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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.
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
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
kerogen begins to decompose into smaller. Although the transformation process is very complex. but only within the last few years have we realized that in many areas a large portion of the natura!-gas reserves are biogenic. As temperature rises. and temperature increases. with many details still poorly understood. oil and gas molecules can be expelled from the source rock into more permeable carrier beds or conduits. These changes lead to a gradual cessation of microbial activity. called methanogens. Certain microorganisms. these are the precursors for petroleum. however. .5 1 . In recent years this relatively simple picture of hydrocarbon generation has been complicated slightly by our growing awareness that kerogens formed from different kinds of organic matter. thermal reactions become increasingly important. are chemically distinct from each other. Once formed. Most of this organic matter is transformed during diagenesis info very large molecules. During this second transformation phase. porosity and permeability decrease. Formation of biogenic methane has been recognized for a long time. called catagenesis.Introduction FORMATI0N OF 0IL AND GAS Proponents of the organic origin of oil and gas have given us a general picture of how organic matter derived from dead plants is converted to hydrocarbons. more mobile molecules. the largest of which are called kerogen. As burial depth increases. These differences can have a significant effect on hydrocarbon generation. where hydrocarbon movement ceases and accumulation occurs. These play a key role as the precursors for oil and much natural gas. and were formed as dead organic matter was converted to microbial tissues. In the early stages of catagenesis most of the molecules produced from kerogen are still relatively large. In the late stages of catagenesis and in the final transformation stage. the principal products consist of smaller gas molecules. convert some of the organic debris to biogenic methane. Migration through these conduits often leads to traps. and are called bitumen . called metagenesis. it is known that organic debris derived from plants and algae is best preserved in fine-grained sediments deposited in the absence of oxygen. and thus eventually bring organic diagenesis to a halt. The earliest stage of hydrocarbon generation occurs during diagenesis. Many of the chemical compounds present in sediments are in fact derived from bacteria.Organic Facies . or under different diagenetic conditions. Low-temperature chemical and biological reactions (called diagenesis) that occur during transport to and early burial in the depositional environment modify this organic matter.
6 2 . Preservation of organic matter begins with photosynthesis. 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. 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. A large fraction. less than 1% of the annual photosynthetic production escapes from the carbon cycle and is preserved in sediments. Because of . as a consequence of the much more rapid reproduction of simple aquatic organisms. however.Organic Facies THE CARBON CYCLE Because oil and gas are generated from organic matter in sedimentary rocks. we need to understand how this organic matter came to be preserved in the rocks. comprises microbial tissue formed within the sediments by the bacterial transformation of plant and algal debris. Preservation of organic material is actually a rare event. Oxidative decay of dead organic matter is a highly efficient process mediated largely by microorganisms. the yearly productivity of both groups is about equal. Zooplankton and higher animals contribute relatively little organic matter to sediments. Despite the great imbalance in biomass between terrestrial plants (450 billion metric tons [t]) and aquatic phytoplankton (5 billion t).Organic Facies .
because under normal circumstances they cannot move upward into the zone of photosynthesis. Shallowmarine environments. volcanism. Namibia. Each of these categories could in turn be further subdivided. and recycling by organic decay. preservation. Upwelling occurs where bulk movement of surface water away from a particular area allows deeper water to ascend to replace it. accumulation of organic-rich sediments cannot occur.000. Peru. In relatively unrestricted marine environments. are therefore much more productive than the open ocean. PRODUCTIVITY A partial listing of the many factors influencing productivity would include nutrient availability. and Northwest Africa that result from the movement of surface waters away from these coasts.7 extensive oxidation of land-plant debris in soils. Depth could interfere with microbial diagenesis when compaction reduces pore sizes and nutrient fluxes in interstitial waters. a great deal of the oxidation of organic matter occurs within the sediments themselves. temperature. There is another zone of seasonal upwelling off the Horn of Africa in the Indian Ocean as a result of . orogeny and erosion.000 billion t. and that the microbes have given up trying to digest it.05%) occurs in economic deposits of fossil fuels. Although oxidative decay destroys most of the yearly production. only one molecule out of about every one million successfully negotiates the journey from living organism to the gasoline pump. Productivity is the logical place to begin our analysis. in fact. and general water chemistry. Although some destruction of organic material occurs during transport to the depositional environment. over vast amounts of geologic time the small fraction that escaped the carbon cycle has built up extremely large quantities of organic matter (20. Nutrients dissolved in waters below the photic zone therefore go unutilized. paleoclimate.Organic Facies . where there is local recycling of nutrients from decaying organisms and influx of fresh nutrients from terrestrial sources. FACTORS INFLUENCING ORGANIC RICHNESS In order for organic-rich rocks to be formed. On the other hand. Total Organic Carbon (TOC) values decrease monotonically through the first 300 meters of burial before levelling out at about 0. significant amounts of organic matter must be deposited and protected from diagenetic destruction. Only where there is upwelling of subsurface waters can these nutrients return to the photic zone. however.1%. Nutrient availability is. predators. If this deeper water is enriched in nutrients. high photosynthetic productivity will occur at the site of upwelling. and dilution. because without adequate productivity. For example. nutrient availability would depend on such factors as water circulation patterns. light intensity. In the modern world there are zones of intense seasonal upwelling off the west coasts of California. one of the critical parameters governing productivity. Bodies of water naturally develop density stratification. 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. Only a small fraction of this (10.000 billion t) dispersed in fine-grained sedimentary rocks. suggesting that either depth or organiccarbon content eventually limits diagenesis. watercirculation patterns are particularly important for supplying nutrients and thus controlling productivity. When we consider inefficiencies in discovery and recovery. Each factor may be dominant under different conditions. carbonate supply. much of the terrestrial organic material is already highly oxidized when it arrives in the sediments. the low TOC values could indicate that the remaining organic matter has no more nutritional value. or about 0.
Secondly. increasing preservation rates is a very efficient way to increase organic richness. especially of woody origin. many species disappear. First. All large organisms require oxygen in order to live. because marine organic matter is consumed preferentially by organisms. the simplest way to limit oxidation is to limit the supply of oxygen. the type of organic matter deposited. The term "anoxic" literally means "having no oxygen. The term dysaerobic has been used to describe processes occurring in the transitional zone (0. and all the other factors that influence upwelling loci is severely limited. respectively. because some of the commonly used indicators of anoxia may be misleading. ANOXIA.2 mL/L. essentially the only viable organisms are those that we call anaerobes. the accuracy with which we can reconstruct continental positions. some problems associated with their application. Processes that occur in these two zones are called aerobic and anaerobic. Such models are interesting. Anoxic sediments always contain elevated TOC values (generally above 2% and always above 1% ). the zone where oxygen falls below 0. The presence of undegraded marine organic material is a strong indication of anoxia. These anaerobic processes are inefficient compared with aerobic diagenesis. especially in the Palaeozoic.5 mL/L). however. and we could coin the term dysoxic to describe the zone itself. its use in practice has been expanded to include very low oxygen levels as well. diagenesis is restricted to anaerobic processes.2 mL/L. if on the average only 1% of organic matter is preserved.2 mL/L is called the anoxic zone. There are many more organic-rich facies resulting from excellent preservation than from extremely high productivity. and may in fact prove useful in future exploration efforts. wind and water circulation patterns. However. There are. After all. landmasses. oxidizing agents are probably the most crucial factor. Its presence in . We call the zone in which oxygen contents are high the oxic zone. the remaining individuals often become dwarfed in an effort to survive in a hostile environment.5 milliliters (mL) per liter (L)). soils. preservation of organic matter will be much enhanced. and the sediment-accumulation rate. microorganisms that utilize materials like sulfate or nitrate ions instead of molecular oxygen as electron acceptors in their metabolic processes. although some species can tolerate extremely low oxygen levels (0. and because most biological oxidation processes require molecular oxygen. because when the availability of oxygen is limited. and are usually limited in scope by the availability of sulfate or nitrate.8 monsoonal winds that drive surface waters away from the coast. paleoclimatic conditions. Anoxia is of tremendous importance in the preservation of organic matter in sediments. and sediments is biological. All these areas exhibit high productivity when upwelling occurs. productivity is probably not as important a factor as preservation. PRESERVATION The principal control on organic richness is the efficiency of preservation of organic matter in sedimentary environments. At dissolved oxygen levels below about 0. much oxic sediment also contains large amounts of organic matter. Theoretical models have been developed to predict upwelling (and consequent productivity) in ancient seas from input data on continental configurations. Because most of the oxidation occurring in the water column. Thus if anoxia can develop. TOC values alone must therefore be used with caution. Of these." hut because of the radical change in biota that occurs at about 0.2-0. At lower levels of dissolved oxygen. Three factors affect the preservation (or destruction) of organic matter: the concentration and nature of oxidizing agents.Organic Facies . and paleoclimates. Anoxic sediments are not always easy to recognize.
and strata from several basins in China. Lake deposits associated with continental rifting. Marine basins are seldom isolated enough to fit well into the stagnant-basin model. Consumption of oxygen results from decay of dead organisms that have sunk from the photic zone above. are anoxic in some of the places where they have been penetrated. It therefore behoves us to understand the conditions under which anoxia develops. The laminae prove that burrowing fauna were absent. they often owe their dark color to finely divided pyrite or to particular chert phases. and if the climate is subtropical or tropical. anoxic sediments. Many black rocks. If an isolated body of water is deep enough. the presence of bioturbation indicates that the bottom waters were not anoxic. Lack of communication between the layers prohibits replenishment of oxygen in the bottom layer. Nevada). Nevertheless. then permanent density stratification will arise as a result of temperature differences within the water column. 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. it has been estimated. slow circulation or turnover of the water column occurs almost everywhere. however. STAGNANT BASINS. The cooler. most likely by absence of oxygen. denser waters remain at the bottom. that most of the world's oil was generated from source beds deposited under anoxic conditions. Color is not a reliable indicator.Organic Facies . especially during the Triassic along the margins of the developing Atlantic Ocean. particularly in understanding lacustrine beds. and therefore that dissolved-oxygen levels were below 0. once the original oxygen has been consumed in oxidizing organic matter. Conversely. The presence of pyrite itself can also be deceptive. Among the ancient lake beds thought to have been deposited in permanently stratified waters are the well-known Green River Shale (middle Eocene. Finally. in fact. The oxygen minimum layer usually begins immediately below the photic zone. Depths in excess of 200 m are required to prevent mixing during storms. Lakes in failed rifts can also contain organic-rich. This oxygen minimum develops when the rate of consumption of oxygen within that layer exceeds the rate of influx of oxygen to it. OXYGEN-MINIMUM LAYER (OML). where photosynthesis and turbulence can no longer contribute oxygen to the water.9 rocks therefore indicates that diagenesis was stopped prematurely. no more oxygen can enter. and warm climates are necessary to avoid overturn caused by freeze-thaw cycles. anoxia can be very local. anoxic sediments show preserved depositional laminae on a millimeter or submillimeter scale. and both the waters in the bottom layer and the underlying sediments will become anoxic. Therefore. Lakes of the Rift Valley of East Africa are excellent modern analogs receiving much attention from both researchers and explorationists at the present time. All anoxic sediments will be very dark gray or black when deposited. leading to the eventual development of a pycnocline (density interface) which prevents interchange between the two layers. Wyoming). Furthermore. The ultimate implications of anoxia for petroleum exploration are great. are not rich in organic carbon. very dark. it is instructive to consider complete stagnation. the Elko Formation (Eocene/Oligocene. and its presence indicates that the anaerobic reduction of sulfate ion did occur. although stunted burrows can be used as evidence of dysoxia. Truly stagnant basins are actually quite rare. Although pyrite does indeed form under anoxic conditions. but limnic environments often are. it cannot represent an anoxic facies. 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. it may well have developed after burial.2 mL/L. there is no guarantee that anoxia was present at the sea floor. The supply of fresh oxygen is therefore limited to horizontal . Color should be used mainly as a negative criterion: If a rock is not very.
high influxes of organic matter. and diminished bacterial activity. mid-Cretaceous. if the basin is deep enough. its intensity varies greatly. to a lesser extent. Bottomset beds associated with prograding delta systems can be rich in organic matter if they are laid down within a well-developed oxygen-minimum layer. Evaporitic environments combine the opportunity for abundant growth of algae with ideal conditions for preservation. Although an oxygen-minimum layer exists virtually everywhere in the ocean. Coal swamps can develop under a variety of conditions in both marine and non-marine environments. Intensely developed OMLs occur in areas of high productivity and. Shallowly silled basins often yield evaporites. Coal Swamps. permanent density stratification will develop. when a major transgression had greatly increased the continental shelf area.Organic Facies . because these horizontally moving waters also lie within the oxygen minimum layer. Late jurassic. In actuality there is a lazy turnover of the bottom waters. In an evaporitic environment (Karabogaz in the Caspian Sea) there is a net flow of water into the basin. In contrast. with the bottom layer almost isolated from the open-marine waters. Settings in which circulation is restricted are much more common than stagnant basins. those environments can also incorporate the features of an oxygen-minimum-layer model.. Although circulation in coal swamps is generally sluggish. and grazers and predatory organism are eliminated by the high salinities. which could be excellent hydrocarbon source rocks.g. because of their connection with the open-marine realm. Late Devonian) the world oceans were severely depleted in dissolved oxygen. During those times the OML expanded both upward and downward because of poor supply of oxygen to subsurface waters. Furthermore. This depletion was probably the result of the complex interplay of several factors. In either case. the shallowness of the swamps prevents the waters themselves from becoming anoxic. since most organic matter was destroyed within the overlying OML. Any organic matter arriving in those sediments will have an excellent chance to escape oxidation. or as lateral facies equivalente thereof. as a result of diminished oxygen demand. foreset beds within the same system are leaner in organic matter because they are deposited above the OML. and high hydrogen-sulfide concentrations create conditions poisonous to predators. Nutrients are concentrated by evaporation. in areas of poor circulation. These include the modern Peru-Chile shelf (high productivity associated with upwelling) and occurrences of black sediments of Aptian to Turonian age in the North Atlantic. Where the sill is shallow. High productivity reduces oxygen levels. the oxygen they can contribute is limited. the waters entering or leaving the basin are near surface. Wherever an intensely developed OML intersects the sediment-water interface. It has been proposed that at certain times in the past (e. whereas in a fluvially dominated system (Black Sea) the net flow of surface water is out over the sill. RESTRICTED CIRCULATION. It is not coincidental that these were times of deposition of large amounts of organic-rich rocks in many parts of the world. Below the OML oxygen levels again increase. Shallow Silling. There are other ancient and modern examples of organic-rich rocks deposited under anoxic or near-anoxic conditions associated with OMLs. the point of connection between the restricted area and the open-marine environment. Large amounts of organic material are preserved in coal swamps as a result of the combined effects of poor water circulation. Circulation is often restricted by the presence of a sill. The result is often deposition of organic-rich laminae within evaporites. sediments will be deposited under low-oxygen conditions. but it is too slow to disturb the anoxia which develops in the bottom layer. an upward expansion of the OML led to a tremendous increase in the surface area covered by anoxic bottom waters. However. including paleoclimate and water circulation.10 movement of oxygen-bearing waters. Anoxia . In times like the mid-Cretaceous.
all of which are chemically quite distinct from each other. That material which remains is dominantly of terrestrial origin. the phenolic components present in lignin-derived terrestrial material are toxic to many micro-organism. thus preventing extensive diagenesis of such material. The net result is a reduction in TOC values. Organic matter of algal (phytoplanktonic) origin is consumed more readily by organisms than are other types of organic material. TYPE OF ORGANIC MATTER. Most depositional settings not specifically catalogued above will be more or less well oxygenated. and other oxidative processes. because extensive decomposition occurs during its fall to the ocean floor. Lack of sulfate in non-marine swamps further prevents anaerobic microbial destruction of the organic matter. Rapid settling of organic debris through the water column is also important. TOC values increase as sediment-accumulation rates increase. Coals also accumulate very rapidly and. Dilution does not reduce the total amount of organic matter preserved. but it does spread that organic material through a larger volume of rock. cellulosic. lignitic. forest fires. with their high concentrations of organic matter. Rapid deposition of inorganic detritus is common in turbidites and in prodelta shales. Any extensive organic diagenesis is therefore likely to eliminate algal organic matter first.11 develops within the sediments rather than in the water column. It may also contain very resistent organic debris derived from erosion of ancient rocks. In fact. very slow sedimentation rates. much of the organic material that does reach the bottom in deep waters arrives in relatively large fecal pellets. and more favorable for gas than for oil. and low productivity in the overlying pelagic realm. and may include woody. Coals are important source rocks for gas accumulations. Nitrogen and phosphorus are in particular demand. The hydrocarbon-source potential of all of these oxidizing facies is low. as a result of more rapid removal of organic material from the zone of microbial diagenesis. RAPID SEDIMENTATION AND BURIAL. but the organic material is almost invariably woody. but their supposedly low potential for generating oil is to be reconsidered. at very high accumulation rate dilution may become a more important factor than increased preservation. Furthermore. provide an ideal means of maintaining low-oxygen conditions. cuticular. DILUTION Although high sediment-accumulation rates enhance preservation of organic matter. The extremely high accumulation rates for biogenic carbonates and siliceous sediments in zones of high productivity promote preservation of the associated algal protoplasm. biogenic inorganic sediment. Abyssal sediments are notoriously low in organic carbon as the result of the combined effects of high oxygen levels in abyssal waters. their virtual absence in much terrestrial organic material. or resinous material. . renders it of little nutritional value. Rapid sedimentation and burial con also enhance preservation. Oxic Settings. Phenolic bactericides derived from lignin hinder bacterial decay in the water and throughout the sediment column. especially in structural (woody) material. because its chemical components are digestible and provide precisely the nutrients required by scavengers and predators. Near-shore oxidizing facies sometimes have high TOC values. which settle several orders of magnitude faster than individual phytoplankton.Organic Facies . or organic material. and therefore wi11 contain primarily oxidized organic matter. Rapid burial is accomplished by a high influx of inorganic detritus.
and the presence of high TOC values coupled with the occurrence of undegraded marine organic matter. and rapid burial. There are a number of mechanisms by which oxygen depletion may be fostered and maintained. Biogenic sediments. lack of knowledge of seawater chemistry and nutrient availability at those times. It is often very difficult to separate the influences of these various factors in a particular depositional environment. Although certain periods undeniably contain more than their share of anoxic rocks. anoxia in bottom waters is a phenomenon whose effects we should learn to recognize in ancient rocks. Anoxic events in the past were probably not as large in scale or as long lasting as some workers have suggested.Organic Facies . dilution is far less marked. however. Facies changes from carbonates to shales may create large dilution effects that can be wrongly interpreted as indicating changes in oxygen levels. Of these. such models are not yet of much practical value for the distant past. in contrast. such events were often interrupted for long periods before anoxia was reinduced. including stagnancy or near-stagnancy. a strongly developed oxygen-minimum layer. Consequently. as a result of high productivity or sluggish circulation. Preservation is best accomplished where oxygen is excluded from bottom waters. dilution effects may lead to lower TOC values in spite of enhanced preservation rates. Our ability to make accurate predictions is limited. by uncertainties about exact continental positions and configurations in the past. SUMMARY There are three principal factors that affect the amount of organic matter in sedimentary rocks: primary photosynthetic productivity. however. anoxic sediments were deposited discontinuously through time and space. where sediment-accumulation rates are directly proportional to organic-carbon-accumulation rates. To derive maximum value from our analyses. Direct control of the anoxia was thus probably local. however. Models that integrate the concepts of organic richness with depositional cycles and facies analysis will be valuable tools for understanding hydrocarbon systems in basins. Rapid accumulation of sediment shortens the residence time of organic matter in the zone of diagenesis and thus promotes preservation. The most reliable criteria for bottom-water anoxia are the preservation of fine depositional laminae.and atmospheric-circulation patterns. in which the organic and inorganic materials arrive together. Shales. It is important to be able to distinguish local anoxia or anoxia developed deep within sediments from anoxia induced by anoxic bottom waters. Some of the commonly applied criteria are apt to be misleading. effectiveness of preservation.12 Dilution effects depend upon rock lithology. preservation is generally the most important. show strong dilution effects when accumulation rates are very high. in contrast. In biogenic sediments or coals. Because of its role in creating rocks with excellent hydrocarbon-source potential. Productivity can be predicted by locating ancient sites of marine upwellings. . we should always strive to place the organic rich rocks in the larger context of basin evolution through time and space. and dilution by inorganic material. and a very imperfect understanding of oceanic. If the rapidly accumulating sediment is mainly clastic. As in the modern oceans. are not as strongly affected by dilution.
in which one must also learn all the reactions of many classes of compounds. especially if one has to do it only occasionally. 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 objective of this chapter is to acquaint the reader with the names of common compounds and with several different conventions for drawing their structures. One common convention is to represent all the hydrogen atoms attached to a given carbon atom by a single H. hydrogen always forms one bond. and indeed in every carbon compound (except a few highly unstable ones created only in laboratories). two bonds. This objective is very different trom that of a normal course in organic chemistry. using a subscript on the H to denote the total number of hydrogens around that atom. however. The chemical reactions of interest to us are very few and are discussed only briefly. three bonds. creating long chains and ring structures. ethane. In each of these compounds. Writing the detailed structure of a simple molecule like methane is no problem.Organic Chemistry INTRODUCTION Anyone who uses petroleum geochemistry must be familiar with basic chemical terminology.Organic Chemistry . elsewhere in this text usage will vary. oxygen and sulfer. and cyclohexane. the explicit inclusion of every atom and every bond becomes extremely tedious. and nitrogen. Carbon atoms like to form bonds with each other. In this chapter we restrict the usage of the term hydrocarbon to the standard chemical one. . Examples of hydrocarbons are methane. trace metals. every carbon atom forms four bonds. as it does in the real world." but that usage is incorrect trom the chemist's point of view because those materials often contain substantial amounts of nitrogen. whose structures are shown below. Petroleum and natural gas are themselves often referred to as "hydrocarbons. Similarly. are termed organic. All compounds containing carbon atoms. Several different types of shorthand have therefore developed to facilitate drawing organic molecules. The following representations of n-pentane are equivalent: CH3CH2CH2CH2CH3 or CH3(CH2)3CH3. If one wants to draw large molecules. carbonates. NAMES AND STRUCTURES HYDROCARBONS In chemical terms a hydrocarbon is a compound containing only the elements carbon and hydrogen. and metal carbides. This unique property of carbon is responsible for the existence of literally millions of different organic compounds. The structures of methane and ethane are thus represented by CH4 and CH3CH3 respectively. Organic chemistry is thus the study of carboncontaining compounds. except carbon dioxide. oxygen.13 3 . and other elements. sulfur. and organic geochemistry the study of organic compounds present in geological environments.
These cyclic compounds (called naphthenes) are named by counting the number of carbon atoms in the ring and attaching the prefix cyclo. The zigzag configuration illustrated for n-pentane is adopted to show clearly each carbon atom. is the adjectival form of the word methane. The simplest series of hydrocarbons has linear structures. and indicates that there is no branching in the carbon chain.14 An even quicker shorthand that uses no letters at all has evolved. Many unsaturated compounds have carbon-carbon double . n-pentane and cyclohexane are represented by the line structures shown below. are able to combine with additional hydrogen. Note that the name of each compound ends in -ane. which. Isoprenoids ranging in length from six to forty carbon atoms have been found in petroleum and rocks. but the prefixes denoting the number of carbon atoms in the other alkanes are derived from Greek numbers. 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. which we used earlier. Each carbon atom is represented by a point. in contrast. simple inspection shows how mant' hydrogen atoms each carbon atom must have. For example. the names of the other nine simplest n-alkanes are given in the following table. Among the most important branched hydrocarbons in organic geochemistry are the isoprenoids. as in "alkane. That is." The first four names are irregular. and carbon-carbon bonds are shown as lines connecting those points. We have also seen that carbon atoms can be arranged in rings. In the case of 2methylhexane (C7H16) the basic structure is hexane.Organic Chemistry . Hydrogen atoms and bonds to hydrogen atoms are not shown at all. ethyl and propyl). 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. a CH3 (methyl) group is attached to the second carbon atom. Another important group of hydrocarbons is the unsaturates. The letter n stands for normal. All the compounds mentioned above are called saturated hydrocarbons or saturates. The term methyl. no more hydrogen can be incorporated into the molecule without breaking it apart. We have ahready encountered n-pentane. these molecules are called n-alkanes or nparains. Branching can occur. Other adjectival forms are made by dropping the -ane ending and adding yl (for example. Because we know that each carbon atom forms four bonds and each hydrogen atom forms one bond. giving rise to a vast number of possible structures.
the compounds in which they occur are called heterocompounds. Aromatics possess a system of alternating single and double bonds within a cyclic structure. They are named in a similar manner to the alkanes.Organic Chemistry . The hydrocarbons present in petroleum are mostly the end products of extensive degradation of biogenic molecules. these compounds are called alkenes. but they actually have completely different chemical properties from alkenes and are unusually stable. Many common NSO compounds are not directly related to biogenic precursors. including hydrogenafion. these compounds are quite different trom the majority of the organic molecules found in living organisms. In the laboratory they are readily converted to alkanes by the addition of hydrogen in the presence of a catalyst. except that the ending -ene indicates the presence of a double bond. Aromatics form an extremely important class of unsaturated hydrocarbons. sulfur. Among the most important NSO compounds are the asphaltenes. At first glance aromatics appear to be nothing more than cyclic alkenes containing several double bonds. nitrogen. The extreme case is graphite. bitumen. Polycyclic aromatic hydrocarbons having fused ring structures are quite common. It is this delocalization of electrons which makes aromatic compounds very stable. and kerogen are called heteroatoms. which are large. Most biological molecules are larger and more complex than the simple hydrocarbons. Although they are unsaturated. they are free to move throughout the cyclic system instead of being held between two particular carbon atoms. because the most common heteroatoms are nitrogen. NONHYDROCARBONS Atoms other than hydrogen and carbon that occur in petroleum. Because alkenes are highly reactive. and cyclohexene (C6H10). highly aromatic materials of . Although they are very important constituents of petroleum. they do not add hydrogen easily. some complex hydrocarbons that are found in fossil organic material can be related directly to individual biological precursors. and oxygen. or other elements. A simplified notation for drawing these molecules permits us to represent the double-bond system by a circle within the ring. Some aromatic molecules are very large. Heterocompounds are also called NSO compounds. By hydrogenation ethene thus reacts to form ethane. The hydrocarbons we discussed so far are relatively simple molecules. The circle indicates that the electrons in the double bonds are delocalized.15 bonds. Examples are ethene (C2H4) . Their stability permits aromatics to be important constituents of oils and sediments. that is. Many of the heterocompounds present in organisms are converted to hydrocarbons during diagenesis and catagenesis. the structures of which are shown below. sulfur. they do not long persist in geologic environments. converts alkenes to alkanes and cyclic compounds during diagenesis. A variety of reactions. In fact. of which some are biogenic and others are formed during diagenesis. propene (C3H6). Fossil organic matter often contains a vide variety of heterocompounds. phosphorus. the majority contain oxygen. which is an almost-endless sheet of aromatic rings.
Organic Chemistry . Amino acids are the building blocks of proteins. however. They are rapidly metabolized by virtually all organisms. most carbohydrates are attacked readily by microorganisms. and thus are seldom preserved in sediments (exceptions occur in shell material and in bones. Lignin is an important component of wood. the latter is the most abundant organic compound in the biosphere. but asphaltene molecules are smaller and more aromatic than most kerogens. Carbohydrates include starch. sugars. Lignin and cellulose are major constituents of humic coals. and thus tends to become concentrated as other organic matter is decomposed. Lignin monomers are linked topether to form molecules having molecular weights from 3000 to 10. Because phenols are potent bactericides. Upon decomposition lignin forms phenolic compounds. Many nonhydrocarbon molecules common to living organisms are also present in sediments. it is an important constituent of terrestrial organic matter. providing much of the structural support for large land plants. carbohydrates. lignin is rather resistant to degradation.000 atomic mass units. Among these are lignin. They have many characteristics in common with kerogen. It is a polymer consisting of many repetitions and combinations of three basic aromatic subunits. Although cellulose is quite resistant to decomposition under some conditions. where small amounts of preserved amino acids can be used to date specimens) .16 varying structure. and cellulose. which are aromatics having a hydroxyl group (OH) attached. and amino acids. Like lignin.
the geopolymers become larger. Today it is used to describe the insoluble organic material in both coals and oil shales. Coals and oil shales should therefore be viewed merely as sedimentary rocks containing special types of kerogens in very high concentrations. Diagenesis results mainly in loss of water.Kerogen . True kerogens. have more mineral matter than algal coals. The detailed chemistry of kerogen formation need not concern us greatly. The term kerogen was originally coined to describe the organic matter in oil shales that yielded oil upon retorting. strongly influence the ability of the kerogen to generate oil and gas. slightly larger ones. because it has patchwork structures formed by the random combination of many small molecular fragments. which are reflected in their chemical and physical properties. and natural gas. having very high molecular weights. and how much oil or gas can be expected. If anaerobic sulfate . large molecules that have no regular or biologically defined structure. as well as the nature of the organic matter from which it was formed. and the individual component parts are either destroyed or used to construct new geopolymers. soils. Coals are a subcategory of kerogen. and less regular in structure.Kerogen INTRODUCTION Kerogen is normally defined as that portion of the organic matter present in sedimentary rocks that is insoluble in ordinary organic solvents. Oil shales. The soluble portion. Diagenetic and catagenetic histories of a kerogen. 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. carbon dioxide. which have molecular weights of several thousand or more. develop after tens or hundreds of meters of burial. will be discussed in a following chapter. Each kerogen molecule is unique. and sediments. Algal (boghead) coals are formed in environments where the source phytoplankton lack both calcareous and siliceous skeletal components. called bitumen. The residual kerogens also undergo important changes. when the chemical and biological destruction and transformation of organic tissues begin. The smallest of these geopolymers are usually called fulvic acids. Lack of solubility is a direct result of the large size of kerogen molecules. Subsurface heating causes chemical reactions that break off small fragments of the kerogen as oil or gas molecules. more complex. A basic understanding of how kerogen is formed and transformed in the subsurface is therefore important in understanding how and where hydrocarbons are generated. These geopolymers are the precursors for kerogen but are not yet true kerogens. and still larger ones. 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. oil. as well as dispersed organic matter in sedimentary rocks. The amount of organic matter tied up in the form of kerogen in sediment is far greater than that in living organisms or in economically exploitable accumulations of coal. During the course of diagenesis in the water column. humic acids. whether these hydrocarbons are mainly oil or gas. in contrast. Large organic biopolymers of highly regular structure (proteins and carbohydrates.17 4 . humins. KEROGEN FORMATION The process of kerogen formation actually begins during senescence of organisms. Humic coals are best thought of as kerogens formed mainly from landplant material without codeposition of much mineral matter. Kerogen composition is also affected by thermal maturation processes (catagenesis and metagenesis) that alter the original kerogen. with some of the inorganic matrix often being contributed by the algae themselves. for example) are partially or completely dismantled. and ammonia from the original geopolymers.
KEROGEN COMPOSITION Because each kerogen molecule is unique. They identified three main types of kerogen (called Types I. contain mainly the most resistant types of biogenic molecules that were ignored by microorganisms during diagenesis. What is within our reach. therefore. it would not be of great and direct significance to exploration geologists. The amount of sulfur contributed by the original organic matter itself is very small. in contrast. because the bacterial enzyme systems do not know how to attack them. large amounts of sulfur may become incorporated into the kerogen structure. is developing a general method of describing gross kerogen composition and relating it to hydrocarbon-generative capacity. Carboncarbon double bonds. Most organic oxidation in sedimentary environments is microbially mediated. In an oxidizing environment many of the small biogenic molecules will be attacked by bacteria before they can form geopolymers. About a decade ago workers at the French Petroleum Institute developed a useful scheme for describing kerogens that is still the standard today. Those kerogens formed under oxidizing conditions. are converted into saturated or cyclic structures. better organic preservation. In a low-oxygen (reducing) environment. Even if such a description were possible. in contrast. the macerals that they are composed of. II. The four types of kerogen. Subsequent investigations have identified Type IV kerogen as well. Kerogen formation competes with the destruction of organic matter by oxidative processes. and their organic precursors Transformation of organic material in sediments and sedimentary rocks. or at least look very much like biogenic molecules. and ultimately of much greater practical value. which are highly reactive. Geopolymers are more or less immune to bacterial degradation. and III) and have studied the chemical characteristics and the nature of the organisms from which all types of kerogens were derived. and if the sediments are depleted in heavy-metal ions (which is often the case in nonclastic sediments but is seldom true in shales).18 reduction is occurring in the sediments. Kerogens formed under reducing conditions will be composed of fragments of many kinds of biogenic molecules.Kerogen . . it is somewhat fruitless to attempt a detailed discussion of the chemical composition of kerogens. the subdued level of bacterial activity allows more time for the formation of geopolymers and. One way that we can begin is by classifying kerogens into a few general types. Microorganisms prefer to attack small molecules that are biogenic.
in contrast. The various Type II kerogens are grouped together. The shaded areas approximately represent diagenesis. Type III kerogens have much lower hydrocarbon-generative capacities than do Type II kerogens and. Type II kerogens arise from several very different sources. Type III kerogens are composed of terrestrial organic material that is lacking in fatty or waxy components. in contrast. are normally considered to generate mainly gas. In the immature state. The best-known example is the Green River Shale. including marine algae. Type IV kerogens.Kerogen . Occurrences of Type I kerogens are limited to anoxic lakes and to a few unusual marine environments. have lower hydrogen contents because they contain extensive aromatic systems. Type IV kerogens contain mainly reworked organic debris and highly oxidized material of various origins. catagenesis. successively. Most Type II kerogens are found in marine sediments deposited under reducing conditions. Type I and Type II kerogens. phenols. They also include contributions from bacterial-cell lipids. have the lowest hydrogen contents. from Wyoming. Type I (algal) kerogens have the highest hydrogen contents because they have few rings or aromatic structures. 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. Type III (humic) kerogens. which mainly contain polycyclic aromatic systems. Heteroatom contents of kerogens also vary with kerogen type. leaf waxes. Cellulose and lignin are major contributors. because they all have great capacities to generate liquid hydrocarbons. unless they have small inclusions of Type II material. Type III kerogens have high oxygen contents because they are formed from lignin. pollen and spores. and Colorado. and metagenesis. of middle Eocene age. and fossil resin. They are generally considered to have essentially no hydrocarbon-source potential. . despite their very disparate origins. Utah. and carbohydrates. Type IV kerogens are highly oxidized and therefore contain large amounts of oxygen.19 Type I kerogen is quite rare because it is derived principally from lacustrine algae. Hydrogen contents of immature kerogens (expressed as atomic H/C ratios) correlate with kerogen type. Van Krevelen diagram showing maturation pathways for Types 1 to IV kerogens as traced by changes in atomic HIC and OIC ratios. Type I kerogens have high generative capacities for liquid hydrocarbons. cellulose. contain far less oxygen because they were formed from oxygen-poor lipid materials. Type II (liptinitic) kerogens are also high in hydrogen.
forcing us to make assumptions about the source organisms. nonclastic sediments). metagenesis is not equivalent to "metamorphism. 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. because fresh waters are usually low in sulfate. which is destroyed rapidly during diagenesis. By convention the term catagenesis usually refers to the stages of kerogen decomposition during which oil and wet gas are produced. High-sulfur kerogens (and coals) are almost always associated with marine deposition. however. Catagenesis refers to transformations of kerogen molecules. The correspondence is not perfect. The division of kerogens into Types I-IV on the basis of chemical and hydrocarbon-generative characteristics has been supported by another independent scheme for classifying kerogens using transmitted-light microscopy. they represent fundamentally different perspectives. marine. a term taken trom coal petrology. break off small molecules and leave behind a more resistant kerogen residue. The kerogen in a given sedimentary rock includes many individual particles that are often derived from a variety of sources. most terrestrially influenced kerogens are low in nitrogen. The biggest problem comes in identifying Type III kerogen. KEROGEN MATURATION INTRODUCTION Very important changes. . called maturation. anoxic. represents drygas generation. In many cases the original cellular structure is still recognizable. Despite its name.20 Sulfur and nitrogen contents of kerogens are also variable and. Catagenesis and hydrocarbon generation occur concurrently. the materials from which a maceral was derived. In principle. The small molecules eventually become petroleum and natural gas. because there is not a perfect biological separation of the various types of living organic matter. however. in contrast. in some cases. Sulfur is only incorporated into kerogens in large quantities where sulfate reduction is extensive and where Fe +2 ions are absent (organic-rich. Macerals are essentially organic minerals. Although the terms catagenesis and oil generation are often used synonymously. In others the original fabric has disappeared completely. but it also continues through the metamorphic stage. Because lignins and carbohydrates contain little nitrogen. but they really represent different aspects of the same process. Microscopic organic analysis has reached a fairly high level of refinement and is often capable of assessing kerogen type with good accuracy. proving the origin of the particle. occur when a kerogen is subjected to high temperatures over long periods of time. is derived mainly from sulfate that was reduced by anaerobic bacteria. 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. Most high-nitrogen kerogens were therefore deposited under anoxic conditions where diagenesis was severely limited. Kerogen types are defined by the morphologies of the kerogen particles. wherever possible. interrelated. Maceral names were developed by coal petrologists to describe. especially when we are discussing both aspects simultaneously. Thus few kerogens consist of a single maceral type. Kerogen sulfur. Nitrogen is derived mainly from proteinaceous material. whereas hydrocarbon generation focuses on the production of hydrocarbon molecules. they are not precisely equivalent.Kerogen . A list of the most common macerals and their precursors is given in the table presented earlier in this chapter. they are to kerogen what minerals are to a rock. called catagenesis and metagenesis. In this text we shall use the terms somewhat interchangeably. The different types of kerogen particles are called macerals. Many high-sulfur kerogens are also high in nitrogen. Thermal decomposition reactions." Metagenesis begins long before true rock metamorphism. Metagenesis.
after hydrogen loss is well advanced.Kerogen . 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. The composition of the products (bitumen. This complex interplay between the effects of time and temperature on maturity is discussed in a later chapter.21 This chapter will focus on those changes in the residual kerogen that accompany catagenesis. and thus are not necessarily valid indicators of hydrocarbon generation. the cracking of any organic molecule requires hydrogen. and III kerogens will therefore be very similar chemically. Because many of the light product molecules are rich in hydrogen. thus allowing us to judge the extent to which kerogen maturation has proceeded. Chemical reaction-rate theory requires that the rates of reactions decrease as temperature decreases. and gas) will be discussed in a following chapter. Furthermore. Kerogen maturation is not a reversible process-any more than baking a cake is reversible. All kerogens become increasingly aromatic and depleted in hydrogen and oxygen during thermal maturation. These reactions are intimately related to important changes in the chemical structure of kerogen. Some of these changes can be measured quantitatively. II. the residual kerogen gradually becomes more aromatic and hydrogen poor as catagenesis proceeds. As we saw earlier. There is a steady color progression yellow-goldenorange-light brown-dark brownblack as a result of polymerization and aromatization reactions. 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. The real reason for following kerogen catagenesis. Types I. In contrast. but it also states that at any temperature above absolute zero reactions will be occurring at some definable rate. but they are not necessarily identical with hydrocarbon generation. It is impossible to set precise and universal temperature limits for catagenesis. Furthermore. is to monitor hydrocarbon generation. Nitrogen and sulfur are also lost from kerogens during catagenesis. The more hydrogen a kerogen contains. Kerogen particles become darker during catagenesis and metagenesis. Old rocks will often generate hydrocarbons at significantly lower temperatures than young rocks. 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. it is also true that other changes in kerogen properties have little or nothing to do with it. the rates of catagenesis are generally not important at temperatures below about 70° C. because time also plays a role. simply because the longer time available compensates for lower temperatures. high-sulfur oils found in a number of areas. Nitrogen loss occurs primarily during late catagenesis or metagenesis. EFFECTS OF MATURATION ON KEROGENS Kerogen undergoes important and detectable changes during catagenesis and metagenesis. For practical purposes. provided that the hydrogen content of the kerogen was known prior to the onset of catagenesis. including the Miocene Monterey Formation of southern California. The most important implication of these chemical changes is that the remaining hydrocarbongenerative capacity of a kerogen decreases during catagenesis and metagenesis. the more hydrocarbons it can yield during cracking. In the late stages of maturity. however. even if drastic decreases in temperature occur. oil. as evidenced by low maturity. the chemical process of maturation never stops completely. There is therefore no necessary cause-and-effect relationship . of course. possessing essentially no remaining hydrocarbon generative capacity. much as a cookie browns during baking. much of the sulfur is lost in the earliest stages of catagenesis. Although it is obvious that many measurable changes in kerogens are related to hydrocarbon generation.
The concentration of free radicals in a given kerogen has been found to increase with increasing maturity.Kerogen . and no guarantee that a particular kerogen color always heralds the onset of oil generation. Free-radical concentrations can be measured by electron-spin resonance. One property that is strongly affected. and the less it will be reflected. If neither expulsion from the source rock nor cracking of bitumen occurred. Because coal rank is merely a measure of coal maturity. carbon-isotopic compositions of kerogens are affected little by maturation. because the flat aromatic sheets can stack neatly. and because vitrinite particles also occur in kerogens. HYDROCARBON GENERATION As kerogen catagenesis occurs. These small compounds are much more mobile than the kerogen molecules and are the direct precursors of oil and gas. however. and which can be used to gauge the extent of molecular reorganization. is the ability of kerogen particles to reflect incident light coherently. small molecules are broken off the kerogen matrix. somewhat beyond the oil-generation window.22 between kerogen darkening and hydrocarbon generation. contain large numbers of unpaired electrons. resulting in lower bitumen contents in the source. What actually occurs. The difference between the two curves represents bitumen expelled from the rock or cracked to light hydrocarbons. Cracking often produces free radicals. Both curves are highly . which are unpaired electrons not yet involved in chemical honds. Kerogens. its structure becomes more ordered. Plot of bitumen generation as a function of maturity (dashed fine) compared to bitumen remaining in rock (solid line). Some of these are hydrocarbons. called vitrinite reflectance. The more random a kerogen's structure. Some properties of kerogen change very little 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. Bitumen generation occurs mainly during catagenesis. the more an incident light beam will be scattered. A general name tor these molecules is bitumen. has been widely and successfully applied in assessing kerogen maturity. Except for darkening. especially highly aromatic ones. 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. while others are small heterocompounds. These structural reorganizations bring about changes in physical properties of kerogens. during metagenesis the chief product is methane. the technique. Kerogens often fluoresce when irradiated. there would be a large and continuous build-up of bitumen in the rock as a result of catagenetic decomposition of kerogen. For example. The intensity and wavelength of the fluorescente are functions of kerogen maturity. is that some of the bitumen is expelled from the source rock or cracked to gas.
when large geopolymers are created from biological molecules. It has become apparent in recent years that not all kerogens generate hydrocarbons at the same catagenetic levels. Kerogens formed from resinite will generate condensates or light oils quite early. Other kerogens usually follow a more traditional model. 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. whereas those kerogens that contain few lipids will generate mainly gas. because natural variations among samples cause much scatter in experimental data. Catagenesis of kerogen produces a more aromatic. residual kerogen as well as small molecules that are the direct precursors for petroleum and natural gas. In such cases the expelled products will be mainly gas. Rich rocks will become overpressured earlier than lean ones and thus will also expel hydrocarbons earlier. The chemical composition and morphology of kerogen macerals depend both on the type of original organic matter and on diagenetic transformations. however. although we know that oil generation does occur during the phase we call catagenesis. Candidates for early expulsion would be very organic rich rocks and those containing resinite or high-sulfur kerogens. High-sulfur kerogens generate heavy. as measured by parameters such as vitrinite reflectance. Conversely. this result is hardly surprising. In very lean rocks expulsion may occur so late that cracking of the generated bitumen is competitive with expulsion. . Microfracturing is related to overpressuring. Sulfur-rich kerogens decompose easily because carbon-sulfur hbonds are weaker than any bonds in sulfur-poor kerogens. We shall consider the latter briefly here. Timing and efficiency of expulsion depend on a number of factors. Numerous methods exist for tracing the history of a kerogen and determining its original chemical and physical characteristics. hydrogen-poor. including rock physics and organic-geochemical considerations. The chemical composition of a kerogen controls the timing of hydrocarbon generation and the type of products obtained. high-sulfur oils at low levels of maturity.Kerogen . but none of these measurements is closely linked to the actual process of hydrocarbon generation. Source rocks that generate large amounts of hydrocarbons early are likely to expel those hydrocarbons early. SUMMARY Kerogen begins to form during early diagenesis.23 idealized. Many workers now believe that microfracturing of source rocks is very important tor hydrocarbon expulsion. Effective generation of hydrocarbons requires that the generated products be expelled from the source-rock matrix and migrated to a trap. which in turn is partly attributed to hydrocarbon generation itself. Thus. Given the significant chemical differences among the various types of kerogens. Kerogens formed from lipid-rich organic material are likely to generate liquid hydrocarbons. we cannot always define the limits of hydrocarbon generation with great confidence. those rocks that generate few hydrocarbons may not expel them until they have been cracked to gas. Resinite consists of polymerized terpanes (ten-carbon isoprenoids) that can decompose easily by reversing the polymerization process. Several methods exist for estimating the extent to which hydrocarbon generation has occurred in a given kerogen.
Asphaltenes tend to aggregate into stacks because of their planarity. Much of this variety is related to source-rock facies and the composition of the kerogens that generated the bitumens. Heavier aromatic and naphthenoaromatic hydrocarbons. n-alkanes. Few of these heterocompounds have been studied carefully. Major compositional changes occur in going from bitumen to petroleum. variously called polars. The lighter of these fractions. and resins. Reservoir transformations in some cases greatly affect oil composition and properties. while others are only trace contributors. Light aromatic hydrocarbons. Petroleum. There is no doubt that they are related. However. indeed. and Natural Gas - 5 . and steranes. Both bitumens and petroleums exhibit a wide range of compositions. Saturated hydrocarbons are the most thoroughly studied of the components of petroleum and bitumen because they are the easiest to work with analytically. contains a wide variety of small and medium-sized molecules with one or more heteroatoms. 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. and cyclics. bitumen is almost universally accepted as the direct precursor for petroleum. triterpanes. but we are not certain whether they occur mainly within the source rock or during migration through the reservoir rock.24 Bitumen. Each of the fractions contains certain types of chemical compounds. Petroleum. Some of these are present in relatively large quantities. highly aromatic asphaltene molecules that are often rich in heteroatoms. have been studied in petroleums. and Natural Gas INTRODUCTION Petroleum obtained from reservoir rocks and bitumen extracted from fine-grained rocks have many similarities. This chapter will compare and contrast bitumen and petroleum compositions and examine the factors responsible for the observed differences. like benzene and toluene. however. branched hydrocarbons (including isoprenoids). we first separate a crude oil or a bitumen into several fractions having distinct properties. Such correlations can be particularly useful in establishing genetic relationships among samples. We also do not know how much of the change involves chemical reactions. Maturity also exerts control over bitumen and petroleum composition. In order to understand bitumen and petroleum compositions and to use them for exploration. NSOs. and how much is due to physical separation of chemical compounds having very different properties.000. but these compounds are lost from bitumens during evaporation of the solvent used in extracting the bitumen from the rock. Bitumen and petroleum compositions can also be used as tools in correlating samples with each other. The large sizes of asphaltene units render . many unanswered questions remain about the processes that transform bitumen into petroleum. The final fraction contains very large.Bitumen. In order to investigate the individual compounds present. A second fraction consists of aromatic hydrocarbons and some light sulfur-containing compounds. Most of the NSO compounds appear in the remaining two fractions. particularly those derived from diterpanes. but they also exhibit many important differences. and form complexes with molecular weights of perhaps 50. COMPOUNDS PRESENT IN BITUMEN AND PETROLEUM GENERAL CLASSES OF COMPOUNDS Both bitumen and petroleum contain a very large number of different chemical compounds. are more commonly studied. The influence of the lithologies of source and reservoir rocks on these compositional changes is poorly understood. One fraction consists mainly of saturated hydrocarbons.
In a few cases specific precursor organisms or molecules can be identified. whereas in other instances we may be able to limit the possible precursors to only a few species. The distributions are quite sharp. the CPI is greater than 1. If the number of odd. Their high concentration in bitumens and oils is best explained by their existence in plant and algal lipids. however. of course. but their sources are simply no longer recognizable due to diagenetic and catagenetic transformations.Bitumen. are essentially molecular fossils. of biological origin. The most useful biomarkers serve as indicators of the organisms from which the bitumen or petroleum was derived.or even-carbon homologs is evident. even-carbon homologs predominate as strongly as do the oddcarbon homologs among the n-alkanes. 27. and no preference for either odd. marine algae produce n-alkanes that have a maximum in their distribution at C-17 or C22. CPI values can therefore . Other compounds. because the concentration of n-alkanes often decreases with increasing carbon number.0. In contrast. SPECIFIC COMPOUNDS Biomarkers. (Among the acids and alcohols present in living organisms. The average of two ranges is taken to minimize bias produced by the generally decreasing n-alkane concentrations with increasing number of carbon atoms. Another important indication of the origin of n-alkanes is the distribution of individual homologs. Because of their molecular complexity and heterogeneity. or CPI. 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. however. the lower-carbon homologs are given more weight in the calculation. However. Their n-alkane distributions reflect this mix. They are. 29. In most cases. where input of terrestrial n-alkanes is minimal and diagenetic conditions are highly reducing. especially 23. or of the diagenetic conditions under which the organic matter was buried. such as pentane or propane. and by their catagenetic formation from long-chain compounds such as fatty acids and alcohols. the CPI is 1.) Even-carbon preferences occur principally in evaporitic and carbonate sediments. Petroleum. Carbon Preference Index. and Natural Gas . or members of the n-alkane series. Sediments are also known that exhibit a strong preference for n-alkanes having an even number of carbon atoms.0.25 them insoluble in light solvents. If odd-carbon homologs predominate. which are derived from biogenic precursor molecules. Many sediments. asphaltene molecules have not been studied in detail. depending upon the species present. and 31 atoms. These compounds.and even-carbon members is equal. FACTORS AFFECTING COMPOSITION OF BITUMEN AND PETROLEUM SOURCE AND DIAGENESIS Biomarkers n-Alkanes were among the first biomarkers to be studied extensively. 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). although we know for certain that the biomarker molecule is biogenic. For the most part n-alkanes present in terrestrial plants have odd numbers of carbon atoms. an abbreviation for biological markers. 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. 25. Asphaltenes can thus be removed from oils or bitumens in the laboratory or refinery by adding a light hydrocarbon. receive contributions of n-alkanes from both terrestrial and marine sources. we are unable to use it as an "index fossil" for specific organisms.
Bitumen, Petroleum, and Natural Gas -
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.
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 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.
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.
Laminated source rocks may therefore expel hydrocarbons with greater efficiency than massive rocks. Momper's value has been widely accepted as a reasonable average. it is probably most effective in immature rocks. By far the most popular mechanism invoked today to explain primary migration is expulsion of hydrocarbons in a hydrophobic (oily) phase. Many cycles of pressure buildup. PRIMARY MIGRATION MECHANISMS Many theories about primary migration (expulsion) have been popular at various times. oil-phase expulsion. Momper (1978) suggested that in most cases no microfracturing or expulsion could occur until a threshold amount of bitumen had been generated in the source rock. the microfractures heal. and pressure release can be repeated. lowpermeability source rock into a carrier bed having much greater permeability. Traps are the means by which migration is stopped and accumulation occurs. When the internal pressures exceed the strength of the rock. particularly along lines of weakness such as bedding planes. Diffusion has been shown to be active on at least a minor scale and over short distances in carefully studied cores.Migration . Accumulation is the concentration of migrated hydrocarbons in a relatively immobile configuration.29 6 . Once the internal pressure has returned to normal. and solution in gas. The hydrocarbons within the pores then become isolated again because of the impermeability of the waterwet source rocks to hydrocarbons. Today there are only three mechanisms of primary migration that are given serious consideration by most petroleum geochemists: diffusion.Migration DEFINITIONS Migration is the movement of oil and gas within the subsurface. There appear to be three distinct ways in which oilphase expulsion can occur. but will describe the most widely held views on the dominant mechanisms of primary and secondary migration and accumulation. An important implication of the microfracturing model is that expulsion cannot take place until the strength of the source rock has been exceeded. Each of these steps is quite distinct from the others. In order to understand the complex sequence of events that we call migration. and overpressuring commences anew. Primary migration is the first phase of the migration process. expulsion. Secondary migration is the movement of oil and gas within this carrier bed. Diffusion would therefore have to be coupled with a powerful concentrating force to yield accumulations of appreciable size. microfracturing occurs. we must look at each of these steps separately. This chapter wi11 not go into the physics and chemistry of migration in detail. it involves expulsion of hydrocarbons from their fine-grained. Although the exact threshold value must vary considerably as a function of rock lithology and other factors. One occurs most commonly as a result of microfracturing induced by overpressuring during hydrocarbon generation. microfracturing. where pre-existing light hydrocarbons bleed out of the rocks prior to the onset of significant generation and expulsion. whereas accumulation of hydrocarbons requires concentration. . The main problem with diffusion as an important mechanism of migration is that diffusion is by definition a dispersive force. but those that have been discounted will not be discussed here. where they can be preserved over long periods of time. During intense hydrocarbon generation. Based on empirical evidence. Furthermore. 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.
Because neither case is of great general significance for petroleum formation. In most cases the distances of primary migration are probably between 10 centimetres and 100 m. Of course. oil-phase expulsion can take place when bitumen forms a continuous network that replaces water as the wetting agent in the source rock. Thus inefficiency of expulsion is responsible for much of the difference in composition of bitumen and petroleum that we noted earlier. therefore. primary migration may be of poor efficiency. Thus a source rock lying between two sands will expel hydrocarbons into both carrier beds. The third mechanism. DISTANCE AND DIRECTION The distances traversed by hydrocarbons during primary migration are short. In most cases hydrocarbons are generated within short distances of viable secondary-migration conduits. Finally.30 Once the threshold has been exceeded. As soon as easier paths become available. also make excellent secondary-migration pathways. Therefore the threshold must represent not only a hurdle to be cleared by the bitumen before it can leave the source rock. but a large proportion of NSO compounds and heavier hydrocarbons are left behind. this approach is rather approximate. it would be expected only in the late stages of catagenesis or in source rocks capable of generating mainly gas. but it does give some idea of the efficiency of expulsion. Thus primary migration ends whenever a permeable conduit for secondary migration is reached. hydrocarbons will be expelled in any direction that offers a lower pressure than that in the source rock. the migrating fluids will take them." We can only estimate the fraction of the bitumen left in the source rock during microfractureinduced expulsion. expulsion of oil dissolved in gas. Expulsion of hydrocarbons is facilitated because water-mineral and water-water interactions no longer need be overcome. most of the hydrocarbons are expelled. Because the driving force for microfracture-induced primary migration is pressure release. This type of expulsion is probably only operative in very rich source rocks during the main phase of oil generation. requires that there be a separate gas phase.Migration . we can estimate that once the expulsion threshold is reached the expulsion efficiency for bitumen is about 50%. where they do exist. Fracture and joint systems. A second way in which oil-phase expulsion can occur is from very organic-rich rocks prior to the onset of strong hydrocarbon generation. but also an "exit tax. This expulsion process probably releases internal pressures in the rock. The organic matter expelled consists mainly of lipids that were present in the sediment during deposition and diagenesis. expulsion can be lateral. Massive. . Such a phase could only exist where the amount of gas far exceeds the amount of liquid hydrocarbons. this early expulsion mechanism seems to be limited to rocks having very high original contents of lipids. particularly in brittle carbonate and opal-chert source rocks. Primary migration is unquestionably the most difficult part of the entire migration process. but the mechanism by which overpressuring is achieved is not understood. Primary migration is difficult and slow. we conclude that solution in gas is a minor mechanism for oil expulsion. and assuming that expulsion of hydrocarbons is ten times as efficient as expulsion of NSO compounds. unfractured source-rock units are relatively rare. or downward. Therefore. By comparing the average hydrocarbon compositions of bitumen and crude oil. upward. depending upon the carrier-bed characteristics of the surrounding rocks. because petroleum is being forced through rocks having low matrix permeabilities. Because the source rock is overpressured. Sand stringers within shale units can provide secondary migration conduits for hydrocarbons sourced in the shales.
secondary migration will occur both laterally and vertically. the pore throat is very tiny or if the buoyant force is small. Within massive sandstone. whereas capillary-entry pressure retards or stops it. The smaller the pore throat. requiring only the existence of two forces. Hydrocarbons are almost all less dense than formation waters. secondary migration will cease until either the capillary-entry pressure is reduced or the buoyant force is increased. the more deformation is required. the globule cannot enter. 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. That is. A third force-namely. hydrodynamic flow. If the upward force of buoyancy is large enough. The upward buoyant force is partly or completely opposed by the capillary-entry pressure. If the capillary-entry pressure exceeds the buoyant force. Where faulting or facies changes create impassable barriers (capillary-entry pressure exceeds buoyant force). Thus movement within a confined migration conduit will be updip perpendicular to structural contours whenever possible. hydrocarbons entering the land from an underlying source rock will move toward the top of the sand even as they migrate laterally updip. however.Migration . Buoyancy promotes migration. migration may have to proceed at an oblique angle to structural contours. Hydrocarbons are thus capable of displacing water downward and moving upward themselves. This model is very simple. and therefore are more buoyant. the force required to deform the oil globule enough to enter the pore throat. Opposing the buoyancy is capillary-entry pressure. Structural contours on the top of the carrier bed will . and becomes stuck until either the buoyant force or the capillary entry pressure changes. the globule must deform to squeeze into the pore.31 SECONDARY MIGRATION MECHANISM Once hydrocarbons are expelled from the source rock in a separate hydrocarbon phase into a secondary-migration conduit. can modify hydrocarbon movement. Whenever a pore throat narrower than the globule is encountered. In contrast. When hydrocarbons cease moving. These modifications to the overall scheme are probably minor. if bulk water movement opposes the direction of buoyant movement. If water is flowing in the subsurface in the same direction as hydrocarbons are moving by buoyancy. the globule will squeeze into the pore throat and continue moving upward. then the rate of hydrocarbon movement should be enhanced somewhat. then the rate of hydrocarbon transport will be retarded. If. which is resistance to entry of the hydrocarbon globule or stringer into pore throats. This fact has important implications for tracing migration pathways through a thick conduit. Coalescence of globules of hydrocarbons after expulsion from the source rock therefore increases their ability to move upward through water-wet rocks. we say that accumulation has occurred. Retardatin of buoyant movement as an oil globule (X) is deformed to fit in to a narrow pore throat (Y). but it is not essential and does not change our basic model. DISTANCE AND DIRECTION Secondary migration occurs preferentially in the direction that offers the greatest buoyant advantage. subsequent movement of the hydrocarbons will be driven by buoyancy.
the heavy oils in the Orinoco Belt of Venezuela. This model greatly simplifies the problem of accumulation. Today we believe that hydrocarbons migrate as a separate phase. The question of long-distance migration has been much discussed and disputed. however. the process of hydrocarbon accumulation was somewhat mystical. all must have migrated long distances. at which time they suddenly became immiscible with the water and formed a separate hydrocarbon phase. Faults may play an important role in vertical migration. for example. not only because they often juxtapose carrier beds from different stratigraphic horizons. Cap rocks having low . are broken up tectonically and have poor lateral continuity of carrier beds. Lateral migration is therefore often stymied. Much more common. ACCUMULATION INTRODUCTION In the old days. as a result of both tectonic disruption and facies changes related to tectonic events. It is possible to have lateral migrations of as much as a few hundred kilometers in exceptional circumstances. although it should be remembered that there are two fundamentally different types of vertical migration. Most basins. Stacked sands in a paleodelta. Migration updip within a single stratum can accomplish a large amount of "vertical" migration rather painlessly. large drainage areas and chances for very large accumulations. are basins in which lateral migration distances do not exceed a few tens of kilometers. Vertical migration distances can also be considerable. Hydrocarbons had to remain in solution until they reached the trap. however. when migration was thought to occur mainly in water solution. Indeed.Migration . However. Unconformities also can juxtapose migration conduits. otherwise it is impossible to account for the incredible volumes of hydrocarbons in place today. distances of several thousand feet are not unheard of. The absence of both tectonic and stratigraphic barriers permits long-distance migration. Vertical migration can also occur across formations. by definition. Nevertheless. and the Saudi Arabian crude oils. There is no a priori reason why secondary migration cannot be a very-long-distance phenomenon. can offer possible pathways (although sometimes rather tortuous ones) for vertical migration. 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). thus providing a potentially very effective system for combined vertical and lateral migration. 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. including the Athabasca Tar Sands of western Canada. the largest hydrocarbon deposits known. Long-distance migration implies. because now accumulation can occur where the buoyancy-driven movement of the hydrocarbon phase is stopped or even strongly impeded. leading to smaller fault-bounded accumulations and vertical migration. The problem in discussing long-distance migration is that such cases are rare. Various mechanisms for exsolution were proposed to explain how all this was supposed to happen. Drainage area is one of the most important factors influencing the size of hydrocarbon accumulations.32 in general be more useful than contours on its base. Vertical migration across stratigraphic boundaries is more difficult. and has provided as carrier beds continuous blankets of sand juxtaposed with these source rocks. but also because an active fault or the brecciated zone adjacent to a fault may itself have high permeability. Lack of long-distance migration opportunities implies that supergiant and giant accumulations are far less likely and that exploration targets will be smaller.
rocks whose capillary-entry pressures are high enough to overcome hydrocarbon buoyancy. . while the structure or lithologic change prevents lateral updip migration. Gas production is actually from the low-permeability sand rather than from the high-permeability sand updip and downdip.Migration . Most hydrocarbon traps are either structural or stratigraphic. and will be covered separately. and vertical migration becomes important. Lateral migration is of necessity short distance. The simple principle behind a kinetic trap is that hydrocarbons are supplied to the trap faster than they can leak away. The low permeability sand thus creates a bottleneck to gas migration. Because gas generation is very rapid. Fracturing associated with high races of oil generation in the Green River Shale has created a supergiant accumulation at Altamont. Much of the hydrocarbon storage at Antelope is apparently in silts and sands juxtaposed with the producible Bakken reservoir. that strong hydrocarbon generation and migration is going on today. Accumulations are small because drainage areas are small. a fractured shale that is both source and reservoir.33 permeabilities to hydrocarbons provide barriers to migration: that is. 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. Classical traps are well understood. of course. Because the high permeability sand updip allows gas to migrate rapidly through. This model requires. 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. No traditional seal exists. the low-permeability sands become filled with gas. CLASSICAL TRAPS. Thus the Elmworth Field exhibits a water-over-gas contact. The seal prevents vertical migration from the reservoir rock into overlying strata. it remains water wet. The Elmworth Field in the Alberta Deep Basin of Canada is the prototype for kinetic gas accumulations. The much smaller Antelope Field produces from the Mississippian Bakken Formation. KINETIC TRAPS Kinetic traps represent a fundamentally new concept in trapping mechanisms for hydrocarbons. Cross section across the Rhine Graben of West Germany showing the discontinuity of strata as a result of extensional tectonism endemic to rift basins. Seals in the traditional sense of the word may not exist.
especially methane. Because hydrate zones are often hundreds of meters thick. but hydrates large enough to accommodate butane molecules are known. When the original hydrocarbon phase contains large amounts of light components. The polar molecules once again interact most strongly with interstitial water and mineral surfaces. A second characteristic is that gas hydrates form effective seals against vertical hydrocarbon migration. and would be incapable of sealing accumulations for long geologic periods. In cases where no other structural or stratigraphic trapping mechanism exists. These gas hydrates consist of a rigid lattice of water molecules that form a cage within which a single molecule of gas is trapped. contain mainly light components. because the same conditions that created the tar mat persist in the subsurface. 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. At the present time the vast potential of gas-hydrate accumulations is just beginning to be recognized. and the poor producibilitv of the hydrocarbons they trap. tar-mat traps are worth discussing because they include the largest hydrocarbon accumulations known: those of the Athabasca Tar Sands and the Orinoco heavy-oil belt. The base of the gas hydrate zone forms a pronounced seismic reflector that often simulates bottom contours and cuts across bedding planes. the quantities of gas in such accumulations are huge. Phase changes occur as a result of decreases in pressure and temperature during migration. these changes in temperature and pressure can cause separation of the original phase into a liquid phase and a gas phase. Gas hydrates form and are stable under pressuretemperature regimes that occur at depths of a few hundred meters below the sea floor in deep water. tar mats may provide the only possible means for retaining any hydrocarbons. GAS HYDRATES Formation of crystalline hydrates of natural gas provides an extremely efficient trapping mechanism for natural gas. and thus get left behind as the oil globule or stringer moves upward. but in the future gas-hydrate accumulations may be of great economic significance. but it may also include some heavier hydrocarbons dissolved in the gas. The technology necessary for producing these hydrocarbons has not yet been developed. Formation of hydrates thus provides an important trapping mechanism. Once expulsion has occurred. The polar (NSO) compounds interact most strongly with both mineral surfaces and water molecules.Migration . and in zones of permafrost. The gas phase will. of course. because much of the methane trapped is biogenic and was formed in young. One important feature of methane hydrates is that they are much more efficient at storing methane than is liquid pore water. Because intense oil generation is going on now. however. unconsolidated sediments that would have no other means of retaining the methane. Cap-rocks in those fields are often poor. As soon as two immiscible phases are formed. Accumulations beneath tar-mat seals are generally biodegraded themselves. and thus are not expelled as efficiently with the oil phase. It will therefore migrate much faster and . Methane is by far the most commonly trapped gas molecule. TAR-MAT TRAPS Tar mats produced by biodegradation can create excellent seals.34 Many of the accumulations in Pliocene reservoirs in southern California are also kinetic accumulations in a slightly different sense. Despite the rarity of tar-mat seals. the lighter (gas) phase will be far more buoyant than the liquid phase. large accumulations have formed despite high rates of leakage. there may be a chromatographic effect during secondary migration.
In using our understanding of secondary migration for exploration. Lateralmigration distances are strongly influenced by tectonic and depositional histories of basins. as explorationists we have very pragmatic interests in migration. and the vertical and horizontal distances involved. Efficiency of expulsion of liquids has already been estimated to be in the neighbourhood of 50% after the expulsion threshold has been reached. We need to know when hydrocarbons moved. the efficiency of expulsion. "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). Pathways. depending upon stacking of reservoirs. as we have seen. we will also have determined the timing of expulsion. Efficiency of expulsion for hydrocarbons is apparently much higher than for NSO compounds. Thus if we can determine the timing of generation. . We already know two important facts about timing from our previous discussion: expulsion based on microfracturing cannot occur before generation. and how far they moved. 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. and expulsion occurs concurrently with generation to relieve generation-induced overpressuring. vertical faulting. Vertical-migration distances can be considerable. When separation of a single hydrocarbon phase into two phases occurs. SIGNIFICANCE FOR EXPLORATION Explorationists who are reading about migration will surely ask. are determined by structural contours on the top of the carrier beds. In summary. by decreases in permeability as a result of facies changes. Polar compounds interact more strongly with water and rock minerals and thus move more slowly than hydrocarbons. and the possibilities of combined vertical and lateral migration. in what direction they moved. or by the presence of tars. and the timing of expulsion.35 will also assume the structurally high position in any reservoirs containing both phases. Tectonically stable basins have the best potential for long-distance migration and supergiant accumulations. the barriers that modify die direction of migration and eventually stop it. both new phases will have compositions that differ drastically from the original phase. leading to an enrichment of hydrocarbons in the expelled liquid. Barriers can be created by folding.Migration . gas is presumably expelled as a gas phase. We have already stated that oil is expelled primarily as a liquid phase. Timing of expulsion must be dealt with in a different way. by faulting. we want to determine the main pathways and conduite through which migration occurs. Proximity to effective source rocks and their permeabilities to hydrocarbons determine conduits. Unstable basins seldom have depositional or tectonic continuities necessary for longdistance lateral migration to occur.
THE REPRESENTATION OF TRAPS Traps are commonly depicted in two ways. Indeed. Note that we commonly highlight petroleum accumulations by shading or colouring the reservoir formations where they contain oil or gas. First. so that the highest points on the map have the lowest values. (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.(2-18) Before we go further. except that the contours are in depth below sealevel. Faults will be marked by jumps of the contours. 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). it will escape to surface as a seepage. If then we are to find any of it still preserved. but it is often convenient to exaggerate the vertical to show the individual beds more clearly.Petroleum Traps We have seen petroleum generated in and expelled from the source rock formation into an overlying or underlying reservoir. If it can. is the spill-point: this is where oil. The lowest point. Nowadays we can do better. drilling a well into it. they should properly be drawn with the same scale for both the vertical and the horizontal. The location of a trap in the subsurface is often the first objective of an exploration program. we need a few definitions. To complement the structure contour map. (a) A simple hypothetical anticline. as the beds on one side are dropped down relative to the other. which may refer either to its depth or to the spot under the ground where it lies. The top of a reservoir formation. but there must also be some sort of blockage to prevent further migration. by displacing the water already there in the porosity. they can be mapped by means of contours drawn on the top of the reservoir formation. and hoping for the best.36 7 . exploration used to consist largely of finding a trap. A structure contour map resembles an ordinary topographic contour map. To give a true representation. Such a configuration of the reservoir is known as a trap. The contours are in feet below mean sea-level. one or more cross-sections may be drawn.Petroleum Traps . where it is lost. is known as the crest of the trap. Any oil getting there will be unable to migrate further and so it starts to accumulate. before we reached our modern understanding of the geology of petroleum. 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. This may be caused either by the reservoir itself dying out or by an interruption of its upwards continuity to the surface. The highest point of the reservoir. the ticks are on the downthrown sides of the faults. up towards the ground surface. which may give a misleading impression of `lakes' of petroleum under the ground! Structure contour maps. is mapped by contours showing depth below sealevel. if more continues to migrate up into the trap than can be . These are illustrated using a simple anticline as an example.
so that we can recognize a generally horizontal oil-water contact. or in their layering. in which the trap is formed by changes in the nature of the rocks themselves. will occur as a gas cap above a gas-oil contact. they are embraced by the familiar terms oilfield or gasfield. but not entirely due to either. They are normally classified under four headings (2-21): 1.(or gas-) column. will spill out (under) and migrate on.Petroleum Traps . 3. These have to be discounted and the bits that remain as useful reservoir in a well section may be lumped together as the net reservoir with a net pay. Structural. STRUCTURAL TRAPS The best known type of trap is the anticline: on reaching the crest. and the same term is used loosely to refer to the area of the trap above the level of the spill-point. Similarly gas. perhaps if more than one reservoir is present. The vertical height of the oil (or gas) between the crest of the trap and the water contact is the oil. where the trap has been produced by deformation of the beds after they were deposited. Where there is more than one such pool in the same or overlapping areas. which have porosities and permeabilities too low for them to contribute oil to production. formed partly by structural and partly by stratigraphic effects. When referring to a single well. Some terms used to define a trap. Hydrodynamic traps. i.37 accommodated. separates out on top within the pore-spaces of the reservoir. If there is no oil. Stratigraphic. Let us remember. using a cross-section of a simple anticline as example (2-19). petroleum migrating up along a reservoir can go no further and it accumulates there as a pool. however. Combination traps. 4. the only structural effect being a tilt to allow the oil to migrate through the reservoir. the informal term pay is often used. which are rare and are mentioned mainly for completeness. However. Oil being lighter than water. Just a couple more terms. The vertical height between the spill-point and the crest is referred to as the closure. either by folding or faulting. Now we can start to consider the types of trap whose discovery may await us. 2. there are various types of . A single accumulation of oil or gas is called a pool.e. being lighter still. then we may see a gas-water contact. that most reservoir formations include some tight intervals. The trap is due to water flowing through the reservoir and holding the oil in places where it would not otherwise be trapped.
then the position of the crest will shift with increasing depth. so that the beds maintain a constant thickness throughout. Anticlines. If. These conditions mean that the anticline becomes smaller and tighter at deeper levels until we reach a common `centre of curvature'.38 anticlines with different shapes and geometries that can affect both their prospectivity and the positions of optimum drilling locations: we have to try to understand them. Seismic may help. so that the beds become intensely crushed and thrust together: we may no longer even have an anticline at all. the anticline is asymmetrical. noting the differences in shape and prospectivity that we have to try to interpret. beyond which there may be no trap left to explore as the consequence of decoupling of layers. a well would have to be located off-crest at surface. In practice. Compressive structures have a range of shapes between the purely concentric or parallel anticline and the similar fold. This can only happen if there is an apparent thickening of some beds over the crest of the fold. We will describe in a little detail the most important types of anticline. therefore in order to drill into a reservoir near its highest point (where we would expect the oil to be). (b) The anticline is asymmetrical and the crest shifts with increasing depth. In this case. Let us see what the implications are for exploration. 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. maintains its shape constant down to depth. Cover it with a few more blankets and a duvet or two. The similar anticline. and we may be able to continue exploration down to depths where we have to stop for other reasons. In this type of structure. depending on the nature and strength of the rock layers being folded. The general principles of this are straightforward. (a) The dips are the same on both flanks and the crest is beneath the same locality at all depths. This leads us into the next problem. This is a very different kettle of fish from the concentric anticline. we can thus expect to find only smaller and smaller accumulations of petroleum down to the centre of curvature. Traps can also be formed against faults if a chopped-off reservoir is thrown against a shale or other impervious rock. many structures have forms in-between the two extremes. and we may no longer be able to see where the bottle is. in cross-section. and the blanket bulges upwards with an anticlinal shape.Petroleum Traps .(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. but we commonly have to undertake some form of geometrical construction to interpret what is happening at depth. we can find the trap present at all levels down to the basement. but an understanding of the shape and size of a prospect is clearly critical to programming an exploration well. on the other hand. Below this point we have just too much rock to fit into the anticline. Cross-sections of trap-forming anticlines. with one flank steeper than the other. . There is a definite limit to the depths to which we should drill. To test the crest at depth. we have to know its depth to know where best to locate the well. Other types of anticline can be formed without any lateral compression at all: an important one is the drape or drape-compaction structure.
This creates a rollover anticline. Diagrammatic section through two salt plugs. much of the west coast and continental shelf of Africa. and finally a residual bulge may be left between two nearby plugs: a turtle or turtle-back structure. can be a perfect seal to any underlying accumulations. which contains more than four times as much oil as the whole of the North Sea put together. Extensive salt deposits and plugs with associated traps occur in many parts of the world: the southern North Sea and northern Germany. it may bend up and seal off the strata it cuts through. however. The last type of anticline that we should be aware of is the roll-over anticline. where the beds are draped over the eroded stumps of an old Jurassic volcano. it may extend up to the surface of the ground or only part way if the supply of salt is limited. In effect the downthrown side is being pulled away from the upthrown side which would tend to create an open fissure along the fault. All of these possible traps may contain hydrocarbons. if the first sediments in a basin were deposited over a hilly surface. Note that the anticline dies out upwards towards the surface. it is also liable to fracture the overlying and surrounding beds creating fault traps. a salt pillow or a salt dome. and several others.(2-25) Similarly. Another is the Forties field in the North Sea.(2-26) A wide variety of traps can be associated with salt plugs. A second effect comes into play here: because there is a greater thickness of beds off the structure than over the top. The effect of salt diapirism will be initially to bulge up the overlying sediments as an anticline. Nature. so that it is steep near the surface and flattens with depth. the beds being draped over an upfaulted block (horst) of basement rocks. but also .Petroleum Traps . This occurs alongside a normal fault that is curved.39 A drape-compaction anticline. Note also that salt. bending downwards into the hole. showing the variety of traps that may be associated with them. Note a characteristic of these anticlines: not only do they `grow' with depth. 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. the Middle East. it is not always easy to separate out the two effects. and then to burst through them in the form of a salt plug or salt wall. Ghawar in Saudi Arabia. and the beds on the downthrown side above the curving fault collapse to fill the gap. This compaction enhances the anticline formed by the drape. higher beds will gradually mute and suppress the structure until it is no longer present at shallow levels. In case anyone should think that this is unimportant. note that the largest oilfield in the world. the Canadian Arctic Islands. is in one such trap. does not like empty holes. or over an upfaulted block or horst. Not only may an anticline be pushed up over the plug. and hence the combined name. the Gulf Coast of the USA. then they will blanket the hill as an anticline. being plastic.
Upper Jurassic. Fault traps We indicated above that a trap may be formed where a dipping reservoir is cut off up-dip by a fault. it seems that one and the same fault may act. The oil is in two reservoirs. Lower Cretaceous. (B) a roll-over complicated by subsidiary faulting near the crest. Roll-over anticlines: (A) a simple roll-over into a normal fault. 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. in both ways. the position of the crest is displaced with depth and that accumulations in successive reservoirs will not underlie the same surface position. Tr. W.. and naturally we have some ideas on the subject. It adds further uncertainties to our predictions of the subsurface occurrence of oil and gas. in both cases. therefore. Occasionally indeed. The proviso is that we also have lateral closure: this may be provided by further faulting. Again. The sealing capacity of faults is a major difficulty confronting us. Much of the oil under the Niger and Mississippi Deltas is in such roll-over anticlines. these predated the deposition of the Upper Cretaceous. and in understanding them. to locate an exploration well in the right place. trapped against faults to the south. a fault can provide a seal. thus causing sand against sand to permit migration and sand against shale to be sealing. Middle Jurassic. We know that sometimes. Tertiary. and its depth. down towards the deep ocean. Lower Jurassic. southern England. The large Wytch Farm oilfield of southern England offers a splendid example. It also depends on whether the fault itself is sealing or non-sealing. we still do not fully understand what the difference is due to. setting it against something impermeable. or slumping as a sort of land-slide. (2-28) We do not propose to discuss fault traps in detail. T.40 they are asymmetrical. Upper Cretaceous. although there are many problems in trying to locate them in the subsurface. All very puzzling! Although attempts have been made to investigate the problem in Nigeria and elsewhere. whether or not the reservoir is completely or only partially offset. but we also know that sometimes faults are pathways for migrating petroleum and non-sealing at all. Triassic. UK. Kim+P. BS+MJ+O. will depend on the dip of the reservoir as compared with that of the fault. we have to know whereabouts in the succession our prospective reservoir lies. and how big it is. whether the fault is normal or reverse.Petroleum Traps . Cross-section through the Wytch Farm oilfield. or by opposing dips. and it will depend on the amount of displacement on the fault. Note that. 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. L. as at Wytch Farm. Whether or not there is a trap. . or have acted in the past.
however.(2-29) STRATIGRAPHIC TRAPS Petroleum may be trapped where the reservoir itself is cut off up-dip. The variety in size and shape of such traps is enormous. becoming younger as time goes on. and on the amount of displacement of the reservoir. In this manner. to a large extent reflecting the restricted environments in which the reservoir rocks were deposited. until perhaps the supply of sand runs out. In fact. fan sands provide one of the prime present-day exploration . but nevertheless known. if terminated updip as not infrequently happens. It would be pointless to list all of the possible types of stratigraphic trap that can exist. thus preventing further migration. provides the classic case: the East Texas field. on the direction of dip of the beds relative to the fault plane. depending on whether the fault is normal or reverse. are formed by unconformities. a hill on the old land surface may be formed of permeable rock. We would be left with a sandstone reservoir dying out above the unconformity. A dipping reservoir. and leave the reader to speculate on other possibilities. the beach sands will spread progressively over the land surface. for example. to provide a trap when later covered with. the porosity could be preserved beneath the unconformity. A sand deposited in a river channel will be confined by the banks and. strongly weathered basement rock (granites. but are generally classified as stratigraphic traps. some of them very important.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. claystone. More esoterically. its edges will provide an example of a reservoir dying out laterally. is the biggest in the USA outside Alaska. they differ somewhat in principle from the others. We mention just three examples. may serve as an isolated stratigraphic trap. possibly through a submarine canyon. Consider the sea gradually encroaching over the land as sea level rises. First. say. let us note that a number of traps.Petroleum Traps . Non-unconformity traps are even more diverse. will spread out as a fan over the ocean floor. A coral reef overwhelmed by muds. gneisses) under an unconformity serve as reservoirs in China and North Africa. Unconformity traps can also be found above the break. so we will mention a few to convey the general idea. no structural control is needed. we have an isolated trapping situation. cut across by erosion and later covered above the unconformity by impermeable sediments. if drowned by shales. It is presumed that petroleum cannot escape up the fault plane. A flood of sand washed off the shallow continental shelf into the deeper ocean.
occur in traps formed by a combination of structural and stratigraphic circumstances. and where an oil-water contact is continuous across a fault. An investigation into the sealing qualities of faults affecting roll-over anticlines in the Niger Delta. We may note here one most important consideration. which was tilted west and eroded before deposition of the overlying beds now dipping east. The Prudhoe Bay field in northern Alaska. it is presumed that the fault is non-sealing. A couple of examples may give the idea. The difference is believed to be due to clay being smeared into the fault plane.42 targets. and truncated by erosion. where there is enough of it in the section. neither completely controls the trap. As the more easily found structural traps are running out in much of the world. This combination trap is partly structural (the anticline) and partly stratigraphic (beneath the unconformity). elsewhere it appears to form a trap. these beds were folded into a faulted east-west anticline. or the oil would have been lost. The reservoir beds were folded into an anticline. some of them large. which were eroded and unconformably overlain by Cretaceous shales. The oil in these fields can only have migrated there after the traps were sealed by the higher sequences. This vital factor. Again the range of possibilities is almost infinite. although such prospects are not easy to locate and may require a lot of sophisticated seismic.(230) COMBINATION TRAPS A number of fields. possibly even before it . the biggest field in the USA.(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. tilted westwards.). that the trap must be shown to have been there before the oil migrated. A block representation of the trap at the Prudhoe Bay field in northern Alaska. The oil is held in the reservoirs by younger shales overlying the erosion surface (Fig. where the reservoirs overlie overpressured shales.Petroleum Traps . Where a reservoir is full to spillpoint against a fault. has most of its oil and gas trapped in a Carboniferous to Jurassic sequence which includes more than one reservoir. there always seems to be something new as a challenge. as the fault moved. Both the faulting and the unconformity control the traps.
The timing of trap formation versus oil migration has not always worked out favorably. up in the hills and percolating downwards towards a spring. Oil. The number of structural field of this size may partly reflect the fact that structural traps are easier to find than the others. Oil has found its way into the reservoir and is battling to migrate upwards to the surface against the flow of water. Furthermore. indicating the former presence of an oil accumulation now lost. is held against an unevenness of its upper surface by water flowing in the opposite direction. In this sort of situation.(2-32) THE RELATIVE IMPORTANCE OF TRAPS A review of 200 giant oilfields (those containing 500 million barrels or more) emphasize the importance of structural. This may be one of the reasons why oil accumulations trapped hydrodynamically are rare. perhaps from rain. . Note that the oil-water contact is tilted down in the direction of water flow.Petroleum Traps . but the oil reserves they contain show clearly that generally they are also bigger. entering a reservoir formation. in say ordinary anticlinal traps. are the more obscure and generally smaller prospects. or aquifer. It is totally dependent on the flow of water and is effective. from our present-day point of view. therefore. There is no structural or stratigraphic closure. HYDRODYNAMIC TRAPS Imagine surface water. it may find itself caught against an unevenness of the reservoir surface where there is no conventional trap at all. This is what has been described as a hydrodynamic trap. of course. essentially anticlinal. We would recognize this from residual traces of oil in a water-bearing reservoir. as we do not want to waste the money drilling wells that would miss the oil altogether. Depending on the balance of forces acting on the oil. we would have to be careful where we locate and drill our oil production wells. and the oil will be free to move again. only for as long as the water keeps coming: dry up the supply of water. What our efforts are increasingly directed towards. cases are known where flowing water has apparently been able totally to flush oil out of an anticlinal trap. It is therefore always important to get a handle on the hydrodynamic regime in a reservoir for both exploration and oilfield development purposes. are not all that rare. The trouble.43 was generated. attempting to escape to surface up a reservoir. The oil-water contact in such a hydrodynamic trap is normally tilted in the direction of water flow. traps in both number and size. is that in most parts of the world the larger anticlines have now been drilled. a regime of water flow cannot normally be expected to remain constant for long. geologically speaking. A hydrodynamic trap. they are known in a number of parts of the world. is yet another aspect of the petroleum geology that we have to assess in proposing exploration drilling. Such tilted contacts.
Interpret the geological relationships shown in each by drawing a structural cross-section through the logs. The logs show SP (Self Potential or Spontaneous Potential) on the left and R (Resistivity) on the right.Petroleum Traps . multi-interpretable (D).45 EXERCISES EXERCISE 1: The following well logs have been hung on a structural datum. .Make the interpretations from easy (A) to more difficult.
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).46 EXERCISE PetroleumTraps 2 The Wyckoff Gas Field. Wyckoff Reef Gas Field WellElevation CORNELL DIBBLE GUILD CHASE BANKS RICHARDS 2257' 2098' 2037' 2206' 2182' 2066' .Petroleum Traps . Use this information to construct a northeastsouthwest structural cross section from the Richards well to the Dibble well. showing the interval from top of Onondaga to bottom of Oriskany.Y. Elevations and marked logs are provided for 6 wells in the Wyckoff Field. N.. located in Steuben County. A deep-seated downto-the-southwest fault extends upward along the southwest flank of the reef. produces from Onondaga Limestone and/or Oriskany Sandstone. The Onondaga forms a thick biohermal reef over part of the field.
Petroleum Traps .47 .
Petroleum Traps .48 .
overmature. but if the rocks contain abundant organic matter. However.49 8 . The difference between Go and G represents the hydrocarbons already generated in the effective source rock. where G and Go are identical. we cannot measure G directly for a sample that has already begun to generate hydrocarbons. if G is very low. 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. the remaining source capacity and not the original capacity (Go). and inexpensive analysis serves as the first and most important screening technique in source-rock analysis. the Phosphoria Formation of Wyoming and Idaho belongs to each of these classifications in different areas. When we analyze a rock sample in the laboratory. it is also necessary to know what level of thermal maturity is represented by that particular G value. Potential source rock: any immature sedimentary rock known to be capable of generating and expelling hydrocarbons if its level of thermal maturity were higher. that usage is a bit too broad and loose. Analysis normally requires about one gram of rock. we actually measure its remaining (or untapped) source capacity at the present day. MATURITY OF ORGANIC MATERIAL Knowing a rock's remaining source capacity G solves only one part of the puzzle. quick. The term "effective source rock" obviously encompasses a wide range of generative histories from earliest maturity to overmaturity. in which case virtually all the initial . is most meaningful if we can compare it to the rock's original source capacity. Although the term source rock is frequently used generically to describe fine-grained sedimentary rocks. which we can call G. but which may have generated and expelled hydrocarbons..Source Rock Evaluation .Source-Rock Evaluation DEFINITION OF SOURCE ROCK Much of modern petroleum geochemistry depends upon accurate assessment of the hydrocarbonsource capabilities of sedimentary rocks. or is it because the rock is "burned out" (i. It follows from these definitions that a particular stratum could be an effective source rock in one place. Possible source rock: any sedimentary rock whose source potential has not yet been evaluated. a potential source rock in a less-mature area. Go. 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. The quantity actually measured in the laboratory is always G. For example. This simple. Go can only be measured directly for immature source rocks. For better communication. instead it must be estimated by measuring G for a similar sample that is still immature. is it because the rock never had a high initial source capacity.e. a possible source rock in a nearby unstudied region. much smaller amounts can be analyzed. This quantity. For example. the following distinctions can be made: Effective source rock: any sedimentary rock that has already generated and expelled hydrocarbons.
TAI measurements are carried out on bisaccate pollen grains whenever possible. misidentification of macerals can cause problems. 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.50 hydrocarbon-source capacity has already been used up)? The exploration implications of these two scenarios are. the plot is a straight line. There are many problems with vitrinite reflectance as applied to kerogens. vitrinite reflectance. If no pollen can be found. whenever possible. and then embedding the kerogen particles in an epoxy plug. Thermal Alteration Index (TAI). in fact. even for experienced workers. where the o indicates that the measurements were made with the plug immersed in oil. leading to frequent difficulties in establishing which vitrinite population is indigenous. The darkening of kerogen particles with increasing thermal maturity can be used as an indicator of maturity. Because what is present is often reworked. or TAI). with lower confidence. A few of these parameters will briefly be discussed. in which the vitrinite maceral is usually very common. Because each maceral type increases in reflectance in a slightly different way as thermal stress increases. of course. vitrinite reflectance is the most popular technique today for estimating kerogen maturity. its maturity is not related to that of the rock in which it is found. In other rocks. The method is based on the fact that with increasing thermal stress. and none can be applied in all cases. The ideal histogram of reflectance values is therefore rather rare. Other macerals or solidified bitumens can often be misidentified as vitrinite. Vitrinite-reflectance techniques were developed for measuring the rank of coals. from amorphous kerogen. between 50 and 100 measurements will be taken. The key to using maturity parameters effectively lies in evaluating the measured data carefully (and sometimes with skepticism) and. Reflectance values are normally plotted versus depth in a well. very different. however. Results are reported as Ro values. Reworked vitrinite is. The fraction of the incident beam that is reflected coherently is measured and recorded and stored automatically on a computer. In all cases it is worthwhile to supplement vitrinite with other measures of maturity. In many areas it is easy to use and valuable. Vitrinite reflectance (Ro). A substantial number of techniques for measuring or estimating kerogen maturity have been developed over the years. After the plug is polished. If a log scale is used for the reflectance. in some cases it is essential. paucity of first-cycle vitrinite renders vitrinite-reflectance measurements essentially worthless. At the end of the analysis a histogram of the collected data is printed. far more common in shales than in coals. TAI values are estimated. Such histograms are quite often difficult or impossible to interpret.Source Rock Evaluation . along with a statistical analysis of the data. In many rocks vitrinite is rare or absent. Vitrinite-reflectance measurements begin by isolating the kerogen with HCl and HF. Less commonly used are fluorescence and conodont color (CAI). Despite its weaknesses. All the methods have strengths and weaknesses. the microscopist shines light on an individual vitrinite particle. If enough vitrinite particles can be found. the reflectance value of vitrinite increases. unless surrounding samples help us determine the indigenous vitrinite population. The feeling of most workers today is that there is no single maturity indicator that tells the whole story unerringly all the rime. TAI measurements are made on the same slides prepared for microscopic kerogen-type analysis. . The most commonly used maturity parameters today are spore color (Thermal Alteration Index. All the techniques discussed are useful and probably reasonably accurate if the analytical work is carefully done. In order to minimize differences in color caused by changes in the type or thickness of the kerogen particles. in obtaining more than one maturity parameter. and pyrolysis temperature.
changes in conodont color are apparently due to carbonization of inclusions of small amounts of organic matter during catagenesis and metagenesis. A careful worker can reproduce earlier work with excellent precision. which can vary greatly in its chemical and physical properties.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. and thus are of no value in many areas. CAI is inexpensive and easy to measure and. where pollen and vitrinite are often absent. Although TAI determinations are subjective. because the organic metamorphism displayed by conodonts is not related to hydrocarbon generation or destruction. TAI measurements are therefore often quite accurate and correlate very well with results from other techniques. conodonts are plentiful in carbonate rocks. When palynomorphs are absent. Colors of the specimens thus obtained are determined under a binocular microscope and compared with standards. Conodonts are isolated. The chief problems arise with inexperienced workers. Although conodonts are composed of carbonate apatite. Conodont Alteration Index (CAI). leading to an inaccurate assessment of kerogen maturity. TAI values estimated from amorphous material are always suspect and should be corroborated by other analyses. Finally. Furthermore. Finally.Source Rock Evaluation . with the help of color charts can be carried out by inexperienced personnel. 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. thus defusing to a large degree the criticism that TAI is too subjective to be valid. 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. TAI values must be estimated from amorphous debris. Carbon Preference Index (CPI). Other disadvantages overlap with some of the advantages. Early investigations showed that immature rocks often had high CPI . One advantage of CAI over other maturity parameters is that because conodonts existed as early as the Cambrian. Thirdly. use of careful standards and the same type of palynomorph in each analysis greatly aid reproducibility. by removing the mineral matrix with acetic or formic acid. lack of proper standardization. where most of the interest is. and thus helps expand the range over which maturities can be measured. most commonly from fossiliferous carbonates. the absence of spores and pollen in the samples. The first maturity indicator applied to sediments was the Carbon Preference Index. Conodonts are not very sensitive indicators of maturity within the oil generation window. The technique is simple and quick and can be done even by inexperienced workers. Conodonts do not occur in rocks younger than the Triassic.
because all kerogens have low pyrolysis yields. Like pyrolysis. Furthermore. TOC values will be raised and vitrinite-reflectance values lowered by the presence of adsorbed diesel. In such cases TOC values will be raised and reflectance histograms will show a large population near 0. and can be removed prior to beginning the analytical sequence. vitrinite reflectance measurements offer the best means of recognizing caving.5). Walnut hulls and other organic debris are also easy to detect microscopically. Atomic H/C ratios must therefore be corrected for the effects of . have low CPI values even when immature.2. Pyrolysis yields are. walnut hulls and other solid debris. in which the input of terrestrial lipids was very limited. ESTIMATION OF ORIGINAL SOURCE CAPACITY Of the three major methods of determining kerogen type. 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. Problems with living organic matter are easily avoided by physically removing tiny plant roots and other recognizable debris. whereas those of oils were almost always below 1. where the fluorescence that enables us to distinguish between oil-prone and non-oil-prone disappears toward the end of the oil-generation window. it is impossible to determine which maturation path brought it to that point. It breaks down at high maturity levels. but it can be devastating in cuttings samples. and therefore should be easy to avoid. they can usually be identified with reasonable confidence. Without additional information. Caving is not a problem for conventional or sidewall cores. In contrast to solid additives. Caving is a particular problem for coals. Hydrocarbon contamination is rare except in the immediate vicinity of production or where vehicles are used. palynological analysis can usually detect the presence of lignosulfonates because of the unique pollen assemblages present in the lignite. of course. Drilling-fluid additives have been a severe headache for petroleum geochemists for a long time. As long as kerogen particles are not completely black.52 values (> 1. In particular.Source Rock Evaluation . of course. atomic H/C ratios measure the present day status of the kerogen rather than its original chemical composition.5%. 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. because of their friability. and lignite from lignosulfonates. in the last decade kerogen analyses have replaced bitumen analyses as the routine procedure in source-rock evaluation. In many cases. As a result. The exception to this rule is with amorphous material. strongly affected by maturity. Fortunately. it can lead to an overly optimistic assessment of the organic richness of the section. however. This discovery led to the use of CPI as an indicator of maturity. rocks deposited in pelagic environments. Well Samples . Mold or other surface growth may also be present. This method works fairly well if the kerogen is still within the oil-generation window. which affect only the kerogen portion of the sample. Careful picking of lithologies and comparison with up-hole samples can often recognize caved materials. however. Contaminants of particular notoriety are diesel fuel. fewer CPI determinations are made now. It is capable of impregnating sidewall and conventional cores as well as cuttings. diesel fuel affects both kerogen and bitumen. therefore.The main causes of contamination among samples obtained from wells are caving and adulteration by drilling-fluid additives. only microscopic analysis is relatively unaffected by maturity. 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.
These immature H/C ratios can then be used to calculate Go. cutinite.0% TOC are marginal. In interpreting these observations we normally divide these macerals into oil-generative. that at least some Australian inertinites can generate significant amounts of oil. They will not function as highly effective source rocks. yielding . Rocks containing more than 1% TOC often have substantial source potential. Inertinite is considered by most workers to have no hydrocarbon-source capacity. gas-generative. but they may expel small quantities of hydrocarbons and thus should not be discounted completely. The amount of hydrocarbons generated in such rocks is so small that expulsion simply cannot occur. however. has dissented from this pessimistic view. the kerogen in such lean rocks is almost always highly oxidized and thus of low source potential.5%). Because the density of organic matter is about one-half that of clays and carbonates. claiming.5% and 1.Source Rock Evaluation . A rock containing 3% TOC is likely to have much more than six times as much source capacity as a rock containing 0. the actual volume percent occupied by the organic material is about twice the TOC percentage. have little oil-source potential. TYPE OF ORGANIC MATTER Microscopic kerogen-type analysis describes the proportions of the various macerals present in a sample. Smyth (1983). because the kerogens they contain are woody or highly oxidized. which ones might be of slight interest (TOC between 0. Thus high TOC values are a necessary but not sufficient criterion for good source rocks. 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. and inert. Interpretation of TOC values therefore does not simply focus on the quantity of organic matter present. In some rocks TOC values between 1% and 2% are associated with depositional environments intermediate between oxidizing and reducing. As such these quantities are a measure of the total capacity of a rock to release or generate hydrocarbons or carbon dioxide. We must still determine whether the kerogen present is in fact of good hydrocarbon-source quality. on the basis of deductive reasoning. resinite. We therefore use TOC values as screens to indicate which rocks are of no interest to us (TOC < 0. because the type of kerogen preserved in rich rocks is often more oil-prone than in lean rocks.0%).5% TOC.5% TOC are considered to have negligible hydrocarbon-source potential. however. Many rocks with high TOC values. Rocks containing between 0.0%). Gas-generative kerogen is mainly vitrinite. S2. Kerogens in rocks containing less than 1% TOC are generally oxidized. and S3) are expressed in milligrams of hydrocarbon or carbon dioxide per gram of rock sample. These raw data are then normalized for the organic-carbon content of the sample.53 maturation by using a van Krevelen diagram. and thus of limited source potential. Raw data (S1. TOC values above 2% often indicate highly reducing environments with excellent source potential. fluorescing amorphous kerogen. where preservation of lipid-rich organic matter with source potential for oil can occur. the direct evidence for such a statement is rather meager. Nevertheless. Those rocks containing less than 0. etc. Furthermore. exinite.5% and 1. The oil-generative macerals are those of Type I and Type II kerogens: alginite. and which are definitely worthy of further consideration (TOC > 1. Pyrolysis results are normally reported in two ways.
Measured hydrogen indices must be corrected for maturity effects by using a modified van Krevelen diagram as outlined above. exinite) or from marine algal material. Hydrogen indices above 150 reflect increasing amounts of lipid-rich material. 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. Age of coals is important. Although Tmax values are determined objectively. Some laboratories put the onset of maturity at 435° C. and the end of liquid-hydrocarbon generation is thought to be at about 1. CAI can actually measure high-grade metamorphism. others use 440°. They have excellent potential to generate liquid hydrocarbons. but in most cases is probably not much above 1. A second. The correlations among maturity parameters have been fairly well established. the hydrogen index serves as an indicator of kerogen type.5% Ro. because they vary with kerogen type as well as maturity. Determination of the oil-generation window in a particular section is the objective of most maturity analyses performed on possible source rocks. 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. less common application is to decide whether oil will be stable in a given reservoir. some Cenozoic coals should have better potential for generating liquid hydrocarbons. Kerogens with hydrogen indices above 600 usually consist of nearly pure Type I or Type II kerogens. but there are still some minor variations from one laboratory to another. and the coals were of bituminous to anthracite rank. Because variations in TOC have been removed in the normalizing calculation. It is particularly difficult to generalize about TAI values because the numerical values of TAI scales have not been standardized among laboratories. with CAI of 8 reached in a marble. The ultimate limit of oil stability is not known for certain. . Peak generation is reached near 0. a unified scale for comparing them with Ro values has not been adopted.6% Ro. if you are using TAI determinations determined by an analytical laboratory. Because vitrinite reflectance is the most popular method of determining maturity. Interpretation of hydrogen indices for immature kerogens is straightforward. MATURITY Kerogen Parameters.9% Ro. However. Kerogens with hydrogen indices above about 300 contain substantial amounts of Type II macerals. Those between 150 and 300 contain more Type III kerogen than Type II and therefore have marginal to fair potential for liquids. The limits of the oil generation window vary considerably depending upon the type of organic matter being transformed. because during the Paleozoic the biota was quite different than during the Cenozoic.35% Ro. Because some Cenozoic land plants are richer in resins and waxes than Paleozoic plants.54 values in milligrams per gram of TOC. this generalization has two fallacies: most of the coalfields originally studied were of Paleozoic age. make sure that you have a copy of their equivalency between TAI and Ro. most other maturation parameters are related to Ro values. Thus. and thus are considered to have good source potential for liquid hydrocarbons. for most kerogens the onset of oil-generation is taken to be near 0.Source Rock Evaluation . The normalized S2 and S3 values are called the hydrogen index and the oxygen index. respectively. resinite. Conodont Alteration Index (CAI) values ranging from 1 to 5 were tied loosely to vitrinite reflectance and fixed carbon content of coals. either from terrestrial macerals (cutinite. Nevertheless.
8 3. and organic facies. we should not rely on a single analytical technique. Whenever possible.50 0.0 3.80 1. rather.3 2.Source Rock Evaluation .00 1.60 0. Interpretation of source-rock data on a basic level is quite simple.4 3.0 Pyrolysis Tmax (°C) 420 430 440 450 460 465 470 480 500 500 + 500 + Conodont Alteration Index (CAI) 1 1 1 1. type.55 SUMMARY Any source-rock evaluation should attempt to answer three questions: What are the quantity. To do this intelligently we must have the ability to develop regional models of organic facies and thermal maturity.00 4. In some areas one technique may fail completely or may be only partially successful.00 3.2 3.5 3.35 1.0 2.00 Thermal Alteration Index (TAI) 2. With increasing experience one can also learn to derive important information on thermal histories.50 2.5 2 2 2 3 4 4 5 Correlation of various kerogen-maturity parameters with vitrinite-reflectance (Ro) values .8 4. unconformities and erosional events.0 4.20 1. We should always attempt to extrapolate our measured data over as large an area as possible. we should attempt to corroborate the measured data by other analyses.40 0. therefore.6 2. Vitrinite Reflectance (%Ro) 0. and maturity of the organic matter present in the rocks? Satisfactory methods are available in most cases to answer all these questions.
5 0.72 0.1 2.5 1. however.5 2.41 0.56 EXERCISES Worked out example: Perform a source-rock analysis on the Mauve Well. presenting the kerogen quality factor as a . This can be done easily by plotting H/C versus TAI.7 3.75 0.22 1.Source Rock Evaluation .38 TAI 2.5 2.6 2.2 2.7 2.77 0.6 2. as shown in Figure B (derived from Figure A).3 0.5 0. quality (H /C and %Alginite + Exinite).8 0.65 0. and then tracing the H/C ratio back to its immature value.98 0.1 3.07 1.0 2-2. and maturity (TAI)." To do this.7 2.9 3. one must first convert the measured. B) H/C versus TAI for Mauve Well samples.0 0. so "Total Oil" can be plotted against "Oil Already Generated. The calculated immature H/C ratios are listed in the table on next page.2 3. and both should be utilized and examined for possible discrepancies.86 0.27 1.2 1. A) Calculation of the immature kerogen H/C ratio(at A) from the present-day H/C ratio and vitrinite reflectance data(at P) . To use the H /C data.05 0.2 Atomic H/C 1.5 1. present-day H/C ratios to the ones that the kerogens had when they were thermally immature.7 1.3 1.5 2-2.8 % Alginite + Exinite 75 80 80 75 80 90 85 75 70 50 45 60 45 40 ? ? Core Cuttings Data are available on quantity (%Corg).0 3.7 1. refer to the graph on next page.33 1.6 2.15 0.66 0.6 0. Both the immature H / C ratios and the maceral analysis data need to be scaled to calculate "Total Oil.81 1." Two independent quality measurements have been made.5 2-2.5 2. Source-rock data for the Mauve Well Depth (m) 1000 1200 1500 1750 2000 2300 2700 3000 3500 3600 3800 4000 4500 4600 4800 5000 Type of Sample Sidewall Cores %Corg 0.
05 0.60 0.90 0. In each case.6 1.66 0. such as pyrolysis.98 0. 1750. 1500.33 1.22 1.05 1.30 1.5 1.85 1.65 0. the H/C ratio gives the lower quality factor.27 1.05 0.6 1.90 0.50 1.05 0.0 0.90 0.57 function of H/C ratio of the immature kerogen in order to determine the quality factor from H/C.22 1.90 0. and not .05 1.15 0.9 1. it is impossible to pinpoint the error. The scaled quality factors are given for each parameter in the table on next page.41 0.8 ? ? * * * Indicates discrepancy between quality factors calculated from H /C and from maceral analysis.07 1.75 0.Source Rock Evaluation . The samples at 1000. so some systematic error is likely. 2300.5 1. Kerogen quality factor as a function of H/C ratio of the immature kerogen. however. If these attempts produced no resolution of the problem. 2000.35 0. to check for analytical error.20 1.2 0.60 0.35 0.81 1. The most important point being made here is that these discrepanties must be taken seriously by the interpreter.60 ? ? * * * * * 1.77 0. and 4500 meters all show differences in the quality factors calculated from the two types of data.65 0.8 1.70 1.72 0. Without more knowledge.5 1.6 1.35 1. 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 1.81 1.00 0. The prudent interpreter might now ask that some of the H/C ratios be rerun.77 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 1.43 1.4 1. and would certainly request that the slides made for maceral analysis be reviewed.7 1.38 Immature H/C 1.86 0. the interpreter might then decide to try a third technique.07 1.9 0. 4000. It is apparent that there are serious discrepanties between the H/C and maceral analysis results for several of the samples.17 0.
"Total Oil" and "Oil Already Generated" profiles tor the Mauve Well. . "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. and the H/C ratios are not helpful because the maceral types cannot be ascertained from such low H/C values. no maceral analysis was possible here. 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.58 be overlooked or swept under the rug. These two kerogens are highly mature and quite black. "Total Oil" values are generally unexciting. Let us take this last approach to this problem. The only sample where the discrepancy is significant is that from 2000 meters. "Total Oil" and "Oil Already Generated" profiles are plotted in above figure.Source Rock Evaluation . It may be necessary occasionally to offer two alternative interpretations without choosing between them. One can say little. More samples between 3000 and 3500 meters should be obtained to define better the zone of high "Total Oil" values. The relative organic richness of the blackened samples below 4600 meters makes them interesting for further investigation. therefore. about the oil-source history of the section below 4600 meters. In fact. although the section between 2000 and 3500 meters shows fairly good potential. because sourcerock potential is not good for most of the section. Most of the discrepanties among the different quality factors turn out to be unimportant. Future exploratory activity could include an attempt to find such a section. except for the two deepest samples. Finally. The rest of the section shows a good correspondente between the two parameters.
52 0.6 4.49 0.06 0.1 0.5 2.26? 1.02 0.0 2.08 0.5-3.60 0.5 2.02 Atomic H/C 0.5 2.86 1.25 1.5 2.0-2.65 0.2 0.5 2.5 TOC = Total Organic Carbon Bit/TOC = Bitumen/Total organic carbon ? indicates a poor histogram TAI = Thermal Alteration Index Ro = Vitrinite reflectance .06 0.66 0.51 0.5-3 2.99 1.4 0.5-3 2.49 0.5-3 3.0 0.41? 1.48 Ro 0.9 1.11 0.0-2.88 0.Source Rock Evaluation .5 2.59 0.91 0.5 3-3.63 0.60 0.1 2.5 2.0 3-3.21 0.65 0. Explain how you resolved any apparent discrepancies.66 0.0 2.2 2.21 1.7 0.10 0.03 0.05 0. Source-rock data tor the Turquoise Well Depth (ft) 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500 8000 8500 9000 9500 10. EXERCISE Source Rock 2 Perform a source-rock evaluation of the section penetrated in the Turquoise Well.5-3 2.03 0.0 2.59 0.000 Type of Sample Cuttings Cuttings TOC 1.6 0.02 0.07 0.08 0.22 0.5 2.55 0.09 0.07 1.90 0.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10 2-2.5 3.25 0.00 1.17 0.07 0.5-3 2.5 3.09 0.33? 1.0 2.8 0.3 2.91 1.51 0.59 EXERCISE Source Rock 1 Combine the data from the Blue Well to give a coherent picture of thermal maturity in the section drilled.7 0.8 1.60 0.05 0.0 2.5-3 2.17 0.5 2.3 2.51 0.3 1.44 0.18 0.3 Bit/TOC 0.0-2.91 1.71 0.27 1.42 0.3 2.61 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 2.0 2.01 0.27 0.67 0.5 0.85 0.6 2.12 *TAI and Ro are interconverted according to the correlation table at the end of chapter 7.5 2.21 1.03 0.08 0.06 0.46 0.5 2.08 0.
. 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. This assumption is a logical and defensible one. Even in maturely explored basins the samples available for analysis often do not give a representative picture of maturity in the basin. 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. If our measurements indicate that a rock has already passed through the oil-generation window. estimates can be made. especially if the seismic reflectors can be tied to well data. for it is in keeping with the predictions of chemical-kinetic theory.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. In most cases. In 1971. It has even been suggested that maturity models are more accurate than measured data for determining the extent of petroleum generation. He developed a "Time-Temperature Index" of maturity (TTI) to quantify his method. expulsion. however. a time stratigraphy can sometimes be constructed using seismic data. Part of this problem is a consequence of the limitations we face in attempting to obtain reliable maturity measurements. The common thread running through all these models is the assumption that oil generation depends upon both the temperature to which the kerogen has been heated and the duration of the heating. we still have no clue as to when oil generation occurred. 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. in frontier basins there may not be a single well within tens or hundreds of kilometers. methods have been developed for calculating maturity levels where measurements are not available. Time-stratigraphic data are usually available as formation tops and ages obtained by routine biostratigraphic analysis of well cuttings. If no subsurface data are available.60 9 . In some areas there are no well samples available. 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. Furthermore. nor do we know at what depth or temperature it occurred. We need data that will enable us to construct a time stratigraphy for the location of interest and to specify its temperature history. In order to circumvent these difficulties. and migration with timing of structure development or trap formation. Nevertheless. 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. indeed. If no well data are available. 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. measured maturity data are of limited value in exploration. however. maturity measurements can only tell us about present-day maturity levels. perhaps from thicknesses of exposed sections nearby. These considerations are important when we want to compare timing of generation.Predicting Thermal Maturity .
Burial-history curves are based on the best information available to the geologist. In cases where biostratigraphic data are lacking or where the sediments have had complex tectonic histories. a burial-history curve may represent only a rather uncertain guess. that the Tiger well was logged. sediment has accumulated continuously but at varying rates since deposition of the oldest rock 100 million years ago (Ma). In cases where biostratigraphic data are available and deposition has been reasonably continuous. burial-history curves represent our best understanding of the geological history of an area. we can construct the complete figure. are marked on the age-depth plot. Nevertheless. by 80 Ma the sediment had been buried to a depth of 900 m (point C). Today the rock is at a depth of 3700 m. 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. In the Tiger well. it is easy to construct burial-history curves with a high level of confidence. This geometry is a direct consequence of ignoring compaction effects. An example is shown in the following figure.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. Neglecting compaction effects. if constructed as carefully as the data permit. for example. Connecting the six dots completes the burial-history curve. The next step is to locate the first control point from the time-stratigraphic data on the input table. . 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.Predicting Thermal Maturity . The burial-history curve was constructed in the following way: two points. The subsurface temperature must be specified for every depth throughout the relevant geologic past. Suppose further that local weather records indicate a yearly average surface temperature of 19° C. representing the initial deposition of the sediment (point A) and its position today (point B). and that a corrected bottom-hole temperature of 133° C was obtained at 3800 m. Suppose.(9-2) All of the shallower and younger horizons will have burial-history curves whose segments are parallel to those of the oldest horizon. TEMPERATURE HISTORY The next step is to provide a temperature history to accompany our burial-history curve. Using these present-day data and extrapolating them into the past. which was constructed from the time stratigraphy for the Tiger well.
If deposition resumes later. Erosion is indicated in a burial-history curve by an upward movement of the curve.62 Where measured bottom-hole temperatures are not available. burial-history curves for both hanging wall and footwall can be represented on a single diagram. but the geothermal gradient varies in response to heating or cooling events. the burial-history curve again begins to trend downward. temperature profiles will be based largely on guesswork. maps of regional geothermal gradients can be useful in estimating the gradient at a particular location. Faulting can be dealt with by considering the hanging wall and footwall as separate units having distinct burial histories. The effects of thrusting on thermal maturity are not well understood. For example (9-7). SPECIAL CONSIDERATIONS ABOUT BURIAL-HISTORY CURVES The most common complicating factor in constructing burial-history curves is erosional removal. however. If thrusting is rapid compared to the rate of thermal equilibration between thrust sheets. the resultant thinning of the section must be represented in the entire family of burial-history curves. the movement of hot rocks from the bottom of the overthrusted slab over cool rocks at the top of the underthrusted slab will affect . If. There is no theoretical limit to the complexity that can be introduced into our temperature histories. the data necessary for highly sophisticated temperature reconstructions are simply not available. There are numerous other variations that can be employed in creating temperature grids. some part of the section is repeated as a result of thrusting. 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. Given adequate data or an appropriate model on which to base complex temperature reconstructions. The individual segments of each of the burial-history curves in a family will remain parallel. Causes for such events could include global warming and cooling or local climatic variations resulting from continental drift or elevation changes. In other cases the surface temperature remains constant. If part of the section is missing as a result of faulting. we are limited only by our own creativity. we can change surface temperatures through time without altering the geothermal gradient.Predicting Thermal Maturity . however. Whenever erosional removal occurs. In many poorly explored areas. In most cases. two separate diagrams should be used for the sake of clarity. More complicated temperature histories account for changes in thermal conductivities caused by variations in lithology.
Individual burial-history curves remain parallel. The temperature factor. Because the rate of maturation was assumed to increase by a factor of two for every 10° C rise in temperature. Lopatin defined each time factor simply as the length of time. Index values increase or decrease regularly at higher or lower temperatures intervals. A Time interval is the length of time that the rock has spent in a particular temperature interval. 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). but the distance between the two lines which bracket the erosion. respectively. Now we can carry out the maturity calculations. expressed in millions of years. we must paste them together. increases exponentially with increasing temperature. more work is required before we will understand fully how thrusting influences hydrocarbon generation and destruction.(9-12) CALCULATION OF MATURITY Once the burial-history curves and temperature grids have been constructed.400 cal/mol will approximately double with every 10° C increase in reaction temperature. spent by the rock in each temperature interval.63 organic maturation by causing important perturbations in subsurface temperatures. Testing of his model and the successful application of Lopatin's method in numerous published examples have confirmed the general validity of this assumption. Temperature intervals are defined by successive isotherms spaced 10° C apart. Lopatin (1971) assumed that the rate of maturation followed this doubling rule. for any temperature interval the temperature factor (?) was given by: ? = 2n The temperature-factor thus reflects the exponential dependence of maturity on temperature. we need to define both a time factor and a temperature factor for each temperature interval. in contrast. However. In order to carry out maturity calculations conveniently. Lopatin chose the 100°-110° C interval as his base and assigned to it an index value n = 0. 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. This intervalTTI value represents the maturity acquired by the rock in that temperature interval during the time . Loss of 1000 m of section by erosion during an uplift event lasting from 70 Ma to 60 Ma. Total maturity is calculated by summing the incremental maturity added in each succeeding temperature interval.Predicting Thermal Maturity . Studies in the Overthrust Belt of Wyoming indicate that a slow-equilibration model is superior to a simple model invoking rapid thermal equilibration. Intersections of the burial-history curve with each isotherm are marked with dots. These dots define the time and temperature intervals that we shall use in our calculations.
no matter how much or how rapidly we cool it down. the cake will bake slowly at first but will bake faster and faster as the temperature rises. we cannot "unburn" it. . FACTORS AFFECTING THERMAL MATURITY Because maturity is affected by both baking time and baking temperature. Maturity always increases. although at increasingly slower rates. Furthermore. if we forget about the cake when the oven is hot and let it burn. followed by a nonerosional depositional hiatus for the last 50 Ma. even if a rock cools down. Four of the many paths by which an 80-Ma-old rock could have reached a present burial depth of 3000 m is indicated in the figure (9-21). where the time factors and yfactors for each temperature interval are shown on the burial-history curve.Predicting Thermal Maturity . it can never go backward because interval-TTI values are never negative. The first step in calculating TTI is illustrated in the following figure. we simply sum all the interval-TTI values for the rock. finally. A good analogy can be drawn between oil generation and baking. maturity continues to increase (albeit at a slower rate) because y is always greater than zero. If we put a cake in a cold oven and turn the oven on.64 given.(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. In D 40 Ma of rapid burial to a depth of 4000 m was followed by a hiatus lasting 30 Ma and. baking will continue. as the oven cools down. Figure C shows rapid burial during the first 20 Ma. the specific burial history of a rock can strongly affect its maturity. but quite rapid in the last 10 my. On the other hand. In B burial was very slow during the first 70 Ma of the rock's existence. In the adjoining table interval-TTI values and total-TTI values up to the present day are calculated. In A the rock was buried at a constant rate for its entire 80-my history. To obtain total maturity. If we turn off the oven but leave the cake inside. by 10 Ma of uplift and erosion. TTI values differ appreciably among these four scenarios.
The model includes an extensive nonerosional depositional hiatus. might we anticipate possible problems with time. Kc = Cody-Frontier formations. so even a rather large error in baking time will not produce a catastrophic change in maturity. Tfu = Fort Union Formation. The sensitivity of maturity to temperature is clearly indicated by the exponential dependence of maturity on temperature predicted by the Arrhenius equation. Age calls are often made within a million years.(9-29) Furthermore. Wyoming. and can be even better in Cenozoic rocks. but there is no guarantee of their accuracy in any particular case. . we usually have excellent control on rock ages through micropaleontology. B) Revised burial-history model for Well #1 based on the poor correlation with measured maturity data.65 A) Initial proposed burialhistory model for Well #1. Secondly. Various methods have been developed for this purpose. time data are seldom a problem. Present-day subsurface temperatures are difficult to measure accurately. Temperature. 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. In actuality.Predicting Thermal Maturity . Only in cases where micropaleontological dating was not or could not be carried out. First. Most logged temperatures are too low and require correction. the dependence of maturity on time is linear. Family of burial-history curves for a well in the Big Horn Basin. our uncertainties about the true values of subsurface temperatures are much greater than about time. in contrast. is the single most important cause of uncertainty and error in maturity calculations. showing the evolution of the oilgeneration window through time. Km = Lance-Meeteetse formations. Tu = undifferentiated Tertiary.
85 0.27 0. Base Pleistocene 2 Ma Base Pliocene 5 Base Upper Miocene 11 Base Middle Miocene 50 Ma .7 0.41? 1. however.18 0.21 1.08 0. 3500 ft of Pliocene.05 0.06 0.9 1. do not utilize different kinetic parameters for the various kerogen types.3 Bit/TOC 0.5-3 2.8 0.67 0.5-3 3.86 1. we still would have to extrapolate the present somehow into the past.90 0.07 1.22 0.5 2.5-3 2. The corrected bottom-hole temperature was 270° F.0 0.33? 1.5-3 2.5 3-3.5 3.5-3 2. In other cases.02 0.5-3 2.0 3-3. even an inaccurate extrapolation into the past may not cause significant problems.49 0.Predicting Thermal Maturity .52 0.5 0.66 0.71 0. where presentday temperatures are maximum paleotemperatures.5 3.59 0.3 1. particularly where Paleozoic rocks are involved.25 1. however.65 0.8 1.000 ft of Upper Miocene before being abandoned at 16.00 1.88 0.08 0.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10 2-2. EXERCISES EXERCISE Thermal Maturity 1 Perform a source-rock evaluation of the section penetrated in the Turquoise Well.000 Type of Sample Cuttings Cuttings TOC 1.7 0.03 0. In such cases we should be very careful about using predicted maturities unless we have some independent confirmation of the validity of our model from a comparison with measured maturity data.1 2.06 0.51 0.03 0. A question of some concern comes from the previously mentioned fact that most of the maturity models treat all types of kerogen identically.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.26? 1. and 11. In many cases. Source-rock data tor the Turquoise Well Depth (ft) 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500 8000 8500 9000 9500 10.150 ft in the Middle Miocene.4 0.48 Ro 0. A plausible average surface temperature is 20° C.08 0. an accurate interpretation of the ancient geothermal history may be critical.02 Atomic H/C 0.5-3.99 1.21 1.01 0.65 0.91 1.2 0.60 0.91 1. Despite experimental evidence indicating that different kerogens decompose to yield hydrocarbons at different levels of maturity models.27 1.51 0. It penetrated 1000 ft of Pleistocene sediments. Construct a family of burial-history curves for the well and calculate the present-day TTI at total depth.5 2.5 2.66 Even if we could measure present-day subsurface temperatures with perfect accuracy.5 2.91 0.1 0.6 4.3 2.17 0.
Determine when each of the strata began to generate oil.end Cretaceous: 15° C 141° C 25° C EXERCISE Thermal Maturity 4 The Ultraviolet Well is spudded in Paleocene sediments. Corrected BHT (4200 m): Estimated surface temp. draw a burial-history curve for the section penetrated and calculate maturity for the Kimmeridgian shale. At a depth of 1500 ft. Age data top Paleocene base Paleocene base Maastrichtian base Campanian base Santonian base Coniacian 55 Ma 65 73 83 87.Predicting Thermal Maturity . 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. Assuming a surface temperature of 10° C and a geothermal gradient of 2° F/100 ft.5 base Turonian base Cenomanian base Cretaceous top Kimmeridgian base Kimmeridgian 91 Ma 97 144 150 156 Ma . 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. Total depth is reached at 6120 ft in Middle Jurassic rocks. 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.5 88. micropaleontology indicates the rocks to be of Maestrichtian age.67 EXERCISE Thermal Maturity 3 Calculate present-day TTI at 3000 m in the Red Well. Evidence from related sections indicates that the Paleocene was originally about 3000 ft thick and that no other Cenozoic sediments were ever deposited. assuming a constant geothermal gradient through time. Total original thickness of the Kimmeridgian is thought to be 1500 ft.
Carboniferous '' Ordovician '' Depth (ft) 7.500 21. "A regional study of the area suggests the probable presence of a thin. Because of the high operations cost. The source rock is thought to be about 300 Ma old. From 40 Ma to the present about 500m of additional burial occurred. Nearby well control indicates that a geothermal gradient of 3.65°C/100 m and a surface intercept of 15°C are reasonable for the area. At that time nearby orogenic activity caused the first traps to be formed during a gradual 1200m uplift lasting until 40 Ma. The following geological summary is available to you. The basin filled at a generally uniform rate from about 300 Ma to 100 Ma. and the surface temperature today is about 15° C.000 11.0° F/100 ft. Carboniferous '' '' '' '' E." Utilizing the principles of hydrocarbon generation and preservation.000 25. The geothermal gradient was found to be 1.500 EXERCISE Thermal Maturity 6 You have been asked to evaluate an undrilled prospect in a remote area that is available in an expensive farm-in deal. they are in turn overlain at 2750m by a sandstone of excellent reservoir quality.000 18.500 27. evaluate the prospect.000 8. No other reservoirs are anticipated. The traps at the prospect location formed slightly prior to the beginning of erosional removal in the basin and have retained integrity to the present.000 23. Top of Permian Virgil Missouri Des Moines Atoka Morrow Mississippian Kinderhook Sylvan Arbuckle Age (Ma) 230 280 288 296 304 309 320 340 425 470 Period Permian 0 L. The reservoir is sealed by a thick salt layer.68 EXERCISE Thermal Maturity 5 Analyze the timing of oil generation in the Pink Well. oil-prone source rock at about 4300m depth near the prospect. No unconformities are recognized within the Paleozoic. Your responsibility is to make a recommendation regarding the nature of hydrocarbons that might be present in die prospect. rich. Time-stratigraphic data are given in the following table.Predicting Thermal Maturity . . Erosional removal since the Permian probably totals about 2000 ft. Highly fractured carbonates overlie the source rock.000 13. No other source rocks were noted. upper management has decided that gas and condensate are not economical.
half a mile or whatever. we are involved with a greater or less degree of uncertainty about quantities. which can be produced using assisted or enhanced recovery techniques. Note. but the same considerations. 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. and therefore without any dissolved gas of significance. just what these changes amount to.69 10 . What they think is beyond that in the accumulation. We will refer to oil. it is desirable to be able to express our degree of confidence in it. 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. Because anyway there is uncertainty about this amount. How do we handle these problems? Before we get into this. or predict. located at surface near the well-head. once a discovery is made. It usually refers to what was there originally. So. since we are never able to recover all of the oil that is down there in the reservoir. there is no way that we can know precisely how much we have found: the geology. Some might use the term to refer to the amount of recoverable oil that is believed to lie within a given radius. 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. let us again emphasize that we are dealing all the time with uncertainties. Similarly. The stock tank is. before we started to take any of it out. 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. and tertiary reserves using more exotic techniques. and oil may be produced directly into it. of a well. However. This section is included to give an idea of what is involved. Proven reserves: Here we start to enter a minefield! Different companies have different definitions of what is proven. unless we can be more specific about how we are going to produce them. We have to try to understand. in the case of small fields. We may distinguish between primary reserves that can be produced without any artificial assistance other than pumping. we have to clear a good deal of misunderstanding and misuse. they might designate as `probable'. Increasingly these days. This may be done via a standard deviation or by a statistical probability (see below). 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. Recoverable reserves: The volume of oil that can actually be produced to surface from an accumulation.Quantitative Assessment So far we have been talking in rather generalized terms. companies tend to use `proven' for those reserves that are believed to be present with an 85 or maybe 90 per cent degree of . And yet oil companies need to know what to expect. until actually all of the oil has been produced. even within oil companies.Quantitative Assessment . which controls the amounts of oil in the reservoir. First. methods. A bald figure for `recoverable reserves' is somewhat meaningless. is liable to change between our information points. of the following terms: OIL IN PLACE This is the total volume of oil. measured in barrels or other units that is present in an accumulation under the ground. our wells. however. or hope to find. We cannot regard these quantities as `reserves'. secondary reserves. You may see the engineers using the term STOOIP: stock tank oil originally in place. let alone how much. we have to remember that we are dealing with a resource and that we are very concerned with the quantities involved.
This will be controlled by variations in the nature of the sediments that comprise the reservoir. and regional and local geological interpretation.Quantitative Assessment . We then eliminate progressively everything from this volume that is not oil. the volume of the gas cap and the water-bearing rock below the oil-water contact being discounted. if we do. What this means and how we arrive at the figure. it is the remaining reserves.Sw)] * RF * Constant FVF where: – BV is the volume of the reservoir formation within the closure of the trap above the spill-point. meaning that we have to try to interpret in detail the environments that the sediments were deposited in. or rather the average porosity of the net reservoir across the entire accumulation. it shrinks because gas bubbles out of it as its pressure is eased during production. DISCOVERED RESERVES Once a discovery of oil has been made. and the quality and strength of the cap rock. BV will be determined from seismic and well data. Again we need an average value for the field. to refer to a degree of confidence or probability. They refer respectively to what was there and recoverable before we started producing. in this case 50 per cent. which is the percentage of the bulk volume that actually contains the oil. So we multiply the bulk volume of the reservoir in the trap by those factors that represent the non-oil. the higher will be the water saturation. If we do not know where the gas-oil and oil-water contacts are. It is affected by many factors. `probable'. faulting. 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. 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. that are meant. even when we have information from a lot of wells. – ? is the porosity. like `proven'. Usually. We have to discount those parts of it that are useless and just consider the net reservoir thickness. and what is still there for the taking at a given date. It may well be that it is best to avoid the terms `proven'. . Recoverable reserves = [BV * Fill * N/G * ? * (1 . and `possible' altogether. then we can go straight to the bulk reservoir volume containing the oil.70 confidence or statistical probability. This can be pretty subjective. we shall see shortly. We do our best from measurements on core samples and from wireline log interpretation. Not all of a reservoir formation is going to be sufficiently porous and permeable to contribute oil to production. and the thickness of the reservoir govern it. – Fill is the `fill factor'. if we hear simply about `reserves'. The shape of the trap. – FVF is the formation volume factor. then this factor may be little more than a guess. the percentage of the porosity that is occupied by the immovable water. We may actually be able to measure the FVF if we have a sample of oil collected under subsurface pressures from the bottom of our well. We 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. Probable reserves: Equally dodgy! One definition was given above: the term may be 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. to cover the reserves that have only a 15 or 10 per cent chance of being present. What anyway should we regard as net reservoir? A rather arbitrary porosity cut-off value is often used. including the adequacy of the source rock to provide enough oil to the trap. Sometimes `possible' is also seen. – N/G is the net to gross ratio. but what happens between and beyond our well control? – Sw is the water saturation.
So we usually have to base our estimate on prior experience elsewhere. this is commonly about 50-60 per cent. It is a figure that we cannot know exactly until we have finished producing. Different geologists will certainly come up with different values for at least some of the input factors. but biassing its pick towards our best estimate. More commonly. If we plot out the answers on our list falling within successive size ranges (in barrels of oil). we can work out the standard deviation (the ±) which will give an idea of our confidence in our answer. then. It will be clear to anyone that. The number of answers in successive reserve ranges is plotted against the size ranges themselves. having regard to all of the geology. the proportion of the oil in the reservoir that we can actually recover and produce. Most commonly these days. known as a Monte Carlo simulation.. but it may be a good deal less from carbonates. If we are working entirely in the metric system. from minimum possible to maximum possible. there must be considerable uncertainty to say the least. In a sandstone reservoir. until we begin to wonder whether our answer has any reality or meaning at all. and we also specify the total range. 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. doubtful estimates by doubtful estimates. So we have a whole list of answers. What we are doing. maybe 500 or 1000 times. somewhere within which the `true' figure must be. however.71 – – RF is the recovery factor. The computer does the sum using these values.). and governments must have numbers that they can use for planning purposes. and again. and again. . and arrive at perhaps wildly different answers. then we don't have to worry. To get an answer to our sum in barrels of oil. the problem is tackled through a statistical technique. Who is right? Whose answer should we use? Can we indeed believe any of them? Unfortunately we cannot escape from the problem. our best estimate. The list is put into order from the smallest to the largest. Then we get a computer to pick a value for each factor at random from the range we have given. companies. is to multiply uncertainties by uncertainties. Note that the preferred answer that is usually used is the mean value. we give as our preferred figure the average of all the answers (the mean). Instead of estimating single figures for the factors that go into the reserves formula. The Americans measure reservoir volume in acre-feet: area in acres multiplied by reservoir thickness in feet. and to try to be as honest and objective as possible. since it is about this that the standard deviation can be calculated.. in producing figures for all of these factors. any one of which could be the real value. even though they may be well aware that any such figures will eventually turn out to be wrong. Diagrammatic plots of the outputs from two Monte Carlo simulations. for this average value. A constant is needed to adjust the units. for each of the factors we work out our best estimate. we shall find that the bulk of them tend to cluster round the middle (Fig. and then analysed statistically. we have to multiply the figure we calculate by 7758. Alternatively one may plot the frequencies as percentages of the total number of answers: the statistical probabilities. Then we ask it to do the same thing again.This is because.Quantitative Assessment .
management can then decide whether or not to take the gamble on developing the field at those odds. So this type of graph has now become one of the standard key tools in exploration/development decision. It is this sort of thing that helps to make the oil exploration business so competitive. that is exactly what it is. objective.the risk factor. but rather it is the number an individual geologist might produce to reflect his/her personal interpretation of the geology. We have to give not only our best estimate of how much petroleum there might be.). then no oil. and possible at. 50. UNDISCOVERED RESERVES This is all very well.at least until we start also considering the costs and economics. it doesn't take any account of the fact that our exploration well may. for geological reasons. you may say. the same values are discounted by a 50 per cent risk factor. we can read off from the graph the chances of our field containing that much oil or more. we have to go a stage further. It is also used to assist management in making their exploration/development decisions.Quantitative Assessment . turn out to be totally dry-lacking in hydrocarbons. This chance (probability) is known as the risk factor: it is an expression. now gives a more complete picture of the viability of an undrilled prospect . if any one of them fails or is lacking. The risk factor. as opposed to assessing what we already know to be there. and honest as can be in assessing exploration risk. but also the chance of there in fact being any oil at all. And if all this sounds like a gambling game.72 The output from a Monte Carlo simulation with the percentages plotted cumulatively. one of the main benefits from all of this is that it forces us to think carefully about the geological requirements for oil to be present. different geologists will arrive at different figures for the probability of success. the curve represents the chance (probability) that the reserves are a certain size or greater. By plotting the answers from the 100 per cent probability downwards. Incidently. say. It cannot be worked out completely objectively. This is what is used to determine those reserves that may be called proven. . Most usefully. It will give a graph which shows the probability that the reserves will be of a certain size or more. there really is no such thing as the risk factor. if the engineers say that a field of so many million barrels is going to be needed to justify development and production costs. and then merely combine the probabilities to give an overall probability . Indeed it does not! When we are looking at exploration of the unknown. combined with the estimate of how much. The way it is commonly approached is to go back to the basic conditions for oil acumulation: all of the essential requirements have to be met if there is to be oil in a particular place and that. in numbers. we can plot out the percentages of answers in successive size ranges cumulatively as we work down the list (Fig. to give the chance of discovering certain reserves or more including the 50 per cent chance that we may find nothing at all. of our confidence that there will be at least some oil. Of course we try to be as scientific. and ensures that all possibilities are considered. perhaps. In the lower plot. the 90. but it assumes that we have already discovered oil. and 10 per cent levels of probability respectively. We try to assess the probability that each factor will be satisfied. When it comes down to risk. probable. For example.
otherwise we may be doing little more than guessing. to believe that we can do this would be the height of conceit. 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. on this tack. 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. Many `experts' have scratched their heads over the estimation of undiscovered reserves. ULTIMATE RESERVES So far we have been talking about a single oil accumulation or a single prospect. and the area under that bit will represent what. Adding this to the original reserves will give us what is sometimes called the `ultimate reserves'-a grand total for the basin. But we have to admit that. we are said to be consulting the oracles! All of the above techniques have been used. qualify it by a statistical probability. In a similar vein the amount of oil found world-wide each year from the beginning of the century can be plotted.73 Lastly. the built-in risk factor takes care of this. it is a pretty wild sort of plot. This is known as the Delphi technique. We could make comparisons between known and unknown basins. and as such can be very useful in planning an exploration program. knowing how rich it is. 5. then the area under it represents the total volume of oil found to date. unless we really have a lot of information (we never have enough!). Let us look at the more important ones. or would our money be better spent on drilling a smaller but safer one? The risked reserves.Quantitative Assessment . Should we. If all else fails. This figure is extremely imprecise and may be not much more than a guess. 4. on average. 6. This combines in a single estimate. Undiscovered are thus what we hope to find in a prospect area or sedimentary basin in the future. The obvious thing to do is to add together the risked reserves estimates of all the remaining prospects. and some may be more appropriate in given circumstances than the others. sometimes in combination. is a hypothetical figure. this technique may bring us into the right ball-park. We might look at explored and known parts of the basin. Forcing these experts to agree a figure amongst them might refine the approach. If we have a reasonable amount of information and control. go for a large but very risky prospect.). if we draw a smooth line through it to even out the peaks and the troughs. However. However. How now do we estimate what still remains to be discovered over a wider area or even an entire sedimentary basin? There really is no objective way of doing it-but still companies and governments want to know. all of them are very dodgy . we can. merely use the average of the figures they produce. the two elements of size and chance of success. and a number of techniques have been employed. for our `best estimate'. get a number of experts to make their forecasts by whatever technique they prefer and. and made available for entrapment (the `charge') can be calculated. the amount of oil generated. Use past statistics (number of barrels of oil found on average for each 100m of exploration drilling?) and extrapolate to future drilling. then use these figures for the unexplored parts of the basin. and use the figures for the known also for the unknown ones. Delphi was the place in ancient Greece where one went to consult the oracle about one's future. 1. however. There are lots of uncertainties in this but the calculation would be amenable to a Monte Carlo type of simulation. We could adopt what is known as a `geochemical material balance' approach. or underlying each square mile of surface area. Some of these will be successful. but some will be dry. and calculate average quantities of oil per cubic mile of sediment. 2. remains to be found. however. we have to assume that today we can identify and assess all of the prospects that ever will be found in the basin. 3. expelled. for example. Extrapolate this smoothing line out into the future. let us note a number known as the risked reserves. This starts with the volume of mature source rock in the basin and then.