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

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

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

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

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

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

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

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

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

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

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

providing much of the structural support for large land plants. and amino acids. It is a polymer consisting of many repetitions and combinations of three basic aromatic subunits. Like lignin. Upon decomposition lignin forms phenolic compounds. it is an important constituent of terrestrial organic matter. They are rapidly metabolized by virtually all organisms. sugars. They have many characteristics in common with kerogen. and thus are seldom preserved in sediments (exceptions occur in shell material and in bones. most carbohydrates are attacked readily by microorganisms.Organic Chemistry . and cellulose. Lignin is an important component of wood. Many nonhydrocarbon molecules common to living organisms are also present in sediments. Carbohydrates include starch. however. Lignin monomers are linked topether to form molecules having molecular weights from 3000 to 10.16 varying structure. Lignin and cellulose are major constituents of humic coals. the latter is the most abundant organic compound in the biosphere. which are aromatics having a hydroxyl group (OH) attached. Although cellulose is quite resistant to decomposition under some conditions. where small amounts of preserved amino acids can be used to date specimens) . Amino acids are the building blocks of proteins.000 atomic mass units. lignin is rather resistant to degradation. Because phenols are potent bactericides. Among these are lignin. and thus tends to become concentrated as other organic matter is decomposed. carbohydrates. but asphaltene molecules are smaller and more aromatic than most kerogens.

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

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

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

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

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

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

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

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

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

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deviate from 1.0 even when no preference is distinguishable by visual inspection of the distribution curve. n-Alkane distributions are greatly modified by thermal maturity. Chain lengths gradually become shorter, and the original n-alkanes present in the immature sample are diluted with new n-alkanes generated during catagenesis. Because the newly generated n-alkanes show little or no preference for either odd- or even-carbon homologs, CPI values approach 1.0 as maturity increases. n-Alkane distributions in bitumens and oils derived from algae do not show the influences of maturity as clearly because the original CPI values are already very close to 1.0. It is therefore often difficult to estimate maturity levels in pelagic rocks on the basis of n-alkane data. Parameters other than Biomarkers. Sulfur contents are also strongly influenced by diagenetic conditions. For economic and environmental reasons, oils having more than about 0.5% sulfur are designated as high-sulfur. Many high-sulfur oils contain 1% sulfur or less, but in some areas sulfur contents can reach 7% (Monterey oils from the onshore Santa Maria area, southern California, for example). A few oils contain more than 10%. These high-sulfur bitumens and crude oils are derived from high-sulfur kerogens. As we saw earlier, sulfur is incorporated into kerogens formed in nonclastic sediments that accumulate where anaerobic sulfate reduction is important. Most oils and bitumens derived from lacustrine or ordinary clastic marine source rocks will be low in sulfur content, whereas those from euxinic or anoxic marine source rocks will be high-sulfur. Sulfur occurs predominantly in the heavy fractions of oils and bitumens, particularly in the asphaltenes. High-sulfur oils therefore have elevated asphaltene contents.

RESERVOIR TRANSFORMATIONS
Introduction. There are two main types of reservoir transformations that can affect crude oils (reservoir transformations are not applicable to bitumen because, by definition, the material in a reservoir is petroleum). Thermal processes occurring in reservoirs include cracking and deasphalting. Nonthermal processes are water washing and biodegradation. Of these, cracking and biodegradation are by far the most important. Cracking and Deasphalting. Cracking, which breaks large molecules down into smaller ones, can convert a heavy, heteroatom-rich off into a lighter, sweeter one. Waxy oils become less waxy. API gravities increase, and pour points and viscosities decrease. When cracking is extreme, the products become condensate, wet gas, or dry gas. Cracking is a function of both time and temperature, as well as of the composition of the oil and the catalytic potential of the reservoir rock. It is therefore impossible to state that cracking always occurs at a certain depth or reservoir temperature. Most oils, however, will be reasonably stable at reservoir temperatures below about 90° C, regardless of the length of time they spend there. On the other hand, a reservoir above 120° C will contain normal oil only if the oil is a recent arrival. Although the role of catalysis in hydrocarbon cracking in reservoirs has not been proven, many workers suspect that clay minerals are important facilitators of hydrocarbon breakdown. Catalytic effectiveness varies greatly from one clay mineral to another, however, and our partial understanding of this difficult subject is not of much practical use at the present time. Cracking also brings about deasphalting, because asphaltene molecules become less soluble as the oil becomes lighter. Precipitation of asphaltenes in the reservoir will lower sulfur content and increase API gravity appreciably. Biodegradation and water washing. Water washing involves selective dissolution of the most soluble components of crude oils in waters that come in contact with the oils. The smallest hydrocarbon molecules and the light aromatics, such as benzene, are the most soluble. The effects of water washing are rather difficult to determine because they do not affect the oil fractions that

Bitumen, Petroleum, and Natural Gas - 27

are most frequently studied. Furthermore, in most cases the effects are quite small because of the low solubilities of all hydrocarbons in water. Finally, water washing and biodegradation often occur together, with the more dramatic effects of biodegradation obscuring those of water washing. Biodegradation is a transformation process of major importance. Under certain conditions some species of bacteria are able to destroy some of the compounds present in crude oil, using them as a source of energy. The bacteria responsible for biodegradation are probably a mixture of aerobic and anaerobic strains. Only aerobic bacteria are believed to actually attack hydrocarbons, but anaerobes may consume some of the partially oxidized byproducts of initial aerobic attack. Because biodegradation changes the physical properties of oils, it can have serious negative financial implications. Heavily biodegraded oils are often impossible to produce (Athabasca Tar Sands of Alberta, Canada, and the Orinoco heavy oils of Venezuela, for example). If production is physically possible, it may be expensive or uneconomic. It is therefore important to understand where and why biodegradation occurs, and what its effects are on oil composition. Biodegradation may actually start during oil migration (provided required temperature and oxygen conditions are met), because oil-water interactions are maximized then. Most biodegradation probably occurs within reservoirs, however, since the length of time an oil spends in a reservoir is usually much longer than its transit time during migration. Biodegradation can vary in intensity from very light to extremely heavy. Because the chemical and physical properties of an oil change dramatically in several predictable ways during biodegradation, biodegraded oils are easily recognized. Many basins have at least a few biodegraded oils, and in some areas they are epidemic. Bacteria that consume petroleum hydrocarbons have strong preferences. Hydrocarbons are not their very favorite foods, and they eat them only because there is nothing else available. The preferred hydrocarbons are n-alkanes, presumably because their straight-chain configurations allow the bacterial enzymes to work on them most efficiently. Also attractive to the "bugs" are long, alkyl side-chains attached to cyclic structures. After the n-alkanes and alkyl groups are consumed, the bacteria begin to destroy compounds having only a single methyl branch or those having widely spaced branches. Then they move on to morehighly branched compounds, such as the isoprenoids. In the last stages of biodegradation, polycyclic alkanes are attacked. Because the hierarchy of bacterial attack on crude oils is well known, it is possible to assess the degree of biodegradation by observing which compounds have been destroyed. Sulfur contents of crude oils also increase as a result of biodegradation. In a heavily biodegraded oil the sulfur content may increase by a factor of two or three. Sulfur is undoubtedly concentrated in the oil by selective removal of hydrocarbons, and may also be added by bacterially mediated sulfate reduction.

COMPARISON OF BITUMEN AND PETROLEUM
Although bitumens and crude oils contain the same compounds, the relative amounts are quite different. In the process of converting bitumen to petroleum, either the NSO compounds are lost in large quantities, or they are converted to hydrocarbons. In actuality, both processes probably occur, although selective loss of nonhydrocarbons during expulsion is probably most effective in concentrating the hydrocarbons. Bitumen composition depends strongly on the lithology of the host rock. Carbonates contain bitumens that are much richer in heterocompounds than are shales, and their hydrocarbon fractions are more aromatic. These differences are the result of the higher sulfur contents of kerogens in carbonates. Oils derived from carbonate sources are also richer in heterocompounds than oils sourced from shales.

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NATURAL GAS
Natural gas contains many different compounds, although most of them are present only in trace quantities. The principal components with which we shall be concerned are light hydrocarbons (methane through butanes), C02, H2S, and N2. Carbon dioxide and N2 are generally associated with very hot reservoirs. C02 is derived either by oxidation of oil or gas or by decomposition of carbonates. The origin of the C02 can be determined easily by carbon-isotope measurements: the very different isotopic compositions of organic-carbon species and carbonates are carried over into any C02 derived from these materials. Nitrogen is thought to be an indicator of high levels of maturity formed primarily by metagenetic transformation of organic nitrogen and ammonia bound to clay minerals. Hydrogen sulfide is usually derived from high-sulfur kerogens or oils. These in turn are formed most readily in carbonates. Thus sour gas is most common in carbonate reservoirs or in places where the source rock was a carbonate. H2S could also be formed by the reaction of hydrocarbons with sulfate in reservoirs, especially carbonates containing anhydrite. Biogenic gas, most of which occurs at shallow depths, but which can apparently form (or at least persist) at depths of a few thousand meters, is very dry, containing only trace amounts of hydrocarbons heavier than methane. In contrast, the first gas produced during catagenesis is quite wet. With increasing maturity, gas again becomes progressively drier as a result of cracking of the heavier hydrocarbons to methane.

SUMMARY
Bitumens and crude oils contain the same classes of compounds, but their relative concentrations are quite different. These differences are in some cases related to differences in maturity; in other examples they are probably a result of preferential expulsion of hydrocarbons from source rocks. Individual compounds occur in quite variable proportions in bitumens. Source, diagenesis, and maturity all exert control over these distributions. When source and diagenetic influences have been removed, the porphyrins, steranes, triterpanes, and n-alkanes in mature bitumens are found to be very similar to those in crude oils and quite different from those in immature bitumens. Oil compositions can also be strongly affected by reservoir transformations, including biodegradation, water washing, cracking, and deasphalting. Many of the factors that influence the composition of oils and bitumens are well understood and predictable, and can be used to obtain information about paleoecology, thermal history, and reservoir conditions. Gas composition is governed first of all by whether the gas is of biogenic or thermal origin. Biogenic gas is always dry, whereas thermal gas may be wet or dry. Carbon-isotope ratios are good indicators of the source of gas; biogenic gas is much lighter isotopically than thermal gases. Other important components, such as CO2, N2, and H2S, are indicative of high temperatures or sulfur-rich source material.

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

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

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

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

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

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

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

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

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

In this case. In this type of structure. we can thus expect to find only smaller and smaller accumulations of petroleum down to the centre of curvature. the anticline is asymmetrical. We will describe in a little detail the most important types of anticline. a well would have to be located off-crest at surface. on the other hand. but an understanding of the shape and size of a prospect is clearly critical to programming an exploration well. noting the differences in shape and prospectivity that we have to try to interpret. so that the beds maintain a constant thickness throughout. and we may no longer be able to see where the bottle is.(2-22) In the concentric fold the tops and bottoms of all the layers remain strictly parallel to each other. . These compressive structures pose one problem right from the start. To test the crest at depth. This is a very different kettle of fish from the concentric anticline. we can find the trap present at all levels down to the basement. 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. Compressive structures have a range of shapes between the purely concentric or parallel anticline and the similar fold. Anticlines. The similar anticline. therefore in order to drill into a reservoir near its highest point (where we would expect the oil to be). so that the beds become intensely crushed and thrust together: we may no longer even have an anticline at all. Let us see what the implications are for exploration. Below this point we have just too much rock to fit into the anticline. Cross-sections of trap-forming anticlines. Cover it with a few more blankets and a duvet or two. with one flank steeper than the other. in cross-section. maintains its shape constant down to depth. many structures have forms in-between the two extremes.Petroleum Traps . (b) The anticline is asymmetrical and the crest shifts with increasing depth. (a) The dips are the same on both flanks and the crest is beneath the same locality at all depths. If. In practice. There is a definite limit to the depths to which we should drill. beyond which there may be no trap left to explore as the consequence of decoupling of layers. then the position of the crest will shift with increasing depth. This leads us into the next problem. The general principles of this are straightforward. and we may be able to continue exploration down to depths where we have to stop for other reasons. Other types of anticline can be formed without any lateral compression at all: an important one is the drape or drape-compaction structure. depending on the nature and strength of the rock layers being folded. Seismic may help. These conditions mean that the anticline becomes smaller and tighter at deeper levels until we reach a common `centre of curvature'. and the blanket bulges upwards with an anticlinal shape. we have to know its depth to know where best to locate the well.38 anticlines with different shapes and geometries that can affect both their prospectivity and the positions of optimum drilling locations: we have to try to understand them. This can only happen if there is an apparent thickening of some beds over the crest of the fold. but we commonly have to undertake some form of geometrical construction to interpret what is happening at depth. Traps can also be formed against faults if a chopped-off reservoir is thrown against a shale or other impervious rock.

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

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

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

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

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

.

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

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

47 .Petroleum Traps .

Petroleum Traps .48 .

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

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

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

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

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

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

type.2 3. and maturity of the organic matter present in the rocks? Satisfactory methods are available in most cases to answer all these questions.00 4.50 0.5 2 2 2 3 4 4 5 Correlation of various kerogen-maturity parameters with vitrinite-reflectance (Ro) values .50 2.60 0.00 1.80 1. unconformities and erosional events. To do this intelligently we must have the ability to develop regional models of organic facies and thermal maturity.55 SUMMARY Any source-rock evaluation should attempt to answer three questions: What are the quantity.0 3.6 2. Whenever possible.20 1.0 2.4 3.8 4.00 3.0 Pyrolysis Tmax (°C) 420 430 440 450 460 465 470 480 500 500 + 500 + Conodont Alteration Index (CAI) 1 1 1 1. With increasing experience one can also learn to derive important information on thermal histories. therefore. We should always attempt to extrapolate our measured data over as large an area as possible. rather.40 0.0 4.Source Rock Evaluation . In some areas one technique may fail completely or may be only partially successful. Vitrinite Reflectance (%Ro) 0.35 1.5 3.3 2. and organic facies.8 3. we should attempt to corroborate the measured data by other analyses.00 Thermal Alteration Index (TAI) 2. Interpretation of source-rock data on a basic level is quite simple. we should not rely on a single analytical technique.

5 0.2 1.2 2. as shown in Figure B (derived from Figure A).1 2.22 1.56 EXERCISES Worked out example: Perform a source-rock analysis on the Mauve Well. and then tracing the H/C ratio back to its immature value. and both should be utilized and examined for possible discrepancies.41 0.5 2.5 2. one must first convert the measured.15 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) .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).Source Rock Evaluation .86 0. This can be done easily by plotting H/C versus TAI. Both the immature H / C ratios and the maceral analysis data need to be scaled to calculate "Total Oil." Two independent quality measurements have been made. 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 0.5 0. refer to the graph on next page.33 1.9 3.7 1.6 2.05 0.7 2.72 0.7 1.81 1.27 1.5 1.0 0.07 1.6 0.0 3.66 0.98 0.1 3.0 2-2. To use the H /C data.77 0. and maturity (TAI).3 1.7 2.38 TAI 2. present-day H/C ratios to the ones that the kerogens had when they were thermally immature.5 2.75 0.5 2-2.8 0.2 3. however.2 Atomic H/C 1.5 2-2. presenting the kerogen quality factor as a . B) H/C versus TAI for Mauve Well samples.65 0. quality (H /C and %Alginite + Exinite). The calculated immature H/C ratios are listed in the table on next page." To do this. so "Total Oil" can be plotted against "Oil Already Generated.5 1.7 3.3 0.6 2.6 2.

the H/C ratio gives the lower quality factor.6 1.20 1.90 0. It is apparent that there are serious discrepanties between the H/C and maceral analysis results for several of the samples. The prudent interpreter might now ask that some of the H/C ratios be rerun.7 1.65 0.00 0. Without more knowledge.2 0.35 0.30 1.22 1.77 0.60 0. The most important point being made here is that these discrepanties must be taken seriously by the interpreter.81 1.6 1.35 0.0 0.05 0. 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 1.8 1.05 0. The samples at 1000.15 0.9 1. it is impossible to pinpoint the error.07 1.60 0. If these attempts produced no resolution of the problem.4 1.90 0.66 0. In likewise manner (not illustrated here) the quality factor can be determined from maceral analysis data.90 ? ? Quality Factor Quality Factor (from H/ C) (from 1.07 1.17 0.5 1.6 1. Kerogen quality factor as a function of H/C ratio of the immature kerogen.33 1. 1500.50 1. such as pyrolysis.85 1.98 0. 4000.35 1.05 1. so some systematic error is likely. 2300. 1750.8 ? ? * * * Indicates discrepancy between quality factors calculated from H /C and from maceral analysis.05 0. and not .90 0.9 0. the interpreter might then decide to try a third technique.72 0. 2000. however.81 1.Source Rock Evaluation .90 0.05 1.57 function of H/C ratio of the immature kerogen in order to determine the quality factor from H/C.41 0.77 0.43 1. and would certainly request that the slides made for maceral analysis be reviewed. The scaled quality factors are given for each parameter in the table on next page. In each case. and 4500 meters all show differences in the quality factors calculated from the two types of data.5 1.60 ? ? * * * * * 1.70 1. to check for analytical error.5 1.86 0.65 0.22 1.27 1.75 0.38 Immature H/C 1.

The rest of the section shows a good correspondente between the two parameters. 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. It may be necessary occasionally to offer two alternative interpretations without choosing between them. One can say little.58 be overlooked or swept under the rug. except for the two deepest samples. although the section between 2000 and 3500 meters shows fairly good potential. .Source Rock Evaluation . Future exploratory activity could include an attempt to find such a section. Finally. "Total Oil" values are generally unexciting. "Oil Already Generated" values indicate that only the section lying below 4500 meters is likely to have generated anything approaching a commercially attractive amount of oil. The only sample where the discrepancy is significant is that from 2000 meters. about the oil-source history of the section below 4600 meters. Most of the discrepanties among the different quality factors turn out to be unimportant. Let us take this last approach to this problem. and the H/C ratios are not helpful because the maceral types cannot be ascertained from such low H/C values. "Total Oil" and "Oil Already Generated" profiles are plotted in above figure. More samples between 3000 and 3500 meters should be obtained to define better the zone of high "Total Oil" values. "Total Oil" and "Oil Already Generated" profiles tor the Mauve Well. In fact. no maceral analysis was possible here. These two kerogens are highly mature and quite black. The relative organic richness of the blackened samples below 4600 meters makes them interesting for further investigation. because sourcerock potential is not good for most of the section. therefore.

Source-rock data tor the Turquoise Well Depth (ft) 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500 8000 8500 9000 9500 10.0 2.08 0.25 1.2 2.02 0.60 0.02 0.5 3.4 0.49 0.07 1.59 0.42 0.5-3 3.22 0.91 0.5 3.6 0.1 0.88 0.67 0.5-3 2.03 0.17 0.52 0.51 0.33? 1.07 0.51 0.06 0.7 0.46 0.5 2.48 Ro 0. Explain how you resolved any apparent discrepancies.26? 1.03 0.63 0.0 2.5 TOC = Total Organic Carbon Bit/TOC = Bitumen/Total organic carbon ? indicates a poor histogram TAI = Thermal Alteration Index Ro = Vitrinite reflectance .3 Bit/TOC 0.5 2.06 0.90 0.17 0.66 0.25 0.0-2.02 Atomic H/C 0.0 2.65 0.66 0.71 0.51 0.09 0.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10 2-2.5-3.0 2.5-3 2.7 0.0 3-3.59 EXERCISE Source Rock 1 Combine the data from the Blue Well to give a coherent picture of thermal maturity in the section drilled.5 0.9 1.5-3 2.65 0.60 0.5 2.8 1.3 2.21 1.8 0.09 0.59 0.5 2.10 0.5 2.99 1.5 2.41? 1.91 1.05 0.3 2.03 0.3 1.2 0.18 0.5 3-3.60 0.1 2.08 0.21 1. EXERCISE Source Rock 2 Perform a source-rock evaluation of the section penetrated in the Turquoise Well.21 0.55 0.5 2.0 2.86 1.6 4.06 0.0-2.05 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 2.5 2.07 0.91 1.49 0.5-3 2.0-2.27 0.27 1.11 0.0 0.08 0.3 2.00 1.000 Type of Sample Cuttings Cuttings TOC 1.5 2.85 0.5 2.01 0.44 0.6 2.5-3 2.5 2.12 *TAI and Ro are interconverted according to the correlation table at the end of chapter 7.0 2.61 0.Source Rock Evaluation .08 0.

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

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

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

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

TTI values differ appreciably among these four scenarios. although at increasingly slower rates. no matter how much or how rapidly we cool it down. If we put a cake in a cold oven and turn the oven on. maturity continues to increase (albeit at a slower rate) because y is always greater than zero.(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. Furthermore. Figure C shows rapid burial during the first 20 Ma. The first step in calculating TTI is illustrated in the following figure. as the oven cools down. baking will continue. by 10 Ma of uplift and erosion. where the time factors and yfactors for each temperature interval are shown on the burial-history curve. If we turn off the oven but leave the cake inside.Predicting Thermal Maturity . the cake will bake slowly at first but will bake faster and faster as the temperature rises. but quite rapid in the last 10 my. finally. In B burial was very slow during the first 70 Ma of the rock's existence. A good analogy can be drawn between oil generation and baking. To obtain total maturity. On the other hand. if we forget about the cake when the oven is hot and let it burn. FACTORS AFFECTING THERMAL MATURITY Because maturity is affected by both baking time and baking temperature. we simply sum all the interval-TTI values for the rock. 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. In the adjoining table interval-TTI values and total-TTI values up to the present day are calculated. even if a rock cools down. In D 40 Ma of rapid burial to a depth of 4000 m was followed by a hiatus lasting 30 Ma and. Maturity always increases. it can never go backward because interval-TTI values are never negative. . In A the rock was buried at a constant rate for its entire 80-my history.64 given. the specific burial history of a rock can strongly affect its maturity. followed by a nonerosional depositional hiatus for the last 50 Ma.

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

EXERCISES EXERCISE Thermal Maturity 1 Perform a source-rock evaluation of the section penetrated in the Turquoise Well.07 1. Base Pleistocene 2 Ma Base Pliocene 5 Base Upper Miocene 11 Base Middle Miocene 50 Ma . where presentday temperatures are maximum paleotemperatures. Construct a family of burial-history curves for the well and calculate the present-day TTI at total depth. In other cases. It penetrated 1000 ft of Pleistocene sediments. The corrected bottom-hole temperature was 270° F.5-3 2.0 3-3.Predicting Thermal Maturity .27 0.08 0.0 0.00 1.67 0. Despite experimental evidence indicating that different kerogens decompose to yield hydrocarbons at different levels of maturity models.7 0.03 0.66 Even if we could measure present-day subsurface temperatures with perfect accuracy.7 0.06 0.66 0. however.03 0.3 1. A plausible average surface temperature is 20° C.1 0.08 0.5 3.65 0.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10 2-2.01 0.99 1. Source-rock data tor the Turquoise Well Depth (ft) 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500 8000 8500 9000 9500 10.6 4. 3500 ft of Pliocene.22 0.88 0.5-3.000 ft of Upper Miocene before being abandoned at 16. In such cases we should be very careful about using predicted maturities unless we have some independent confirmation of the validity of our model from a comparison with measured maturity data.5 2.5 2.71 0.21 1.25 1.8 1.02 0.17 0.90 0.48 Ro 0. and 11.59 0.5 2.18 0.5 3-3.000 Type of Sample Cuttings Cuttings TOC 1.26? 1.5-3 2.8 0.2 0.33? 1. do not utilize different kinetic parameters for the various kerogen types.4 0.21 1.41? 1.51 0.86 1.27 1.85 0.49 0.02 Atomic H/C 0.3 Bit/TOC 0.5 TOC = Total Organic Carbon Bit/TOC = Bitumen/Total organic carbon ? indicates a poor histogram TAI = Thermal Alteration Index Ro = Vitrinite reflectance EXERCISE Thermal Maturity 2 The Black Well was drilled off the Louisiana Gulf Coast.52 0.08 0.06 0.91 1.65 0.5-3 3.5 2.91 0.3 2.9 1.60 0. In many cases.150 ft in the Middle Miocene. we still would have to extrapolate the present somehow into the past. an accurate interpretation of the ancient geothermal history may be critical.5 0. A question of some concern comes from the previously mentioned fact that most of the maturity models treat all types of kerogen identically. even an inaccurate extrapolation into the past may not cause significant problems.5-3 2.5-3 2.05 0.5-3 2.91 1. however.1 2.5 3. particularly where Paleozoic rocks are involved.51 0.

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

Predicting Thermal Maturity . The following geological summary is available to you. Carboniferous '' '' '' '' E. The source rock is thought to be about 300 Ma old. The geothermal gradient was found to be 1. At that time nearby orogenic activity caused the first traps to be formed during a gradual 1200m uplift lasting until 40 Ma. Because of the high operations cost.500 21. Erosional removal since the Permian probably totals about 2000 ft.000 18. From 40 Ma to the present about 500m of additional burial occurred. The basin filled at a generally uniform rate from about 300 Ma to 100 Ma.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.500 27. Carboniferous '' Ordovician '' Depth (ft) 7. No other reservoirs are anticipated. 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.000 13. The reservoir is sealed by a thick salt layer. rich. they are in turn overlain at 2750m by a sandstone of excellent reservoir quality.0° F/100 ft.000 11.68 EXERCISE Thermal Maturity 5 Analyze the timing of oil generation in the Pink Well.000 23.000 8. 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. Time-stratigraphic data are given in the following table. and the surface temperature today is about 15° C. No unconformities are recognized within the Paleozoic. . No other source rocks were noted.65°C/100 m and a surface intercept of 15°C are reasonable for the area.000 25." Utilizing the principles of hydrocarbon generation and preservation. "A regional study of the area suggests the probable presence of a thin. Highly fractured carbonates overlie the source rock. upper management has decided that gas and condensate are not economical. evaluate the prospect. Your responsibility is to make a recommendation regarding the nature of hydrocarbons that might be present in die prospect. Nearby well control indicates that a geothermal gradient of 3. oil-prone source rock at about 4300m depth near the prospect.

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

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

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

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

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

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