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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Except for darkening. especially highly aromatic ones. Some properties of kerogen change very little during catagenesis. Bitumen generation occurs mainly during catagenesis. during metagenesis the chief product is methane. The intensity and wavelength of the fluorescente are functions of kerogen maturity. Kerogens often fluoresce when irradiated. which are unpaired electrons not yet involved in chemical honds. and the less it will be reflected. the visual appearance of kerogen also does not change during catagenesis: kerogen types are generally recognizable until the particles become black and opaque. Cracking often produces free radicals. The concentration of free radicals in a given kerogen has been found to increase with increasing maturity. and no guarantee that a particular kerogen color always heralds the onset of oil generation. One property that is strongly affected. Both curves are highly . small molecules are broken off the kerogen matrix.Kerogen . the technique. As kerogen matures and becomes more aromatic. and which can be used to gauge the extent of molecular reorganization. resulting in lower bitumen contents in the source. These structural reorganizations bring about changes in physical properties of kerogens. called vitrinite reflectance.22 between kerogen darkening and hydrocarbon generation. 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. The difference between the two curves represents bitumen expelled from the rock or cracked to light hydrocarbons. is the ability of kerogen particles to reflect incident light coherently. somewhat beyond the oil-generation window. Kerogens. however. has been widely and successfully applied in assessing kerogen maturity. its structure becomes more ordered. Free-radical concentrations can be measured by electron-spin resonance. and because vitrinite particles also occur in kerogens. What actually occurs. Because coal rank is merely a measure of coal maturity. the more an incident light beam will be scattered. HYDROCARBON GENERATION As kerogen catagenesis occurs. Half a century ago coal petrologists discovered that the percentage of light reflected by vitrinite particles could be correlated with coal rank measured by other methods. Some of these are hydrocarbons. The more random a kerogen's structure. there would be a large and continuous build-up of bitumen in the rock as a result of catagenetic decomposition of kerogen. A general name tor these molecules is bitumen. These small compounds are much more mobile than the kerogen molecules and are the direct precursors of oil and gas. Plot of bitumen generation as a function of maturity (dashed fine) compared to bitumen remaining in rock (solid line). contain large numbers of unpaired electrons. because the flat aromatic sheets can stack neatly. carbon-isotopic compositions of kerogens are affected little by maturation. For example.

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

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

and by their catagenetic formation from long-chain compounds such as fatty acids and alcohols. and Natural Gas . 27. Because of their molecular complexity and heterogeneity. receive contributions of n-alkanes from both terrestrial and marine sources. Another important indication of the origin of n-alkanes is the distribution of individual homologs. and no preference for either odd. In most cases.0. 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). Many sediments.and even-carbon members is equal. These compounds. Asphaltenes can thus be removed from oils or bitumens in the laboratory or refinery by adding a light hydrocarbon. of course. but their sources are simply no longer recognizable due to diagenetic and catagenetic transformations. FACTORS AFFECTING COMPOSITION OF BITUMEN AND PETROLEUM SOURCE AND DIAGENESIS Biomarkers n-Alkanes were among the first biomarkers to be studied extensively. The most useful biomarkers serve as indicators of the organisms from which the bitumen or petroleum was derived. 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. Sediments are also known that exhibit a strong preference for n-alkanes having an even number of carbon atoms. which are derived from biogenic precursor molecules. SPECIFIC COMPOUNDS Biomarkers. and 31 atoms. where input of terrestrial n-alkanes is minimal and diagenetic conditions are highly reducing. These n-alkanes are believed to be formed by hydrogenation (reduction) of longchain fatty acids and alcohols having even numbers of carbon atoms. For the most part n-alkanes present in terrestrial plants have odd numbers of carbon atoms. In a few cases specific precursor organisms or molecules can be identified. whereas in other instances we may be able to limit the possible precursors to only a few species. are essentially molecular fossils.) Even-carbon preferences occur principally in evaporitic and carbonate sediments. even-carbon homologs predominate as strongly as do the oddcarbon homologs among the n-alkanes. In contrast. Their n-alkane distributions reflect this mix. although we know for certain that the biomarker molecule is biogenic. CPI values can therefore . Other compounds. 25. or of the diagenetic conditions under which the organic matter was buried.Bitumen. however. (Among the acids and alcohols present in living organisms. the CPI is 1. marine algae produce n-alkanes that have a maximum in their distribution at C-17 or C22. 29. Carbon Preference Index. However. the lower-carbon homologs are given more weight in the calculation. If the number of odd. depending upon the species present. Many of the compounds and classes of compounds that we find in crude oils and bitumens are called biomarkers. They are. Their high concentration in bitumens and oils is best explained by their existence in plant and algal lipids. because the concentration of n-alkanes often decreases with increasing carbon number. Petroleum. or members of the n-alkane series. we are unable to use it as an "index fossil" for specific organisms.0. The distributions are quite sharp. If odd-carbon homologs predominate.or even-carbon homologs is evident. an abbreviation for biological markers. of biological origin. the CPI is greater than 1. such as pentane or propane. asphaltene molecules have not been studied in detail. The average of two ranges is taken to minimize bias produced by the generally decreasing n-alkane concentrations with increasing number of carbon atoms. or CPI. especially 23.25 them insoluble in light solvents.

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

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

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

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

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

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

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

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

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

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

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

and how big it is. (B) a roll-over complicated by subsidiary faulting near the crest. southern England. and its depth. to locate an exploration well in the right place. down towards the deep ocean. although there are many problems in trying to locate them in the subsurface. therefore. we have to know whereabouts in the succession our prospective reservoir lies. (2-28) We do not propose to discuss fault traps in detail. Fault traps We indicated above that a trap may be formed where a dipping reservoir is cut off up-dip by a fault. Whether or not there is a trap. UK. Occasionally indeed. or slumping as a sort of land-slide. Upper Cretaceous. in both cases. as at Wytch Farm. Again. whether or not the reservoir is completely or only partially offset. L. whether the fault is normal or reverse. . the position of the crest is displaced with depth and that accumulations in successive reservoirs will not underlie the same surface position. but we also know that sometimes faults are pathways for migrating petroleum and non-sealing at all. thus causing sand against sand to permit migration and sand against shale to be sealing. The sealing capacity of faults is a major difficulty confronting us. or by opposing dips. at deeper levels the crest will shift away from the position of the fault at surface. and in understanding them. we still do not fully understand what the difference is due to. Lower Cretaceous. Much of the oil under the Niger and Mississippi Deltas is in such roll-over anticlines. W. The oil is in two reservoirs. it seems that one and the same fault may act. T. trapped against faults to the south. Middle Jurassic.40 they are asymmetrical. or have acted in the past. BS+MJ+O. Upper Jurassic. a fault can provide a seal. Kim+P. Note that. It also depends on whether the fault itself is sealing or non-sealing. will depend on the dip of the reservoir as compared with that of the fault. setting it against something impermeable. (2-27) These roll-over structures are particularly important where the `stretching' is caused by a very thick pile of sediments at the edge of a continent gently slipping. The large Wytch Farm oilfield of southern England offers a splendid example. in both ways. Tr. and it will depend on the amount of displacement on the fault. Roll-over anticlines: (A) a simple roll-over into a normal fault.. We know that sometimes. Tertiary. Triassic. All very puzzling! Although attempts have been made to investigate the problem in Nigeria and elsewhere. Cross-section through the Wytch Farm oilfield. and naturally we have some ideas on the subject. Lower Jurassic. The reader may care to think through the various situations sketched as bits of cross-sections in the following figure in which the faults themselves are non-sealing. It adds further uncertainties to our predictions of the subsurface occurrence of oil and gas.Petroleum Traps . The proviso is that we also have lateral closure: this may be provided by further faulting. these predated the deposition of the Upper Cretaceous.

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

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

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

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

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

47 .Petroleum Traps .

Petroleum Traps .48 .

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

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

Thirdly. One disadvantage of CAI measurements is that CAI values can be dramatically increased in the presence of hot brines. TAI values must be estimated from amorphous debris. Early investigations showed that immature rocks often had high CPI . Finally. most commonly from fossiliferous carbonates. lack of proper standardization.Source Rock Evaluation . where pollen and vitrinite are often absent. leading to an inaccurate assessment of kerogen maturity. Other disadvantages overlap with some of the advantages. One advantage of CAI over other maturity parameters is that because conodonts existed as early as the Cambrian. The chief problems arise with inexperienced workers. The first maturity indicator applied to sediments was the Carbon Preference Index. they offer a means of measuring maturity in rocks that do not contain pollen grains or vitrinite. CAI is only an indirect indicator of hydrocarbon maturity. CAI is inexpensive and easy to measure and. Although conodonts are composed of carbonate apatite. Furthermore. and thus are of no value in many areas. with the help of color charts can be carried out by inexperienced personnel. Conodont Alteration Index (CAI). or most commonly. changes in conodont color are apparently due to carbonization of inclusions of small amounts of organic matter during catagenesis and metagenesis. The technique is simple and quick and can be done even by inexperienced workers. which can vary greatly in its chemical and physical properties. TAI values estimated from amorphous material are always suspect and should be corroborated by other analyses.51 Each laboratory has reference slides so that microscopists can continually compare the color determinations they are now making with those they and their colleagues made in the past. the absence of spores and pollen in the samples. Carbon Preference Index (CPI). Conodonts are isolated. TAI measurements are therefore often quite accurate and correlate very well with results from other techniques. by removing the mineral matrix with acetic or formic acid. because the organic metamorphism displayed by conodonts is not related to hydrocarbon generation or destruction. the CAI scale is most sensitive at levels of maturity much higher than can be measured by TAI. Conodonts are not very sensitive indicators of maturity within the oil generation window. and thus helps expand the range over which maturities can be measured. A careful worker can reproduce earlier work with excellent precision. Colors of the specimens thus obtained are determined under a binocular microscope and compared with standards. thus defusing to a large degree the criticism that TAI is too subjective to be valid. Finally. use of careful standards and the same type of palynomorph in each analysis greatly aid reproducibility. Conodonts do not occur in rocks younger than the Triassic. Although TAI determinations are subjective. conodonts are plentiful in carbonate rocks. When palynomorphs are absent. where most of the interest is.

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

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

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

5 3.8 3.3 2. rather.5 2 2 2 3 4 4 5 Correlation of various kerogen-maturity parameters with vitrinite-reflectance (Ro) values .2 3.55 SUMMARY Any source-rock evaluation should attempt to answer three questions: What are the quantity.00 4.00 3. To do this intelligently we must have the ability to develop regional models of organic facies and thermal maturity. Whenever possible. and maturity of the organic matter present in the rocks? Satisfactory methods are available in most cases to answer all these questions.Source Rock Evaluation .50 2.80 1.0 4. and organic facies. therefore. type.50 0.4 3.20 1.8 4.35 1. In some areas one technique may fail completely or may be only partially successful.40 0. Vitrinite Reflectance (%Ro) 0.00 Thermal Alteration Index (TAI) 2.0 Pyrolysis Tmax (°C) 420 430 440 450 460 465 470 480 500 500 + 500 + Conodont Alteration Index (CAI) 1 1 1 1.60 0. Interpretation of source-rock data on a basic level is quite simple. We should always attempt to extrapolate our measured data over as large an area as possible. we should attempt to corroborate the measured data by other analyses. unconformities and erosional events.0 3.6 2.0 2. With increasing experience one can also learn to derive important information on thermal histories.00 1. we should not rely on a single analytical technique.

33 1.15 0. presenting the kerogen quality factor as a .2 3.38 TAI 2.0 3. one must first convert the measured. B) H/C versus TAI for Mauve Well samples.6 2.98 0.6 0.5 0.5 0.7 1.5 2. 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. and then tracing the H/C ratio back to its immature value.5 2-2.8 % Alginite + Exinite 75 80 80 75 80 90 85 75 70 50 45 60 45 40 ? ? Core Cuttings Data are available on quantity (%Corg).05 0. quality (H /C and %Alginite + Exinite).7 2.3 1.72 0.1 2.86 0.7 3. however.2 Atomic H/C 1.77 0.41 0.5 2.1 3.0 2-2.Source Rock Evaluation .2 1.65 0.6 2.3 0. A) Calculation of the immature kerogen H/C ratio(at A) from the present-day H/C ratio and vitrinite reflectance data(at P) . The calculated immature H/C ratios are listed in the table on next page. so "Total Oil" can be plotted against "Oil Already Generated.66 0. as shown in Figure B (derived from Figure A).5 1.0 0. present-day H/C ratios to the ones that the kerogens had when they were thermally immature.27 1.07 1.9 3. and both should be utilized and examined for possible discrepancies. To use the H /C data.8 0.75 0.56 EXERCISES Worked out example: Perform a source-rock analysis on the Mauve Well.5 2." To do this. Both the immature H / C ratios and the maceral analysis data need to be scaled to calculate "Total Oil.2 2.6 2.5 1.7 2. and maturity (TAI). refer to the graph on next page.22 1. This can be done easily by plotting H/C versus TAI.7 1.5 2-2.81 1." Two independent quality measurements have been made.

00 0.5 1.17 0. The samples at 1000. Without more knowledge.Source Rock Evaluation .9 0.65 0.90 0.41 0. 1750.8 1.60 0.05 0. and 4500 meters all show differences in the quality factors calculated from the two types of data.22 1. The prudent interpreter might now ask that some of the H/C ratios be rerun.5 1.22 1. so some systematic error is likely.72 0.8 ? ? * * * Indicates discrepancy between quality factors calculated from H /C and from maceral analysis. 2300. 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 1.35 1. such as pyrolysis.81 1. 4000.07 1.98 0.6 1. 1500. In each case.65 0.30 1.4 1.38 Immature H/C 1.07 1.6 1.05 0. The scaled quality factors are given for each parameter in the table on next page.86 0. Kerogen quality factor as a function of H/C ratio of the immature kerogen. 2000.05 1.2 0. If these attempts produced no resolution of the problem.7 1.35 0.05 1.75 0.66 0.60 0.77 0.43 1. the H/C ratio gives the lower quality factor. The most important point being made here is that these discrepanties must be taken seriously by the interpreter.20 1.5 1. the interpreter might then decide to try a third technique.15 0.90 ? ? Quality Factor Quality Factor (from H/ C) (from 1.27 1.05 0.0 0.60 ? ? * * * * * 1.6 1.35 0. it is impossible to pinpoint the error.85 1.77 0.90 0. however. and not .57 function of H/C ratio of the immature kerogen in order to determine the quality factor from H/C.90 0.33 1. It is apparent that there are serious discrepanties between the H/C and maceral analysis results for several of the samples.50 1. In likewise manner (not illustrated here) the quality factor can be determined from maceral analysis data.81 1.70 1.9 1.90 0. to check for analytical error. and would certainly request that the slides made for maceral analysis be reviewed.

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

44 0.1 2.0-2.59 0.08 0.7 0.07 0.5-3 2.61 0.02 Atomic H/C 0.49 0.06 0. Thermal-maturity data for the Blue Well Depth (ft) TAI Ro Bitumen/TOC 1000 1200 1500 2000 2300 2600 3000 3200 3400 3700 4000 4200 4800 5000 5200 5400 5700 6000 2.12 *TAI and Ro are interconverted according to the correlation table at the end of chapter 7.5 2.05 0.5-3 2.90 0.5-3 2.5 2.08 0.5 3-3.51 0.000 Type of Sample Cuttings Cuttings TOC 1.60 0.22 0.6 2.55 0.86 1. Source-rock data tor the Turquoise Well Depth (ft) 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500 8000 8500 9000 9500 10.25 1.5 0. EXERCISE Source Rock 2 Perform a source-rock evaluation of the section penetrated in the Turquoise Well.0 2.5-3.42 0.5-3 2.60 0.5 2.3 Bit/TOC 0.21 1.11 0.03 0.0 0.02 0.88 0.5 2.09 0.5 3.99 1.2 2.7 0.66 0.02 0.07 0.91 1.71 0.51 0.67 0.09 0.Source Rock Evaluation .8 0.91 0.48 Ro 0.5 2.5 2.10 0.63 0.5 2.85 0.66 0.5 2.00 1.0 2.06 0.03 0.65 0.91 1.17 0.26? 1.05 0.2 0.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10 2-2.17 0.21 1.5-3 2.5-3 3.25 0.6 0.8 1.01 0.18 0.08 0.6 4.65 0.27 0.49 0.0 2.3 2.3 2.33? 1.27 1. Explain how you resolved any apparent discrepancies.9 1.0 3-3.3 2.60 0.0 2.3 1.21 0.51 0.5 2.5 2.1 0.0-2.0 2.41? 1.5 TOC = Total Organic Carbon Bit/TOC = Bitumen/Total organic carbon ? indicates a poor histogram TAI = Thermal Alteration Index Ro = Vitrinite reflectance .59 0.5 3.52 0.46 0.08 0.4 0.5 2.06 0.07 1.0-2.03 0.0 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.

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

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

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

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

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

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

86 1.59 0.1 0.21 1.17 0.91 1. however. In many cases.3 1.06 0.60 0.67 0. A question of some concern comes from the previously mentioned fact that most of the maturity models treat all types of kerogen identically.66 0.7 0.48 Ro 0.91 1. an accurate interpretation of the ancient geothermal history may be critical.21 1. we still would have to extrapolate the present somehow into the past.65 0.5-3 2.51 0.5 2. The corrected bottom-hole temperature was 270° F.8 0.71 0.7 0.18 0. however.5 3.01 0.06 0.3 2.5 2.51 0.66 Even if we could measure present-day subsurface temperatures with perfect accuracy. A plausible average surface temperature is 20° C.000 Type of Sample Cuttings Cuttings TOC 1.41? 1.5 TOC = Total Organic Carbon Bit/TOC = Bitumen/Total organic carbon ? indicates a poor histogram TAI = Thermal Alteration Index Ro = Vitrinite reflectance EXERCISE Thermal Maturity 2 The Black Well was drilled off the Louisiana Gulf Coast. Base Pleistocene 2 Ma Base Pliocene 5 Base Upper Miocene 11 Base Middle Miocene 50 Ma .27 0.25 1.6 4. particularly where Paleozoic rocks are involved.9 1.08 0.90 0. In such cases we should be very careful about using predicted maturities unless we have some independent confirmation of the validity of our model from a comparison with measured maturity data.02 0.91 0.5 3. even an inaccurate extrapolation into the past may not cause significant problems.49 0.5-3 2.0 3-3. Source-rock data tor the Turquoise Well Depth (ft) 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500 8000 8500 9000 9500 10.52 0.03 0.05 0.8 1.07 1. Construct a family of burial-history curves for the well and calculate the present-day TTI at total depth.00 1.000 ft of Upper Miocene before being abandoned at 16.0 0.5 2. EXERCISES EXERCISE Thermal Maturity 1 Perform a source-rock evaluation of the section penetrated in the Turquoise Well.5 2.3 Bit/TOC 0.2 0.33? 1.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10 2-2.02 Atomic H/C 0.27 1.1 2.22 0.26? 1.5 0.85 0. do not utilize different kinetic parameters for the various kerogen types.4 0.5-3 2.5-3 2.5 3-3. where presentday temperatures are maximum paleotemperatures.65 0.5-3.88 0.08 0.03 0.5-3 3. and 11.150 ft in the Middle Miocene.99 1. 3500 ft of Pliocene.Predicting Thermal Maturity . Despite experimental evidence indicating that different kerogens decompose to yield hydrocarbons at different levels of maturity models.5-3 2. In other cases.08 0. It penetrated 1000 ft of Pleistocene sediments.

Time-stratigraphic data Temperature data Age (Ma) 0 2 38 65 80 100 Depth (m) 0 500 1200 2700 3000 4000 Present-day average surface temp. 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. Corrected BHT (4200 m): Estimated surface temp. Assuming a surface temperature of 10° C and a geothermal gradient of 2° F/100 ft. Age data top Paleocene base Paleocene base Maastrichtian base Campanian base Santonian base Coniacian 55 Ma 65 73 83 87. micropaleontology indicates the rocks to be of Maestrichtian age.67 EXERCISE Thermal Maturity 3 Calculate present-day TTI at 3000 m in the Red Well. draw a burial-history curve for the section penetrated and calculate maturity for the Kimmeridgian shale.5 88.5 base Turonian base Cenomanian base Cretaceous top Kimmeridgian base Kimmeridgian 91 Ma 97 144 150 156 Ma . At a depth of 1500 ft. Determine when each of the strata began to generate oil. It is also believed that 500 ft of Lower Cretaceous sediments were deposited before uplift and erosion began. Total original thickness of the Kimmeridgian is thought to be 1500 ft. Evidence from related sections indicates that the Paleocene was originally about 3000 ft thick and that no other Cenozoic sediments were ever deposited.end Cretaceous: 15° C 141° C 25° C EXERCISE Thermal Maturity 4 The Ultraviolet Well is spudded in Paleocene sediments. assuming a constant geothermal gradient through time. Find when the rock at 3000 m began to generate oil (TTI = 10).Predicting Thermal Maturity . Total depth is reached at 6120 ft in Middle Jurassic rocks.

000 23. . From 40 Ma to the present about 500m of additional burial occurred. they are in turn overlain at 2750m by a sandstone of excellent reservoir quality." Utilizing the principles of hydrocarbon generation and preservation. 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.000 11. The source rock is thought to be about 300 Ma old.500 27. Carboniferous '' '' '' '' E.65°C/100 m and a surface intercept of 15°C are reasonable for the area. The following geological summary is available to you. Highly fractured carbonates overlie the source rock. evaluate the prospect. rich. Erosional removal since the Permian probably totals about 2000 ft.000 13. The geothermal gradient was found to be 1.000 8. 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.500 21. "A regional study of the area suggests the probable presence of a thin. Because of the high operations cost. Carboniferous '' Ordovician '' Depth (ft) 7.000 18. No other source rocks were noted. and the surface temperature today is about 15° C.500 EXERCISE Thermal Maturity 6 You have been asked to evaluate an undrilled prospect in a remote area that is available in an expensive farm-in deal. The reservoir is sealed by a thick salt layer.0° F/100 ft.000 25.68 EXERCISE Thermal Maturity 5 Analyze the timing of oil generation in the Pink Well. upper management has decided that gas and condensate are not economical. The basin filled at a generally uniform rate from about 300 Ma to 100 Ma.Predicting Thermal Maturity . No unconformities are recognized within the Paleozoic. oil-prone source rock at about 4300m depth near the prospect. Nearby well control indicates that a geothermal gradient of 3. Your responsibility is to make a recommendation regarding the nature of hydrocarbons that might be present in die prospect. No other reservoirs are anticipated. At that time nearby orogenic activity caused the first traps to be formed during a gradual 1200m uplift lasting until 40 Ma. Time-stratigraphic data are given in the following table.

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

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

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

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

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

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