling off the Horn of Africa in the Indian Ocean as a result of . volcanism. Upwelling occurs where bulk movement of surface water away from a particular area allows deeper water to ascend to replace it. watercirculation patterns are particularly important for supplying nutrients and thus controlling productivity. temperature. one of the critical parameters governing productivity. orogeny and erosion. high photosynthetic productivity will occur at the site of upwelling. Although oxidative decay destroys most of the yearly production.000 billion t) dispersed in fine-grained sedimentary rocks. Namibia. Bodies of water naturally develop density stratification. preservation. and dilution. PRODUCTIVITY A partial listing of the many factors influencing productivity would include nutrient availability. suggesting that either depth or organiccarbon content eventually limits diagenesis. because without adequate productivity.7 extensive oxidation of land-plant debris in soils. a great deal of the oxidation of organic matter occurs within the sediments themselves.1%. FACTORS INFLUENCING ORGANIC RICHNESS In order for organic-rich rocks to be formed. The three primary factors influencing the amount of organic matter in a sedimentary rock are productivity. with a preference for horizontal water movement within each density layer. carbonate supply. and Northwest Africa that result from the movement of surface waters away from these coasts. light intensity. or about 0. where there is local recycling of nutrients from decaying organisms and influx of fresh nutrients from terrestrial sources. Depth could interfere with microbial diagenesis when compaction reduces pore sizes and nutrient fluxes in interstitial waters. over vast amounts of geologic time the small fraction that escaped the carbon cycle has built up extremely large quantities of organic matter (20. paleoclimate. Nutrient availability is. When we consider inefficiencies in discovery and recovery. Nutrients dissolved in waters below the photic zone therefore go unutilized. For example. and recycling by organic decay. Only where there is upwelling of subsurface waters can these nutrients return to the photic zone. nutrient availability would depend on such factors as water circulation patterns. Peru. however. Productivity is the logical place to begin our analysis. the low TOC values could indicate that the remaining organic matter has no more nutritional value.

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

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

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

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

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

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

That is. Names and formulas of the ten smallest n-alkanes Methane CH4 CH4 Ethane C2H6 CH3CH3 Propane C3H8 CH3CH2CH3 Butane C4H10 CH3 (CH2)2 CH3 Pentane C5H12 CH3 (CH2)3 CH3 Hexane C6H14 CH3 (CH2)4 CH3 Heptane C7H16 CH3 (CH2)5 CH3 Octane C8H18 CH3 (CH2)6 CH3 Nonane C9H20 CH3 (CH2)7 CH3 Decane C10H22 CH3 (CH2)8 CH3 Carbon atoms need not always bond together in a linear arrangement. in contrast. and carbon-carbon bonds are shown as lines connecting those points. because they are saturated with respect to hydrogen. the names of the other nine simplest n-alkanes are given in the following table. Hydrogen atoms and bonds to hydrogen atoms are not shown at all. but the prefixes denoting the number of carbon atoms in the other alkanes are derived from Greek numbers. Among the most important branched hydrocarbons in organic geochemistry are the isoprenoids. Regular isoprenoids consist of a straight chain of carbon atoms with a methyl branch on every fourth carbon. as in "alkane. Isoprenoids ranging in length from six to forty carbon atoms have been found in petroleum and rocks. All the compounds mentioned above are called saturated hydrocarbons or saturates.Organic Chemistry . is the adjectival form of the word methane. giving rise to a vast number of possible structures. The simplest series of hydrocarbons has linear structures. These cyclic compounds (called naphthenes) are named by counting the number of carbon atoms in the ring and attaching the prefix cyclo." The first four names are irregular. Many unsaturated compounds have carbon-carbon double . which we used earlier. The zigzag configuration illustrated for n-pentane is adopted to show clearly each carbon atom. no more hydrogen can be incorporated into the molecule without breaking it apart. Another important group of hydrocarbons is the unsaturates. Note that the name of each compound ends in -ane. simple inspection shows how mant' hydrogen atoms each carbon atom must have. In the case of 2methylhexane (C7H16) the basic structure is hexane. We have also seen that carbon atoms can be arranged in rings. Other adjectival forms are made by dropping the -ane ending and adding yl (for example. which. The term methyl. We have ahready encountered n-pentane. Because we know that each carbon atom forms four bonds and each hydrogen atom forms one bond. For example. ethyl and propyl). The letter n stands for normal. these molecules are called n-alkanes or nparains. a CH3 (methyl) group is attached to the second carbon atom.14 An even quicker shorthand that uses no letters at all has evolved. are able to combine with additional hydrogen. n-pentane and cyclohexane are represented by the line structures shown below. Branching can occur. Each carbon atom is represented by a point. and indicates that there is no branching in the carbon chain.

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

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

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

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

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

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

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

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

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

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

Many sediments. however. even-carbon homologs predominate as strongly as do the oddcarbon homologs among the n-alkanes. 29. The distributions are quite sharp. Sediments are also known that exhibit a strong preference for n-alkanes having an even number of carbon atoms.25 them insoluble in light solvents. 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). and no preference for either odd. However.or even-carbon homologs is evident. Other compounds. are essentially molecular fossils. SPECIFIC COMPOUNDS Biomarkers. especially 23. marine algae produce n-alkanes that have a maximum in their distribution at C-17 or C22. FACTORS AFFECTING COMPOSITION OF BITUMEN AND PETROLEUM SOURCE AND DIAGENESIS Biomarkers n-Alkanes were among the first biomarkers to be studied extensively. The average of two ranges is taken to minimize bias produced by the generally decreasing n-alkane concentrations with increasing number of carbon atoms. Petroleum. They are. 27. and 31 atoms. where input of terrestrial n-alkanes is minimal and diagenetic conditions are highly reducing. and by their catagenetic formation from long-chain compounds such as fatty acids and alcohols. however. Asphaltenes can thus be removed from oils or bitumens in the laboratory or refinery by adding a light hydrocarbon. we are unable to use it as an "index fossil" for specific organisms. of biological origin. receive contributions of n-alkanes from both terrestrial and marine sources. The most useful biomarkers serve as indicators of the organisms from which the bitumen or petroleum was derived. which are derived from biogenic precursor molecules. In most cases. asphaltene molecules have not been studied in detail. the CPI is 1. or members of the n-alkane series. an abbreviation for biological markers. but their sources are simply no longer recognizable due to diagenetic and catagenetic transformations. In a few cases specific precursor organisms or molecules can be identified. whereas in other instances we may be able to limit the possible precursors to only a few species.) Even-carbon preferences occur principally in evaporitic and carbonate sediments. because the concentration of n-alkanes often decreases with increasing carbon number. (Among the acids and alcohols present in living organisms. CPI values can therefore . Carbon Preference Index. the CPI is greater than 1.0. If odd-carbon homologs predominate. Many other types of organic compounds in crude oils and bitumens are not considered to be biomarkers because they cannot be related directly to biogenic precursors. For the most part n-alkanes present in terrestrial plants have odd numbers of carbon atoms.0. of course. depending upon the species present. although we know for certain that the biomarker molecule is biogenic. or of the diagenetic conditions under which the organic matter was buried. Their n-alkane distributions reflect this mix. In contrast. If the number of odd. or CPI. Many of the compounds and classes of compounds that we find in crude oils and bitumens are called biomarkers. Their high concentration in bitumens and oils is best explained by their existence in plant and algal lipids.and even-carbon members is equal. Because of their molecular complexity and heterogeneity. 25. the lower-carbon homologs are given more weight in the calculation. These n-alkanes are believed to be formed by hydrogenation (reduction) of longchain fatty acids and alcohols having even numbers of carbon atoms. These compounds. and Natural Gas . such as pentane or propane. Another important indication of the origin of n-alkanes is the distribution of individual homologs.Bitumen.

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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.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

cases are known where flowing water has apparently been able totally to flush oil out of an anticlinal trap. The oil-water contact in such a hydrodynamic trap is normally tilted in the direction of water flow. are the more obscure and generally smaller prospects. they are known in a number of parts of the world. essentially anticlinal. The number of structural field of this size may partly reflect the fact that structural traps are easier to find than the others. and the oil will be free to move again. perhaps from rain. This may be one of the reasons why oil accumulations trapped hydrodynamically are rare. There is no structural or stratigraphic closure. is held against an unevenness of its upper surface by water flowing in the opposite direction. HYDRODYNAMIC TRAPS Imagine surface water. a regime of water flow cannot normally be expected to remain constant for long. from our present-day point of view. only for as long as the water keeps coming: dry up the supply of water. is that in most parts of the world the larger anticlines have now been drilled. in say ordinary anticlinal traps.43 was generated. as we do not want to waste the money drilling wells that would miss the oil altogether.Petroleum Traps . but the oil reserves they contain show clearly that generally they are also bigger. What our efforts are increasingly directed towards. Depending on the balance of forces acting on the oil. . Such tilted contacts. This is what has been described as a hydrodynamic trap. Oil. we would have to be careful where we locate and drill our oil production wells. up in the hills and percolating downwards towards a spring. therefore. Note that the oil-water contact is tilted down in the direction of water flow. The trouble.(2-32) THE RELATIVE IMPORTANCE OF TRAPS A review of 200 giant oilfields (those containing 500 million barrels or more) emphasize the importance of structural. are not all that rare. is yet another aspect of the petroleum geology that we have to assess in proposing exploration drilling. In this sort of situation. it may find itself caught against an unevenness of the reservoir surface where there is no conventional trap at all. The timing of trap formation versus oil migration has not always worked out favorably. It is totally dependent on the flow of water and is effective. Oil has found its way into the reservoir and is battling to migrate upwards to the surface against the flow of water. We would recognize this from residual traces of oil in a water-bearing reservoir. entering a reservoir formation. geologically speaking. indicating the former presence of an oil accumulation now lost. A hydrodynamic trap. It is therefore always important to get a handle on the hydrodynamic regime in a reservoir for both exploration and oilfield development purposes. traps in both number and size. Furthermore. or aquifer. of course. attempting to escape to surface up a reservoir.

.

The logs show SP (Self Potential or Spontaneous Potential) on the left and R (Resistivity) on the right.45 EXERCISES EXERCISE 1: The following well logs have been hung on a structural datum.Petroleum Traps .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. multi-interpretable (D). .

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

47 .Petroleum Traps .

Petroleum Traps .48 .

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

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

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

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

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

CAI can actually measure high-grade metamorphism. Although Tmax values are determined objectively. Some laboratories put the onset of maturity at 435° C. resinite. and thus are considered to have good source potential for liquid hydrocarbons. Because vitrinite reflectance is the most popular method of determining maturity. The ultimate limit of oil stability is not known for certain.Source Rock Evaluation . make sure that you have a copy of their equivalency between TAI and Ro. the hydrogen index serves as an indicator of kerogen type. Hydrogen indices above 150 reflect increasing amounts of lipid-rich material. They have excellent potential to generate liquid hydrocarbons. . for most kerogens the onset of oil-generation is taken to be near 0. and the end of liquid-hydrocarbon generation is thought to be at about 1. Because some Cenozoic land plants are richer in resins and waxes than Paleozoic plants.5% Ro. either from terrestrial macerals (cutinite. Interpretation of hydrogen indices for immature kerogens is straightforward.6% Ro. Kerogens with hydrogen indices above 600 usually consist of nearly pure Type I or Type II kerogens. exinite) or from marine algal material. others use 440°.54 values in milligrams per gram of TOC. However. but there are still some minor variations from one laboratory to another. Age of coals is important. because during the Paleozoic the biota was quite different than during the Cenozoic. this generalization has two fallacies: most of the coalfields originally studied were of Paleozoic age. if you are using TAI determinations determined by an analytical laboratory. respectively. Those between 150 and 300 contain more Type III kerogen than Type II and therefore have marginal to fair potential for liquids. Determination of the oil-generation window in a particular section is the objective of most maturity analyses performed on possible source rocks. The correlations among maturity parameters have been fairly well established. Thus. but in most cases is probably not much above 1. most other maturation parameters are related to Ro values. The limits of the oil generation window vary considerably depending upon the type of organic matter being transformed. Because variations in TOC have been removed in the normalizing calculation. Nevertheless. 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. Measured hydrogen indices must be corrected for maturity effects by using a modified van Krevelen diagram as outlined above. some Cenozoic coals should have better potential for generating liquid hydrocarbons.9% Ro. Kerogens with hydrogen indices above about 300 contain substantial amounts of Type II macerals. Conodont Alteration Index (CAI) values ranging from 1 to 5 were tied loosely to vitrinite reflectance and fixed carbon content of coals. and the coals were of bituminous to anthracite rank. A second. less common application is to decide whether oil will be stable in a given reservoir. The normalized S2 and S3 values are called the hydrogen index and the oxygen index. a unified scale for comparing them with Ro values has not been adopted. because they vary with kerogen type as well as maturity. with CAI of 8 reached in a marble. MATURITY Kerogen Parameters. Peak generation is reached near 0.35% Ro. It is particularly difficult to generalize about TAI values because the numerical values of TAI scales have not been standardized among laboratories. 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.

50 0. unconformities and erosional events.00 1.00 3. In some areas one technique may fail completely or may be only partially successful. rather. Interpretation of source-rock data on a basic level is quite simple. type.35 1.5 3. therefore.8 4. and organic facies. Whenever possible.2 3.3 2.00 Thermal Alteration Index (TAI) 2.4 3.60 0. we should not rely on a single analytical technique. Vitrinite Reflectance (%Ro) 0. With increasing experience one can also learn to derive important information on thermal histories.80 1.0 2.8 3. we should attempt to corroborate the measured data by other analyses. To do this intelligently we must have the ability to develop regional models of organic facies and thermal maturity. and maturity of the organic matter present in the rocks? Satisfactory methods are available in most cases to answer all these questions.40 0.5 2 2 2 3 4 4 5 Correlation of various kerogen-maturity parameters with vitrinite-reflectance (Ro) values .Source Rock Evaluation .00 4.6 2.50 2.0 Pyrolysis Tmax (°C) 420 430 440 450 460 465 470 480 500 500 + 500 + Conodont Alteration Index (CAI) 1 1 1 1. We should always attempt to extrapolate our measured data over as large an area as possible.55 SUMMARY Any source-rock evaluation should attempt to answer three questions: What are the quantity.0 4.0 3.20 1.

however.77 0.3 0.75 0. present-day H/C ratios to the ones that the kerogens had when they were thermally immature.81 1.66 0.05 0.38 TAI 2. refer to the graph on next page.7 1.33 1. This can be done easily by plotting H/C versus TAI.15 0.5 0.72 0.9 3. Source-rock data for the Mauve Well Depth (m) 1000 1200 1500 1750 2000 2300 2700 3000 3500 3600 3800 4000 4500 4600 4800 5000 Type of Sample Sidewall Cores %Corg 0.0 0.2 2. B) H/C versus TAI for Mauve Well samples.6 2.5 0. and maturity (TAI).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).5 2-2.1 2.27 1. A) Calculation of the immature kerogen H/C ratio(at A) from the present-day H/C ratio and vitrinite reflectance data(at P) .1 3. quality (H /C and %Alginite + Exinite).3 1.65 0. and both should be utilized and examined for possible discrepancies.6 2. presenting the kerogen quality factor as a . Both the immature H / C ratios and the maceral analysis data need to be scaled to calculate "Total Oil.0 3.5 2.5 1.07 1.0 2-2. The calculated immature H/C ratios are listed in the table on next page.56 EXERCISES Worked out example: Perform a source-rock analysis on the Mauve Well.5 2.6 2.86 0.2 Atomic H/C 1.6 0.5 2." To do this. one must first convert the measured.2 3.5 1.2 1.7 1.Source Rock Evaluation . To use the H /C data. as shown in Figure B (derived from Figure A).7 2.7 3. and then tracing the H/C ratio back to its immature value.7 2.5 2-2.41 0.98 0." Two independent quality measurements have been made.8 0. so "Total Oil" can be plotted against "Oil Already Generated.22 1.

05 1.0 0.8 1.77 0.81 1. such as pyrolysis.35 0. it is impossible to pinpoint the error.43 1.9 0.05 1. and would certainly request that the slides made for maceral analysis be reviewed.30 1.65 0. The prudent interpreter might now ask that some of the H/C ratios be rerun. In each case.5 1. and not .9 1.07 1.90 ? ? Quality Factor Quality Factor (from H/ C) (from 1.35 0.05 0.6 1.22 1.90 0. however. In likewise manner (not illustrated here) the quality factor can be determined from maceral analysis data. the interpreter might then decide to try a third technique. 1750. 4000.4 1.72 0.90 0. Kerogen quality factor as a function of H/C ratio of the immature kerogen. 1500.6 1.70 1.5 1.75 0.2 0.90 0. 2000.20 1.27 1.00 0.60 0.65 0.50 1. It is apparent that there are serious discrepanties between the H/C and maceral analysis results for several of the samples.15 0.60 0.90 0.17 0.57 function of H/C ratio of the immature kerogen in order to determine the quality factor from H/C. 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 most important point being made here is that these discrepanties must be taken seriously by the interpreter.60 ? ? * * * * * 1.98 0.38 Immature H/C 1.22 1.Source Rock Evaluation .81 1.05 0.07 1. The scaled quality factors are given for each parameter in the table on next page. so some systematic error is likely.05 0.6 1. If these attempts produced no resolution of the problem. and 4500 meters all show differences in the quality factors calculated from the two types of data. Without more knowledge.33 1.41 0.85 1.5 1.35 1. to check for analytical error.86 0. 2300.8 ? ? * * * Indicates discrepancy between quality factors calculated from H /C and from maceral analysis.66 0.77 0. the H/C ratio gives the lower quality factor.7 1. The samples at 1000.

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

07 1.03 0.09 0.91 1.85 0.02 0.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10 2-2.10 0.3 1.0-2.91 0.11 0.21 0.71 0.0 0.5-3 2.59 0.7 0.18 0.5 2.3 2.000 Type of Sample Cuttings Cuttings TOC 1.8 0.5 2.5-3 3.67 0.63 0.52 0.66 0.5 2.25 1.21 1.Source Rock Evaluation .06 0.51 0.33? 1.5 2.5 2.27 0.60 0.5 3-3.7 0.00 1.44 0.0 2.8 1. Explain how you resolved any apparent discrepancies.5-3 2.05 0.05 0.5 3.03 0.55 0.17 0.88 0.12 *TAI and Ro are interconverted according to the correlation table at the end of chapter 7.22 0.99 1.5-3 2.09 0.0 3-3.60 0.49 0.17 0. EXERCISE Source Rock 2 Perform a source-rock evaluation of the section penetrated in the Turquoise Well.1 2.48 Ro 0.3 2.3 2.5-3 2.66 0.06 0.59 EXERCISE Source Rock 1 Combine the data from the Blue Well to give a coherent picture of thermal maturity in the section drilled.25 0.49 0.6 4.65 0.5-3 2.5 0.08 0.5-3.5 2.5 2.02 Atomic H/C 0.9 1.61 0.08 0.51 0.0 2.5 2.2 0.5 3.4 0.41? 1.06 0.01 0.0 2.0 2.0-2.3 Bit/TOC 0.59 0.27 1.90 0.02 0.91 1.26? 1.6 0.0 2.08 0.03 0.2 2.5 2.6 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 .42 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 2.86 1.51 0.5 2.21 1.46 0.5 2. Source-rock data tor the Turquoise Well Depth (ft) 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500 8000 8500 9000 9500 10.65 0.1 0.60 0.07 0.0 2.07 0.08 0.

60 9 . however. Furthermore.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. He developed a "Time-Temperature Index" of maturity (TTI) to quantify his method. In some areas there are no well samples available. If no well data are available. however. Part of this problem is a consequence of the limitations we face in attempting to obtain reliable maturity measurements. In this chapter you will learn how to carry out maturity calculations using Lopatin's method and how to use Lopatin's method in exploration. The 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. perhaps from thicknesses of exposed sections nearby. If our measurements indicate that a rock has already passed through the oil-generation window. Time-stratigraphic data are usually available as formation tops and ages obtained by routine biostratigraphic analysis of well cuttings. 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. maturity measurements can only tell us about present-day maturity levels. indeed. nor do we know at what depth or temperature it occurred. These considerations are important when we want to compare timing of generation. In most cases. in frontier basins there may not be a single well within tens or hundreds of kilometers. expulsion. In 1971. If no subsurface data are available. In order to circumvent these difficulties. This assumption is a logical and defensible one. we still have no clue as to when oil generation occurred. for it is in keeping with the predictions of chemical-kinetic theory. 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. We need data that will enable us to construct a time stratigraphy for the location of interest and to specify its temperature history. Even in maturely explored basins the samples available for analysis often do not give a representative picture of maturity in the basin. CONSTRUCTION OF THE GEOLOGICAL MODEL One of the advantages of Lopatin's method is that the required input data are very simple and easy to obtain. estimates can be made. These two factors are interchangeable: a high temperature acting over a short time can have the same effect on maturation as a low temperature acting over a longer period. It has even been suggested that maturity models are more accurate than measured data for determining the extent of petroleum generation. methods have been developed for calculating maturity levels where measurements are not available. . a time stratigraphy can sometimes be constructed using seismic data. early efforts to take both time and temperature into account in studying the process of hydrocarbon generation were only partially successful because of the mathematical difficulties inherent in allowing both time and temperature to vary independently. Nevertheless. and migration with timing of structure development or trap formation. measured maturity data are of limited value in exploration.Predicting Thermal Maturity . especially if the seismic reflectors can be tied to well data.

. The subsurface temperature must be specified for every depth throughout the relevant geologic past. burial-history curves represent our best understanding of the geological history of an area. Connecting the six dots completes the burial-history curve. representing the initial deposition of the sediment (point A) and its position today (point B). which was constructed from the time stratigraphy for the Tiger well. by 80 Ma the sediment had been buried to a depth of 900 m (point C). In cases where biostratigraphic data are available and deposition has been reasonably continuous. Neglecting compaction effects. a burial-history curve may represent only a rather uncertain guess. In cases where biostratigraphic data are lacking or where the sediments have had complex tectonic histories. sediment has accumulated continuously but at varying rates since deposition of the oldest rock 100 million years ago (Ma). for example. Using the other control points from the input table. Suppose further that local weather records indicate a yearly average surface temperature of 19° C. The next step is to locate the first control point from the time-stratigraphic data on the input table. In the Tiger well. The burial-history curve was constructed in the following way: two points. if constructed as carefully as the data permit. and that a corrected bottom-hole temperature of 133° C was obtained at 3800 m. are marked on the age-depth plot. we can construct the complete figure. This geometry is a direct consequence of ignoring compaction effects. Suppose. Using these present-day data and extrapolating them into the past. 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. we can construct the temperature grid with equally spaced isotherms parallel to the earth's surface.61 BURIAL-HISTORY CURVES Implementation of Lopatin's method begins with the construction of a burial-history curve for the oldest rock layer of interest. Burial-history curves are based on the best information available to the geologist. TEMPERATURE HISTORY The next step is to provide a temperature history to accompany our burial-history curve.(9-2) All of the shallower and younger horizons will have burial-history curves whose segments are parallel to those of the oldest horizon. Nevertheless. it is easy to construct burial-history curves with a high level of confidence.Predicting Thermal Maturity . that the Tiger well was logged. An example is shown in the following figure. Today the rock is at a depth of 3700 m.

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

63 organic maturation by causing important perturbations in subsurface temperatures. increases exponentially with increasing temperature. but the distance between the two lines which bracket the erosion. Lopatin defined each time factor simply as the length of time. expressed in millions of years. more work is required before we will understand fully how thrusting influences hydrocarbon generation and destruction. Total maturity is calculated by summing the incremental maturity added in each succeeding temperature interval. Temperature intervals are defined by successive isotherms spaced 10° C apart. we must paste them together. This intervalTTI value represents the maturity acquired by the rock in that temperature interval during the time . for any temperature interval the temperature factor (?) was given by: ? = 2n The temperature-factor thus reflects the exponential dependence of maturity on temperature. Multiplying the time factor for any temperature interval by the appropriate temperature-factor for that interval gives a product called the Time-Temperature Index of maturity (TTI). Index values increase or decrease regularly at higher or lower temperatures intervals. Because the rate of maturation was assumed to increase by a factor of two for every 10° C rise in temperature. Testing of his model and the successful application of Lopatin's method in numerous published examples have confirmed the general validity of this assumption.(9-12) CALCULATION OF MATURITY Once the burial-history curves and temperature grids have been constructed. in contrast. respectively. The temperature factor. decreases by 1000 m.400 cal/mol will approximately double with every 10° C increase in reaction temperature. In order to carry out maturity calculations conveniently. Loss of 1000 m of section by erosion during an uplift event lasting from 70 Ma to 60 Ma. Lopatin chose the 100°-110° C interval as his base and assigned to it an index value n = 0. Studies in the Overthrust Belt of Wyoming indicate that a slow-equilibration model is superior to a simple model invoking rapid thermal equilibration. spent by the rock in each temperature interval. Individual burial-history curves remain parallel. However. Intersections of the burial-history curve with each isotherm are marked with dots.Predicting Thermal Maturity . Lopatin (1971) assumed that the rate of maturation followed this doubling rule. These dots define the time and temperature intervals that we shall use in our calculations. Chemical reaction-rate theory states that the rate of a reaction occurring at 90° C (a reasonable average for oil generation) and having a pseudoactivation energy of 16. we need to define both a time factor and a temperature factor for each temperature interval. A Time interval is the length of time that the rock has spent in a particular temperature interval. Now we can carry out the maturity calculations.

In the adjoining table interval-TTI values and total-TTI values up to the present day are calculated. If we put a cake in a cold oven and turn the oven on. On the other hand. followed by a nonerosional depositional hiatus for the last 50 Ma. even if a rock cools down. If we turn off the oven but leave the cake inside.Predicting Thermal Maturity . baking will continue. finally. although at increasingly slower rates. A good analogy can be drawn between oil generation and baking. we simply sum all the interval-TTI values for the rock. In D 40 Ma of rapid burial to a depth of 4000 m was followed by a hiatus lasting 30 Ma and. if we forget about the cake when the oven is hot and let it burn. where the time factors and yfactors for each temperature interval are shown on the burial-history curve. we cannot "unburn" it. Figure C shows rapid burial during the first 20 Ma. Four of the many paths by which an 80-Ma-old rock could have reached a present burial depth of 3000 m is indicated in the figure (9-21). by 10 Ma of uplift and erosion. it can never go backward because interval-TTI values are never negative. but quite rapid in the last 10 my. Furthermore. To obtain total maturity. the specific burial history of a rock can strongly affect its maturity. . no matter how much or how rapidly we cool it down. maturity continues to increase (albeit at a slower rate) because y is always greater than zero. In A the rock was buried at a constant rate for its entire 80-my history.(9-20) It is also possible to determine the total-TTI value at any time in the past simply by stopping the calculation at that time.64 given. FACTORS AFFECTING THERMAL MATURITY Because maturity is affected by both baking time and baking temperature. TTI values differ appreciably among these four scenarios. the cake will bake slowly at first but will bake faster and faster as the temperature rises. In B burial was very slow during the first 70 Ma of the rock's existence. as the oven cools down. Maturity always increases. The first step in calculating TTI is illustrated in the following figure.

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

8 1.27 0.3 Bit/TOC 0.5 2.03 0.25 1.22 0.2 0. we still would have to extrapolate the present somehow into the past.0 0.88 0. EXERCISES EXERCISE Thermal Maturity 1 Perform a source-rock evaluation of the section penetrated in the Turquoise Well.000 Type of Sample Cuttings Cuttings TOC 1.9 1. Source-rock data tor the Turquoise Well Depth (ft) 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500 8000 8500 9000 9500 10.02 Atomic H/C 0.91 1.000 ft of Upper Miocene before being abandoned at 16.Predicting Thermal Maturity .5-3.5-3 2.02 0.1 2.59 0.91 1.06 0.67 0. Base Pleistocene 2 Ma Base Pliocene 5 Base Upper Miocene 11 Base Middle Miocene 50 Ma .21 1. The corrected bottom-hole temperature was 270° F.60 0.05 0.07 1.5 3. even an inaccurate extrapolation into the past may not cause significant problems.5-3 3. It penetrated 1000 ft of Pleistocene sediments.41? 1.5 0.5 2.7 0.85 0.1 0. where presentday temperatures are maximum paleotemperatures.08 0.5 2. Construct a family of burial-history curves for the well and calculate the present-day TTI at total depth. particularly where Paleozoic rocks are involved. an accurate interpretation of the ancient geothermal history may be critical.06 0.00 1.91 0.7 0. A question of some concern comes from the previously mentioned fact that most of the maturity models treat all types of kerogen identically.8 0. In other cases.66 0.65 0. however.21 1. Despite experimental evidence indicating that different kerogens decompose to yield hydrocarbons at different levels of maturity models.08 0.3 2.5-3 2.150 ft in the Middle Miocene.18 0.52 0.26? 1. In many cases. 3500 ft of Pliocene.5 3.49 0.17 0.5-3 2.01 0. however. and 11.65 0.08 0.6 4.51 0. do not utilize different kinetic parameters for the various kerogen types. A plausible average surface temperature is 20° C.99 1.03 0. In such cases we should be very careful about using predicted maturities unless we have some independent confirmation of the validity of our model from a comparison with measured maturity data.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.48 Ro 0.33? 1.0 3-3.66 Even if we could measure present-day subsurface temperatures with perfect accuracy.3 1.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10 2-2.5-3 2.5 3-3.4 0.90 0.27 1.86 1.71 0.5-3 2.5 2.51 0.

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

000 13.000 8. Erosional removal since the Permian probably totals about 2000 ft. Top of Permian Virgil Missouri Des Moines Atoka Morrow Mississippian Kinderhook Sylvan Arbuckle Age (Ma) 230 280 288 296 304 309 320 340 425 470 Period Permian 0 L. The reservoir is sealed by a thick salt layer.500 21. From 40 Ma to the present about 500m of additional burial occurred. The basin filled at a generally uniform rate from about 300 Ma to 100 Ma.65°C/100 m and a surface intercept of 15°C are reasonable for the area. At that time nearby orogenic activity caused the first traps to be formed during a gradual 1200m uplift lasting until 40 Ma. oil-prone source rock at about 4300m depth near the prospect. rich. Carboniferous '' '' '' '' E. they are in turn overlain at 2750m by a sandstone of excellent reservoir quality.000 23.0° F/100 ft. No other source rocks were noted. Nearby well control indicates that a geothermal gradient of 3. "A regional study of the area suggests the probable presence of a thin. Highly fractured carbonates overlie the source rock. and the surface temperature today is about 15° C. Because of the high operations cost. Time-stratigraphic data are given in the following table. No unconformities are recognized within the Paleozoic. . No other reservoirs are anticipated. 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.500 27. Your responsibility is to make a recommendation regarding the nature of hydrocarbons that might be present in die prospect.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. upper management has decided that gas and condensate are not economical. Carboniferous '' Ordovician '' Depth (ft) 7.68 EXERCISE Thermal Maturity 5 Analyze the timing of oil generation in the Pink Well." Utilizing the principles of hydrocarbon generation and preservation.000 25. The following geological summary is available to you. The geothermal gradient was found to be 1. evaluate the prospect.000 18. The source rock is thought to be about 300 Ma old.Predicting Thermal Maturity .

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

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

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

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

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

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