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

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

Productivity is the logical place to begin our analysis.1%. Depth could interfere with microbial diagenesis when compaction reduces pore sizes and nutrient fluxes in interstitial waters. There is another zone of seasonal upwelling off the Horn of Africa in the Indian Ocean as a result of . and recycling by organic decay. with a preference for horizontal water movement within each density layer. because under normal circumstances they cannot move upward into the zone of photosynthesis. Only a small fraction of this (10. and dilution. because without adequate productivity. Each of these categories could in turn be further subdivided.Organic Facies .000. watercirculation patterns are particularly important for supplying nutrients and thus controlling productivity. Although oxidative decay destroys most of the yearly production. accumulation of organic-rich sediments cannot occur. suggesting that either depth or organiccarbon content eventually limits diagenesis. Nutrients dissolved in waters below the photic zone therefore go unutilized. For example. volcanism. high photosynthetic productivity will occur at the site of upwelling. Total Organic Carbon (TOC) values decrease monotonically through the first 300 meters of burial before levelling out at about 0. Nutrient availability is. Only where there is upwelling of subsurface waters can these nutrients return to the photic zone. The three primary factors influencing the amount of organic matter in a sedimentary rock are productivity. carbonate supply.000 billion t) dispersed in fine-grained sedimentary rocks. predators. nutrient availability would depend on such factors as water circulation patterns. and Northwest Africa that result from the movement of surface waters away from these coasts. significant amounts of organic matter must be deposited and protected from diagenetic destruction. the low TOC values could indicate that the remaining organic matter has no more nutritional value. light intensity. however. FACTORS INFLUENCING ORGANIC RICHNESS In order for organic-rich rocks to be formed. Although some destruction of organic material occurs during transport to the depositional environment. over vast amounts of geologic time the small fraction that escaped the carbon cycle has built up extremely large quantities of organic matter (20. or about 0.7 extensive oxidation of land-plant debris in soils. in fact. a great deal of the oxidation of organic matter occurs within the sediments themselves. PRODUCTIVITY A partial listing of the many factors influencing productivity would include nutrient availability. In the modern world there are zones of intense seasonal upwelling off the west coasts of California.000 billion t.05%) occurs in economic deposits of fossil fuels. temperature. preservation. one of the critical parameters governing productivity. Upwelling occurs where bulk movement of surface water away from a particular area allows deeper water to ascend to replace it. In relatively unrestricted marine environments. and that the microbes have given up trying to digest it. are therefore much more productive than the open ocean. On the other hand. Namibia. where there is local recycling of nutrients from decaying organisms and influx of fresh nutrients from terrestrial sources. Shallowmarine environments. paleoclimate. When we consider inefficiencies in discovery and recovery. If this deeper water is enriched in nutrients. Each factor may be dominant under different conditions. and general water chemistry. orogeny and erosion. Bodies of water naturally develop density stratification. much of the terrestrial organic material is already highly oxidized when it arrives in the sediments. only one molecule out of about every one million successfully negotiates the journey from living organism to the gasoline pump. Peru.

the simplest way to limit oxidation is to limit the supply of oxygen. Its presence in . especially of woody origin. and all the other factors that influence upwelling loci is severely limited. diagenesis is restricted to anaerobic processes. At dissolved oxygen levels below about 0. At lower levels of dissolved oxygen. Of these. Such models are interesting. landmasses. Thus if anoxia can develop. Theoretical models have been developed to predict upwelling (and consequent productivity) in ancient seas from input data on continental configurations. microorganisms that utilize materials like sulfate or nitrate ions instead of molecular oxygen as electron acceptors in their metabolic processes. its use in practice has been expanded to include very low oxygen levels as well. and because most biological oxidation processes require molecular oxygen. and are usually limited in scope by the availability of sulfate or nitrate. TOC values alone must therefore be used with caution.2 mL/L. the zone where oxygen falls below 0. There are. We call the zone in which oxygen contents are high the oxic zone.5 mL/L). much oxic sediment also contains large amounts of organic matter.2-0. and may in fact prove useful in future exploration efforts.5 milliliters (mL) per liter (L)). These anaerobic processes are inefficient compared with aerobic diagenesis. PRESERVATION The principal control on organic richness is the efficiency of preservation of organic matter in sedimentary environments. Processes that occur in these two zones are called aerobic and anaerobic. soils. Secondly. if on the average only 1% of organic matter is preserved. the accuracy with which we can reconstruct continental positions. Anoxic sediments are not always easy to recognize. because marine organic matter is consumed preferentially by organisms. respectively. Three factors affect the preservation (or destruction) of organic matter: the concentration and nature of oxidizing agents. Anoxic sediments always contain elevated TOC values (generally above 2% and always above 1% ). All these areas exhibit high productivity when upwelling occurs. the type of organic matter deposited. because when the availability of oxygen is limited.2 mL/L. although some species can tolerate extremely low oxygen levels (0. The presence of undegraded marine organic material is a strong indication of anoxia. some problems associated with their application. paleoclimatic conditions. productivity is probably not as important a factor as preservation. However. because some of the commonly used indicators of anoxia may be misleading. The term dysaerobic has been used to describe processes occurring in the transitional zone (0.2 mL/L is called the anoxic zone. wind and water circulation patterns. First.8 monsoonal winds that drive surface waters away from the coast. essentially the only viable organisms are those that we call anaerobes." hut because of the radical change in biota that occurs at about 0. After all. especially in the Palaeozoic. increasing preservation rates is a very efficient way to increase organic richness.Organic Facies . ANOXIA. and we could coin the term dysoxic to describe the zone itself. There are many more organic-rich facies resulting from excellent preservation than from extremely high productivity. and sediments is biological. The term "anoxic" literally means "having no oxygen. Because most of the oxidation occurring in the water column. preservation of organic matter will be much enhanced. All large organisms require oxygen in order to live. however. and paleoclimates. and the sediment-accumulation rate. oxidizing agents are probably the most crucial factor. many species disappear. Anoxia is of tremendous importance in the preservation of organic matter in sediments. the remaining individuals often become dwarfed in an effort to survive in a hostile environment.

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

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

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

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

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

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

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

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

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

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

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

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

thus allowing us to judge the extent to which kerogen maturation has proceeded. II. There is a steady color progression yellow-goldenorange-light brown-dark brownblack as a result of polymerization and aromatization reactions. including the Miocene Monterey Formation of southern California. but it also states that at any temperature above absolute zero reactions will be occurring at some definable rate. All kerogens become increasingly aromatic and depleted in hydrogen and oxygen during thermal maturation. is to monitor hydrocarbon generation. because time also plays a role. The more hydrogen a kerogen contains. As we saw earlier. These reactions are intimately related to important changes in the chemical structure of kerogen. Furthermore. the cracking of any organic molecule requires hydrogen. the chemical process of maturation never stops completely. even if drastic decreases in temperature occur. In contrast. the rates of catagenesis are generally not important at temperatures below about 70° C. in most cases decreases of temperature in excess of about 20°-30° C due to subsurface events or erosional removal will cause the rates of catagenesis to decrease so much that it becomes negligible for practical purposes. EFFECTS OF MATURATION ON KEROGENS Kerogen undergoes important and detectable changes during catagenesis and metagenesis. much as a cookie browns during baking. 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.Kerogen . Because many of the light product molecules are rich in hydrogen. The real reason for following kerogen catagenesis. however. and III kerogens will therefore be very similar chemically. The composition of the products (bitumen. Kerogen particles become darker during catagenesis and metagenesis. after hydrogen loss is well advanced. Nitrogen loss occurs primarily during late catagenesis or metagenesis. It is impossible to set precise and universal temperature limits for catagenesis. This complex interplay between the effects of time and temperature on maturity is discussed in a later chapter. and gas) will be discussed in a following chapter. Some of these changes can be measured quantitatively. Chemical reaction-rate theory requires that the rates of reactions decrease as temperature decreases. In the late stages of maturity. Furthermore. high-sulfur oils found in a number of areas. Old rocks will often generate hydrocarbons at significantly lower temperatures than young rocks. much of the sulfur is lost in the earliest stages of catagenesis. but they are not necessarily identical with hydrocarbon generation. it is also true that other changes in kerogen properties have little or nothing to do with it. Although it is obvious that many measurable changes in kerogens are related to hydrocarbon generation. Nitrogen and sulfur are also lost from kerogens during catagenesis. simply because the longer time available compensates for lower temperatures. of course. provided that the hydrogen content of the kerogen was known prior to the onset 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 residual kerogen gradually becomes more aromatic and hydrogen poor as catagenesis proceeds. For practical purposes. possessing essentially no remaining hydrocarbon generative capacity. There is therefore no necessary cause-and-effect relationship . Kerogen maturation is not a reversible process-any more than baking a cake is reversible. 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. as evidenced by low maturity.21 This chapter will focus on those changes in the residual kerogen that accompany catagenesis. oil. and thus are not necessarily valid indicators of hydrocarbon generation. the more hydrocarbons it can yield during cracking. Types I.

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

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

Bitumen and petroleum compositions can also be used as tools in correlating samples with each other. Much of this variety is related to source-rock facies and the composition of the kerogens that generated the bitumens. Heavier aromatic and naphthenoaromatic hydrocarbons. This chapter will compare and contrast bitumen and petroleum compositions and examine the factors responsible for the observed differences. and cyclics. like benzene and toluene. are more commonly studied. however. and resins. while others are only trace contributors. triterpanes. Major compositional changes occur in going from bitumen to petroleum. Reservoir transformations in some cases greatly affect oil composition and properties. A second fraction consists of aromatic hydrocarbons and some light sulfur-containing compounds. We also do not know how much of the change involves chemical reactions. branched hydrocarbons (including isoprenoids). and form complexes with molecular weights of perhaps 50.000. NSOs. Some of these are present in relatively large quantities. There is no doubt that they are related. Petroleum. Few of these heterocompounds have been studied carefully.Bitumen. Most of the NSO compounds appear in the remaining two fractions. The lighter of these fractions. and Natural Gas INTRODUCTION Petroleum obtained from reservoir rocks and bitumen extracted from fine-grained rocks have many similarities. but these compounds are lost from bitumens during evaporation of the solvent used in extracting the bitumen from the rock. and how much is due to physical separation of chemical compounds having very different properties. Each of the fractions contains certain types of chemical compounds. Both bitumens and petroleums exhibit a wide range of compositions. Saturated hydrocarbons are the most thoroughly studied of the components of petroleum and bitumen because they are the easiest to work with analytically. However. Asphaltenes tend to aggregate into stacks because of their planarity. and Natural Gas - 5 . and steranes. The large sizes of asphaltene units render . Maturity also exerts control over bitumen and petroleum composition. bitumen is almost universally accepted as the direct precursor for petroleum. we must separate the characteristics related to kerogen composition from those related to the transformation of bitumen to petroleum and from those related to changes occurring in reservoirs. but we are not certain whether they occur mainly within the source rock or during migration through the reservoir rock. have been studied in petroleums. contains a wide variety of small and medium-sized molecules with one or more heteroatoms. variously called polars. COMPOUNDS PRESENT IN BITUMEN AND PETROLEUM GENERAL CLASSES OF COMPOUNDS Both bitumen and petroleum contain a very large number of different chemical compounds. indeed. many unanswered questions remain about the processes that transform bitumen into petroleum. The final fraction contains very large. Petroleum. particularly those derived from diterpanes.24 Bitumen. Light aromatic hydrocarbons. In order to understand bitumen and petroleum compositions and to use them for exploration. highly aromatic asphaltene molecules that are often rich in heteroatoms. but they also exhibit many important differences. Such correlations can be particularly useful in establishing genetic relationships among samples. The influence of the lithologies of source and reservoir rocks on these compositional changes is poorly understood. n-alkanes. we first separate a crude oil or a bitumen into several fractions having distinct properties. One fraction consists mainly of saturated hydrocarbons. In order to investigate the individual compounds present.

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

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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.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

.

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

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

47 .Petroleum Traps .

Petroleum Traps .48 .

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

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

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

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

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

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

50 2.0 4.2 3. Vitrinite Reflectance (%Ro) 0.8 4.4 3.5 3.0 3. and organic facies. In some areas one technique may fail completely or may be only partially successful. unconformities and erosional events.35 1. and maturity of the organic matter present in the rocks? Satisfactory methods are available in most cases to answer all these questions.0 Pyrolysis Tmax (°C) 420 430 440 450 460 465 470 480 500 500 + 500 + Conodont Alteration Index (CAI) 1 1 1 1. type. we should not rely on a single analytical technique. With increasing experience one can also learn to derive important information on thermal histories.55 SUMMARY Any source-rock evaluation should attempt to answer three questions: What are the quantity.60 0.80 1.00 1.20 1. therefore.40 0. rather.0 2.8 3.50 0. Whenever possible.6 2.5 2 2 2 3 4 4 5 Correlation of various kerogen-maturity parameters with vitrinite-reflectance (Ro) values . we should attempt to corroborate the measured data by other analyses.Source Rock Evaluation .00 4.00 3.00 Thermal Alteration Index (TAI) 2.3 2. Interpretation of source-rock data on a basic level is quite simple. To do this intelligently we must have the ability to develop regional models of organic facies and thermal maturity. We should always attempt to extrapolate our measured data over as large an area as possible.

2 Atomic H/C 1.0 3. The calculated immature H/C ratios are listed in the table on next page.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). This can be done easily by plotting H/C versus TAI.98 0. as shown in Figure B (derived from Figure A).6 2.72 0. and both should be utilized and examined for possible discrepancies.66 0.7 2.86 0.1 2.41 0. and maturity (TAI).1 3.6 2.05 0. so "Total Oil" can be plotted against "Oil Already Generated. and then tracing the H/C ratio back to its immature value.7 2.5 2-2. refer to the graph on next page. one must first convert the measured.5 0. B) H/C versus TAI for Mauve Well samples.0 0. presenting the kerogen quality factor as a .7 3.6 0." To do this.Source Rock Evaluation .5 0.7 1.5 2.7 1.5 2.0 2-2.56 EXERCISES Worked out example: Perform a source-rock analysis on the Mauve Well.77 0.75 0.5 1. however. present-day H/C ratios to the ones that the kerogens had when they were thermally immature. A) Calculation of the immature kerogen H/C ratio(at A) from the present-day H/C ratio and vitrinite reflectance data(at P) .81 1." Two independent quality measurements have been made.22 1. quality (H /C and %Alginite + Exinite).6 2.2 1.8 0.2 3.15 0.38 TAI 2.33 1.3 0. To use the H /C data.07 1.9 3.5 2.5 1.5 2-2.2 2. Both the immature H / C ratios and the maceral analysis data need to be scaled to calculate "Total Oil. 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 0.3 1.27 1.65 0.

6 1.72 0.Source Rock Evaluation . In each case. and would certainly request that the slides made for maceral analysis be reviewed.65 0. so some systematic error is likely. The most important point being made here is that these discrepanties must be taken seriously by the interpreter.17 0.05 0.07 1.05 0.60 0.5 1.38 Immature H/C 1.2 0.50 1.70 1.77 0.85 1. 4000.57 function of H/C ratio of the immature kerogen in order to determine the quality factor from H/C.5 1. It is apparent that there are serious discrepanties between the H/C and maceral analysis results for several of the samples. it is impossible to pinpoint the error.9 0.98 0.35 0. 1500.90 0. the interpreter might then decide to try a third technique.60 ? ? * * * * * 1.05 1. 2300.30 1.00 0. The scaled quality factors are given for each parameter in the table on next page.05 0.6 1.0 0.81 1.4 1. Scaled Quality Data tor Mauve Well Samples Depth (m) macerals) 1000 1200 1500 1750 2000 2300 2700 3000 3500 3600 3800 4000 4500 4600 4800 5000 Measured H/C 1.27 1. In likewise manner (not illustrated here) the quality factor can be determined from maceral analysis data.35 1.90 0.15 0.90 ? ? Quality Factor Quality Factor (from H/ C) (from 1.86 0.35 0.22 1. If these attempts produced no resolution of the problem. the H/C ratio gives the lower quality factor.75 0.05 1.33 1.8 ? ? * * * Indicates discrepancy between quality factors calculated from H /C and from maceral analysis.90 0.9 1.07 1.41 0. Kerogen quality factor as a function of H/C ratio of the immature kerogen.20 1.65 0.90 0. and not .43 1. The samples at 1000. The prudent interpreter might now ask that some of the H/C ratios be rerun. and 4500 meters all show differences in the quality factors calculated from the two types of data.5 1.66 0. 1750.60 0.77 0.22 1. however. Without more knowledge.8 1. to check for analytical error.7 1. such as pyrolysis.6 1. 2000.81 1.

One can say little. therefore. "Total Oil" and "Oil Already Generated" profiles are plotted in above figure. In fact. Most of the discrepanties among the different quality factors turn out to be unimportant. except for the two deepest samples. It may be necessary occasionally to offer two alternative interpretations without choosing between them. because sourcerock potential is not good for most of the section. "Total Oil" values are generally unexciting. The relative organic richness of the blackened samples below 4600 meters makes them interesting for further investigation. "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. "Total Oil" and "Oil Already Generated" profiles tor the Mauve Well.58 be overlooked or swept under the rug. 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. Let us take this last approach to this problem.Source Rock Evaluation . 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. and the H/C ratios are not helpful because the maceral types cannot be ascertained from such low H/C values. These two kerogens are highly mature and quite black. The only sample where the discrepancy is significant is that from 2000 meters. Future exploratory activity could include an attempt to find such a section. The rest of the section shows a good correspondente between the two parameters. about the oil-source history of the section below 4600 meters. although the section between 2000 and 3500 meters shows fairly good potential. . Finally.

03 0.59 0.71 0.60 0.3 2.6 0.91 1.17 0.21 0.7 0.3 1.59 0.5 3-3.65 0.5-3 2.18 0.5 2.3 2.55 0.8 1.5 2.59 EXERCISE Source Rock 1 Combine the data from the Blue Well to give a coherent picture of thermal maturity in the section drilled.6 2.46 0.03 0.07 0.09 0.66 0.91 1.02 0.44 0.3 2.22 0.25 1.67 0.2 2.49 0.90 0.5 2.63 0.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10 2-2.60 0.5 2.1 2.21 1. Thermal-maturity data for the Blue Well Depth (ft) TAI Ro Bitumen/TOC 1000 1200 1500 2000 2300 2600 3000 3200 3400 3700 4000 4200 4800 5000 5200 5400 5700 6000 2.08 0.0 2.48 Ro 0.51 0. EXERCISE Source Rock 2 Perform a source-rock evaluation of the section penetrated in the Turquoise Well.9 1.60 0.91 0.05 0.5 2.99 1.21 1.41? 1.10 0.06 0.0 3-3.0 2. Explain how you resolved any apparent discrepancies.49 0.17 0.0-2.0 2.07 1.5 2.06 0.0 2.Source Rock Evaluation .09 0.0 2.5 3.5 3.5 2.08 0.5-3 2.27 0.33? 1.11 0.5 2.3 Bit/TOC 0.5 0.5 2.5 2.5-3 2.02 0.08 0.5-3 3.8 0.7 0.51 0.6 4.88 0.85 0.00 1.07 0.06 0.5-3 2.66 0.42 0.03 0.02 Atomic H/C 0.51 0.0-2.65 0.27 1.25 0.5-3 2.5 2. Source-rock data tor the Turquoise Well Depth (ft) 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500 8000 8500 9000 9500 10.0-2.0 0.5-3.52 0.26? 1.01 0.61 0.0 2.000 Type of Sample Cuttings Cuttings TOC 1.08 0.1 0.5 TOC = Total Organic Carbon Bit/TOC = Bitumen/Total organic carbon ? indicates a poor histogram TAI = Thermal Alteration Index Ro = Vitrinite reflectance .2 0.12 *TAI and Ro are interconverted according to the correlation table at the end of chapter 7.86 1.05 0.4 0.

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

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

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

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

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

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

08 0.9 1.5 3.86 1. Despite experimental evidence indicating that different kerogens decompose to yield hydrocarbons at different levels of maturity models.3 Bit/TOC 0.25 1.000 Type of Sample Cuttings Cuttings TOC 1.67 0.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10 2-2. In many cases.5 3.5 2.5-3 2.51 0.03 0.01 0.85 0.91 0.6 4. A question of some concern comes from the previously mentioned fact that most of the maturity models treat all types of kerogen identically.07 1.7 0. however.5-3 2. we still would have to extrapolate the present somehow into the past. It penetrated 1000 ft of Pleistocene sediments.91 1.48 Ro 0.000 ft of Upper Miocene before being abandoned at 16.Predicting Thermal Maturity . A plausible average surface temperature is 20° C.66 Even if we could measure present-day subsurface temperatures with perfect accuracy.59 0.41? 1.5-3 2.5 3-3.0 0. where presentday temperatures are maximum paleotemperatures.08 0.5-3.5 0.65 0.17 0. however.1 2.8 0.33? 1.3 2.00 1.49 0. do not utilize different kinetic parameters for the various kerogen types.27 1. and 11.03 0. an accurate interpretation of the ancient geothermal history may be critical.06 0.65 0.0 3-3.99 1.66 0.91 1.71 0.27 0.5-3 2. EXERCISES EXERCISE Thermal Maturity 1 Perform a source-rock evaluation of the section penetrated in the Turquoise Well. The corrected bottom-hole temperature was 270° F.02 Atomic H/C 0. Construct a family of burial-history curves for the well and calculate the present-day TTI at total depth.02 0.4 0.5-3 2. 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.3 1.90 0.2 0.150 ft in the Middle Miocene.88 0. 3500 ft of Pliocene.51 0.5 2.5 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.7 0. Base Pleistocene 2 Ma Base Pliocene 5 Base Upper Miocene 11 Base Middle Miocene 50 Ma .08 0.18 0.05 0.5-3 3.5 2.21 1.26? 1. even an inaccurate extrapolation into the past may not cause significant problems.5 2. particularly where Paleozoic rocks are involved.21 1.52 0. Source-rock data tor the Turquoise Well Depth (ft) 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500 8000 8500 9000 9500 10.22 0.8 1.1 0. In other cases.60 0.06 0.

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

000 25. The reservoir is sealed by a thick salt layer. Time-stratigraphic data are given in the following table.500 21.68 EXERCISE Thermal Maturity 5 Analyze the timing of oil generation in the Pink Well.500 27. Carboniferous '' Ordovician '' Depth (ft) 7. The source rock is thought to be about 300 Ma old. From 40 Ma to the present about 500m of additional burial occurred.0° F/100 ft. Highly fractured carbonates overlie the source rock. The basin filled at a generally uniform rate from about 300 Ma to 100 Ma. evaluate the prospect. No other reservoirs are anticipated. oil-prone source rock at about 4300m depth near the prospect. rich.000 11. Your responsibility is to make a recommendation regarding the nature of hydrocarbons that might be present in die prospect." Utilizing the principles of hydrocarbon generation and preservation.65°C/100 m and a surface intercept of 15°C are reasonable for the area. .000 18. 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. No unconformities are recognized within the Paleozoic.000 13. The geothermal gradient was found to be 1. Erosional removal since the Permian probably totals about 2000 ft. Nearby well control indicates that a geothermal gradient of 3.000 8. The following geological summary is available to you. No other source rocks were noted. At that time nearby orogenic activity caused the first traps to be formed during a gradual 1200m uplift lasting until 40 Ma. 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. and the surface temperature today is about 15° C. Carboniferous '' '' '' '' E. Because of the high operations cost. upper management has decided that gas and condensate are not economical.Predicting Thermal Maturity .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. they are in turn overlain at 2750m by a sandstone of excellent reservoir quality. "A regional study of the area suggests the probable presence of a thin.000 23.

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

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

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

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

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

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