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
and are called bitumen . it is known that organic debris derived from plants and algae is best preserved in fine-grained sediments deposited in the absence of oxygen. These play a key role as the precursors for oil and much natural gas. called metagenesis. called methanogens. thermal reactions become increasingly important. Certain microorganisms. but only within the last few years have we realized that in many areas a large portion of the natura!-gas reserves are biogenic. however.Organic Facies . and temperature increases.
. where hydrocarbon movement ceases and accumulation occurs.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. As burial depth increases.5
1 . Although the transformation process is very complex. During this second transformation phase. and thus eventually bring organic diagenesis to a halt. porosity and permeability decrease. Formation of biogenic methane has been recognized for a long time. These differences can have a significant effect on hydrocarbon generation. kerogen begins to decompose into smaller. with many details still poorly understood. called catagenesis. the principal products consist of smaller gas molecules. In the early stages of catagenesis most of the molecules produced from kerogen are still relatively large. these are the precursors for petroleum. or under different diagenetic conditions. Migration through these conduits often leads to traps. the largest of which are called kerogen. and were formed as dead organic matter was converted to microbial tissues. The earliest stage of hydrocarbon generation occurs during diagenesis. Most of this organic matter is transformed during diagenesis info very large molecules. Once formed. convert some of the organic debris to biogenic methane. Low-temperature chemical and biological reactions (called diagenesis) that occur during transport to and early burial in the depositional environment modify this organic matter. more mobile molecules. oil and gas molecules can be expelled from the source rock into more permeable carrier beds or conduits. 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. In the late stages of catagenesis and in the final transformation stage. Many of the chemical compounds present in sediments are in fact derived from bacteria. As temperature rises. These changes lead to a gradual cessation of microbial activity. are chemically distinct from each other.
Preservation of organic material is actually a rare event.6
2 . Preservation of organic matter begins with photosynthesis. we need to understand how this organic matter came to be preserved in the rocks. Most organic carbon is returned to the atmosphere through the carbon cycle. Because of
. less than 1% of the annual photosynthetic production escapes from the carbon cycle and is preserved in sediments. A large fraction. Despite the great imbalance in biomass between terrestrial plants (450 billion metric tons [t]) and aquatic phytoplankton (5 billion t). as a consequence of the much more rapid reproduction of simple aquatic organisms. The recently discovered deep-sea ecosystems in the Pacific Ocean that derive their energy from oxidation of sulfides in hydrothermal vents are interesting
but volumetrically unimportant. Zooplankton and higher animals contribute relatively little organic matter to sediments.Organic Facies
THE CARBON CYCLE
Because oil and gas are generated from organic matter in sedimentary rocks. the yearly productivity of both groups is about equal. Oxidative decay of dead organic matter is a highly efficient process mediated largely by microorganisms. however. comprises microbial tissue formed within the sediments by the bacterial transformation of plant and algal debris. Some of the organic material in sediments consists of fragments of plants or algae that derived their energy from the sun.Organic Facies .
because under normal circumstances they cannot move upward into the zone of photosynthesis. high photosynthetic productivity will occur at the site of upwelling. predators. preservation. Productivity is the logical place to begin our analysis. There is another zone of seasonal upwelling off the Horn of Africa in the Indian Ocean as a result of
. and that the microbes have given up trying to digest it. however. nutrient availability would depend on such factors as water circulation patterns. If this deeper water is enriched in nutrients. in fact. temperature.000 billion t. Only a small fraction of this (10. Nutrients dissolved in waters below the photic zone therefore go unutilized. In relatively unrestricted marine environments. Only where there is upwelling of subsurface waters can these nutrients return to the photic zone. The three primary factors influencing the amount of organic matter in a sedimentary rock are productivity.
A partial listing of the many factors influencing productivity would include nutrient availability. Upwelling occurs where bulk movement of surface water away from a particular area allows deeper water to ascend to replace it.000. Depth could interfere with microbial diagenesis when compaction reduces pore sizes and nutrient fluxes in interstitial waters.05%) occurs in economic deposits of fossil fuels. a great deal of the oxidation of organic matter occurs within the sediments themselves. with a preference for horizontal water movement within each density layer. paleoclimate. where there is local recycling of nutrients from decaying organisms and influx of fresh nutrients from terrestrial sources. Although some destruction of organic material occurs during transport to the depositional environment. the low TOC values could indicate that the remaining organic matter has no more nutritional value. orogeny and erosion. over vast amounts of geologic time the small fraction that escaped the carbon cycle has built up extremely large quantities of organic matter (20. because without adequate productivity. carbonate supply. Although oxidative decay destroys most of the yearly production. Nutrient availability is. significant amounts of organic matter must be deposited and protected from diagenetic destruction. suggesting that either depth or organiccarbon content eventually limits diagenesis. On the other hand. When we consider inefficiencies in discovery and recovery. volcanism.
FACTORS INFLUENCING ORGANIC RICHNESS
In order for organic-rich rocks to be formed. much of the terrestrial organic material is already highly oxidized when it arrives in the sediments. Peru. For example. one of the critical parameters governing productivity. are therefore much more productive than the open ocean. Each factor may be dominant under different conditions. Namibia. Bodies of water naturally develop density stratification. Shallowmarine environments. and dilution. or about 0.7
extensive oxidation of land-plant debris in soils.1%. and Northwest Africa that result from the movement of surface waters away from these coasts. Each of these categories could in turn be further subdivided.000 billion t) dispersed in fine-grained sedimentary rocks. accumulation of organic-rich sediments cannot occur. only one molecule out of about every one million successfully negotiates the journey from living organism to the gasoline pump. Total Organic Carbon (TOC) values decrease monotonically through the first 300 meters of burial before levelling out at about 0. and recycling by organic decay. and general water chemistry. light intensity. In the modern world there are zones of intense seasonal upwelling off the west coasts of California. watercirculation patterns are particularly important for supplying nutrients and thus controlling productivity.Organic Facies .
preservation of organic matter will be much enhanced. however.2 mL/L. because marine organic matter is consumed preferentially by organisms. its use in practice has been expanded to include very low oxygen levels as well. and we could coin the term dysoxic to describe the zone itself. diagenesis is restricted to anaerobic processes. and because most biological oxidation processes require molecular oxygen.8
monsoonal winds that drive surface waters away from the coast. The presence of undegraded marine organic material is a strong indication of anoxia." hut because of the radical change in biota that occurs at about 0.
The principal control on organic richness is the efficiency of preservation of organic matter in sedimentary environments.2 mL/L. microorganisms that utilize materials like sulfate or nitrate ions instead of molecular oxygen as electron acceptors in their metabolic processes. Three factors affect the preservation (or destruction) of organic matter: the concentration and nature of oxidizing agents.5 mL/L). Theoretical models have been developed to predict upwelling (and consequent productivity) in ancient seas from input data on continental configurations. essentially the only viable organisms are those that we call anaerobes. Anoxia is of tremendous importance in the preservation of organic matter in sediments. Such models are interesting. First. the accuracy with which we can reconstruct continental positions. the type of organic matter deposited.5 milliliters (mL) per liter (L)). However. and all the other factors that influence upwelling loci is severely limited. Because most of the oxidation occurring in the water column. oxidizing agents are probably the most crucial factor. Processes that occur in these two zones are called aerobic and anaerobic. The term "anoxic" literally means "having no oxygen. if on the average only 1% of organic matter is preserved.2 mL/L is called the anoxic zone. landmasses. All these areas exhibit high productivity when upwelling occurs. paleoclimatic conditions. ANOXIA. many species disappear. because when the availability of oxygen is limited. Secondly. and may in fact prove useful in future exploration efforts. After all. The term dysaerobic has been used to describe processes occurring in the transitional zone (0. increasing preservation rates is a very efficient way to increase organic richness. At dissolved oxygen levels below about 0. There are many more organic-rich facies resulting from excellent preservation than from extremely high productivity. There are. wind and water circulation patterns. Anoxic sediments always contain elevated TOC values (generally above 2% and always above 1% ). productivity is probably not as important a factor as preservation. although some species can tolerate extremely low oxygen levels (0. We call the zone in which oxygen contents are high the oxic zone. At lower levels of dissolved oxygen. and the sediment-accumulation rate. especially in the Palaeozoic. Anoxic sediments are not always easy to recognize. some problems associated with their application. respectively.Organic Facies . the simplest way to limit oxidation is to limit the supply of oxygen. Of these. the remaining individuals often become dwarfed in an effort to survive in a hostile environment.2-0. because some of the commonly used indicators of anoxia may be misleading. the zone where oxygen falls below 0. soils. and are usually limited in scope by the availability of sulfate or nitrate. and sediments is biological. and paleoclimates. much oxic sediment also contains large amounts of organic matter. Its presence in
. Thus if anoxia can develop. TOC values alone must therefore be used with caution. All large organisms require oxygen in order to live. These anaerobic processes are inefficient compared with aerobic diagenesis. especially of woody origin.
although stunted burrows can be used as evidence of dysoxia. Truly stagnant basins are actually quite rare. This oxygen minimum develops when the rate of consumption of oxygen within that layer exceeds the rate of influx of oxygen to it. and both the waters in the bottom layer and the underlying sediments will become anoxic. 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. Color should be used mainly as a negative criterion: If a rock is not very. however. and warm climates are necessary to avoid overturn caused by freeze-thaw cycles. Therefore. there is no guarantee that anoxia was present at the sea floor. denser waters remain at the bottom. Color is not a reliable indicator.9
rocks therefore indicates that diagenesis was stopped prematurely. OXYGEN-MINIMUM LAYER (OML). 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. and strata from several basins in China. the presence of bioturbation indicates that the bottom waters were not anoxic. The laminae prove that burrowing fauna were absent. especially during the Triassic along the margins of the developing Atlantic Ocean. it cannot represent an anoxic facies. All anoxic sediments will be very dark gray or black when deposited. where photosynthesis and turbulence can no longer contribute oxygen to the water. in fact. most likely by absence of oxygen. Among the ancient lake beds thought to have been deposited in permanently stratified waters are the well-known Green River Shale (middle Eocene. The ultimate implications of anoxia for petroleum exploration are great. The cooler. The oxygen minimum layer usually begins immediately below the photic zone. Consumption of oxygen results from decay of dead organisms that have sunk from the photic zone above. Many black rocks. Conversely. anoxic sediments. the Elko Formation (Eocene/Oligocene. are not rich in organic carbon. and its presence indicates that the anaerobic reduction of sulfate ion did occur. The supply of fresh oxygen is therefore limited to horizontal
. it is instructive to consider complete stagnation. anoxic sediments show preserved depositional laminae on a millimeter or submillimeter scale. no more oxygen can enter. Wyoming). Furthermore. Nevada). Lakes of the Rift Valley of East Africa are excellent modern analogs receiving much attention from both researchers and explorationists at the present time. Marine basins are seldom isolated enough to fit well into the stagnant-basin model. it may well have developed after burial. Although pyrite does indeed form under anoxic conditions. they often owe their dark color to finely divided pyrite or to particular chert phases. It therefore behoves us to understand the conditions under which anoxia develops. The presence of pyrite itself can also be deceptive. once the original oxygen has been consumed in oxidizing organic matter. slow circulation or turnover of the water column occurs almost everywhere. leading to the eventual development of a pycnocline (density interface) which prevents interchange between the two layers.Organic Facies . Lakes in failed rifts can also contain organic-rich. and therefore that dissolved-oxygen levels were below 0. it has been estimated. but limnic environments often are. If an isolated body of water is deep enough. Depths in excess of 200 m are required to prevent mixing during storms. are anoxic in some of the places where they have been penetrated. STAGNANT BASINS. then permanent density stratification will arise as a result of temperature differences within the water column. anoxia can be very local.2 mL/L. that most of the world's oil was generated from source beds deposited under anoxic conditions. Lake deposits associated with continental rifting. particularly in understanding lacustrine beds. Lack of communication between the layers prohibits replenishment of oxygen in the bottom layer. Finally. Nevertheless. very dark. and if the climate is subtropical or tropical.
Late Devonian) the world oceans were severely depleted in dissolved oxygen. when a major transgression had greatly increased the continental shelf area. permanent density stratification will develop. Coal Swamps. Intensely developed OMLs occur in areas of high productivity and. an upward expansion of the OML led to a tremendous increase in the surface area covered by anoxic bottom waters. foreset beds within the same system are leaner in organic matter because they are deposited above the OML. the waters entering or leaving the basin are near surface. It has been proposed that at certain times in the past (e. Nutrients are concentrated by evaporation. Wherever an intensely developed OML intersects the sediment-water interface. Below the OML oxygen levels again increase. In contrast. Late jurassic.10
movement of oxygen-bearing waters. High productivity reduces oxygen levels. and diminished bacterial activity. its intensity varies greatly. In either case. in areas of poor circulation. Shallowly silled basins often yield evaporites. Settings in which circulation is restricted are much more common than stagnant basins. mid-Cretaceous. 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. whereas in a fluvially dominated system (Black Sea) the net flow of surface water is out over the sill. including paleoclimate and water circulation. Coal swamps can develop under a variety of conditions in both marine and non-marine environments. This depletion was probably the result of the complex interplay of several factors. which could be excellent hydrocarbon source rocks. Circulation is often restricted by the presence of a sill. It is not coincidental that these were times of deposition of large amounts of organic-rich rocks in many parts of the world. those environments can also incorporate the features of an oxygen-minimum-layer model. In actuality there is a lazy turnover of the bottom waters. high influxes of organic matter. or as lateral facies equivalente thereof. since most organic matter was destroyed within the overlying OML. Anoxia
. Any organic matter arriving in those sediments will have an excellent chance to escape oxidation. 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. Although an oxygen-minimum layer exists virtually everywhere in the ocean. sediments will be deposited under low-oxygen conditions. Where the sill is shallow. However. Furthermore. In an evaporitic environment (Karabogaz in the Caspian Sea) there is a net flow of water into the basin. because of their connection with the open-marine realm. as a result of diminished oxygen demand. There are other ancient and modern examples of organic-rich rocks deposited under anoxic or near-anoxic conditions associated with OMLs. In times like the mid-Cretaceous.g. the oxygen they can contribute is limited. RESTRICTED CIRCULATION. the shallowness of the swamps prevents the waters themselves from becoming anoxic. Shallow Silling. and grazers and predatory organism are eliminated by the high salinities. Although circulation in coal swamps is generally sluggish.Organic Facies . The result is often deposition of organic-rich laminae within evaporites. if the basin is deep enough. because these horizontally moving waters also lie within the oxygen minimum layer. and high hydrogen-sulfide concentrations create conditions poisonous to predators. the point of connection between the restricted area and the open-marine environment. but it is too slow to disturb the anoxia which develops in the bottom layer.. with the bottom layer almost isolated from the open-marine waters. to a lesser extent. Large amounts of organic material are preserved in coal swamps as a result of the combined effects of poor water circulation. Evaporitic environments combine the opportunity for abundant growth of algae with ideal conditions for preservation. During those times the OML expanded both upward and downward because of poor supply of oxygen to subsurface waters.
as a result of more rapid removal of organic material from the zone of microbial diagenesis. Organic matter of algal (phytoplanktonic) origin is consumed more readily by organisms than are other types of organic material. Rapid deposition of inorganic detritus is common in turbidites and in prodelta shales. Rapid settling of organic debris through the water column is also important. much of the organic material that does reach the bottom in deep waters arrives in relatively large fecal pellets.Organic Facies . but their supposedly low potential for generating oil is to be reconsidered. provide an ideal means of maintaining low-oxygen conditions. or resinous material. because extensive decomposition occurs during its fall to the ocean floor. and low productivity in the overlying pelagic realm. and therefore wi11 contain primarily oxidized organic matter. and more favorable for gas than for oil. RAPID SEDIMENTATION AND BURIAL. forest fires. all of which are chemically quite distinct from each other. It may also contain very resistent organic debris derived from erosion of ancient rocks. and may include woody. Coals also accumulate very rapidly and. Most depositional settings not specifically catalogued above will be more or less well oxygenated. but it does spread that organic material through a larger volume of rock. Furthermore. cuticular.
Although high sediment-accumulation rates enhance preservation of organic matter. Lack of sulfate in non-marine swamps further prevents anaerobic microbial destruction of the organic matter. the phenolic components present in lignin-derived terrestrial material are toxic to many micro-organism. which settle several orders of magnitude faster than individual phytoplankton. thus preventing extensive diagenesis of such material. Abyssal sediments are notoriously low in organic carbon as the result of the combined effects of high oxygen levels in abyssal waters. Dilution does not reduce the total amount of organic matter preserved. at very high accumulation rate dilution may become a more important factor than increased preservation. because its chemical components are digestible and provide precisely the nutrients required by scavengers and predators. very slow sedimentation rates. That material which remains is dominantly of terrestrial origin.
. Oxic Settings. biogenic inorganic sediment. TOC values increase as sediment-accumulation rates increase. Coals are important source rocks for gas accumulations. cellulosic. their virtual absence in much terrestrial organic material. Nitrogen and phosphorus are in particular demand. Any extensive organic diagenesis is therefore likely to eliminate algal organic matter first. and other oxidative processes. especially in structural (woody) material. Rapid sedimentation and burial con also enhance preservation.11
develops within the sediments rather than in the water column. Near-shore oxidizing facies sometimes have high TOC values. The net result is a reduction in TOC values. In fact. or organic material. Rapid burial is accomplished by a high influx of inorganic detritus. lignitic. renders it of little nutritional value. The hydrocarbon-source potential of all of these oxidizing facies is low. with their high concentrations of organic matter. TYPE OF ORGANIC MATTER. Phenolic bactericides derived from lignin hinder bacterial decay in the water and throughout the sediment column. but the organic material is almost invariably woody. The extremely high accumulation rates for biogenic carbonates and siliceous sediments in zones of high productivity promote preservation of the associated algal protoplasm.
and the presence of high TOC values coupled with the occurrence of undegraded marine organic matter. such events were often interrupted for long periods before anoxia was reinduced. however. It is important to be able to distinguish local anoxia or anoxia developed deep within sediments from anoxia induced by anoxic bottom waters. Rapid accumulation of sediment shortens the residence time of organic matter in the zone of diagenesis and thus promotes preservation. including stagnancy or near-stagnancy. Shales.12
Dilution effects depend upon rock lithology. however. in contrast. and rapid burial. To derive maximum value from our analyses. Because of its role in creating rocks with excellent hydrocarbon-source potential. There are a number of mechanisms by which oxygen depletion may be fostered and maintained. Direct control of the anoxia was thus probably local. Biogenic sediments. anoxic sediments were deposited discontinuously through time and space. are not as strongly affected by dilution. we should always strive to place the organic rich rocks in the larger context of basin evolution through time and space. preservation is generally the most important. by uncertainties about exact continental positions and configurations in the past. and a very imperfect understanding of oceanic. Consequently. The most reliable criteria for bottom-water anoxia are the preservation of fine depositional laminae. Facies changes from carbonates to shales may create large dilution effects that can be wrongly interpreted as indicating changes in oxygen levels. Models that integrate the concepts of organic richness with depositional cycles and facies analysis will be valuable tools for understanding hydrocarbon systems in basins. Although certain periods undeniably contain more than their share of anoxic rocks.and atmospheric-circulation patterns. where sediment-accumulation rates are directly proportional to organic-carbon-accumulation rates. and dilution by inorganic material. such models are not yet of much practical value for the distant past. If the rapidly accumulating sediment is mainly clastic. however. Some of the commonly applied criteria are apt to be misleading. a strongly developed oxygen-minimum layer. Anoxic events in the past were probably not as large in scale or as long lasting as some workers have suggested.
There are three principal factors that affect the amount of organic matter in sedimentary rocks: primary photosynthetic productivity. anoxia in bottom waters is a phenomenon whose effects we should learn to recognize in ancient rocks. As in the modern oceans. 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. Of these. Productivity can be predicted by locating ancient sites of marine upwellings. as a result of high productivity or sluggish circulation. In biogenic sediments or coals. dilution is far less marked. 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.
. in contrast. show strong dilution effects when accumulation rates are very high.Organic Facies . effectiveness of preservation. Our ability to make accurate predictions is limited. in which the organic and inorganic materials arrive together.
. oxygen and sulfer. whose structures are shown below. The structures of methane and ethane are thus represented by CH4 and CH3CH3 respectively. The chemical reactions of interest to us are very few and are discussed only briefly. This objective is very different trom that of a normal course in organic chemistry. We can make other logical simplifications for longer carbon chains. every carbon atom forms four bonds. are termed organic.
Examples of hydrocarbons are methane. elsewhere in this text usage will vary. and organic geochemistry the study of organic compounds present in geological environments. ethane.Organic Chemistry . the explicit inclusion of every atom and every bond becomes extremely tedious. oxygen. and cyclohexane. and metal carbides. This usage is historical and does not imply that all such compounds are necessarily derived from living organisms. in which one must also learn all the reactions of many classes of compounds. If one wants to draw large molecules." but that usage is incorrect trom the chemist's point of view because those materials often contain substantial amounts of nitrogen. hydrogen always forms one bond. All compounds containing carbon atoms.
NAMES AND STRUCTURES HYDROCARBONS
In chemical terms a hydrocarbon is a compound containing only the elements carbon and hydrogen. as it does in the real world. using a subscript on the H to denote the total number of hydrogens around that atom. Several different types of shorthand have therefore developed to facilitate drawing organic molecules. Carbon atoms like to form bonds with each other. One common convention is to represent all the hydrogen atoms attached to a given carbon atom by a single H.Organic Chemistry
Anyone who uses petroleum geochemistry must be familiar with basic chemical terminology. trace metals. and indeed in every carbon compound (except a few highly unstable ones created only in laboratories). Writing the detailed structure of a simple molecule like methane is no problem. three bonds. especially if one has to do it only occasionally. two bonds. however. Similarly. except carbon dioxide. and other elements. 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. Petroleum and natural gas are themselves often referred to as "hydrocarbons. creating long chains and ring structures.13
3 . Organic chemistry is thus the study of carboncontaining compounds. In each of these compounds. and nitrogen. This unique property of carbon is responsible for the existence of literally millions of different organic compounds. In this chapter we restrict the usage of the term hydrocarbon to the standard chemical one. sulfur. The following representations of n-pentane are equivalent: CH3CH2CH2CH2CH3 or CH3(CH2)3CH3.
The term methyl. n-pentane and cyclohexane are represented by the line structures shown below. which. ethyl and propyl). simple inspection shows how mant' hydrogen atoms each carbon atom must have. The simplest series of hydrocarbons has linear structures. We have ahready encountered n-pentane. The letter n stands for normal. Hydrogen atoms and bonds to hydrogen atoms are not shown at all. and carbon-carbon bonds are shown as lines connecting those points. Regular isoprenoids consist of a straight chain of carbon atoms with a methyl branch on every fourth carbon. That is. All the compounds mentioned above are called saturated hydrocarbons or saturates. no more hydrogen can be incorporated into the molecule without breaking it apart. but the prefixes denoting the number of carbon atoms in the other alkanes are derived from Greek numbers.14
An even quicker shorthand that uses no letters at all has evolved. For example. Note that the name of each compound ends in -ane. Another important group of hydrocarbons is the unsaturates. in contrast. Isoprenoids ranging in length from six to forty carbon atoms have been found in petroleum and rocks. We have also seen that carbon atoms can be arranged in rings. which we used earlier. The zigzag configuration illustrated for n-pentane is adopted to show clearly each carbon atom. Other adjectival forms are made by dropping the -ane ending and adding yl (for example. the names of the other nine simplest n-alkanes are given in the following table. because they are saturated with respect to hydrogen. are able to combine with additional hydrogen. as in "alkane. these molecules are called n-alkanes or nparains. and indicates that there is no branching in the carbon chain. Branching can occur. is the adjectival form of the word methane. 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.Organic Chemistry . a CH3 (methyl) group is attached to the second carbon atom. Among the most important branched hydrocarbons in organic geochemistry are the isoprenoids. Many unsaturated compounds have carbon-carbon double
. giving rise to a vast number of possible structures. In the case of 2methylhexane (C7H16) the basic structure is hexane. These cyclic compounds (called naphthenes) are named by counting the number of carbon atoms in the ring and attaching the prefix cyclo. Because we know that each carbon atom forms four bonds and each hydrogen atom forms one bond." The first four names are irregular. Each carbon atom is represented by a point.
which is an almost-endless sheet of aromatic rings. phosphorus. but they actually have completely different chemical properties from alkenes and are unusually stable.
Atoms other than hydrogen and carbon that occur in petroleum. the compounds in which they occur are called heterocompounds. Their stability permits aromatics to be important constituents of oils and sediments. Most biological molecules are larger and more complex than the simple hydrocarbons. Although they are very important constituents of petroleum. except that the ending -ene indicates the presence of a double bond. The circle indicates that the electrons in the double bonds are delocalized. Fossil organic matter often contains a vide variety of heterocompounds. It is this delocalization of electrons which makes aromatic compounds very stable. they do not add hydrogen easily. which are large. Aromatics form an extremely important class of unsaturated hydrocarbons. Although they are unsaturated. In fact. A variety of reactions. including hydrogenafion. Many common NSO compounds are not directly related to biogenic precursors. They are named in a similar manner to the alkanes. Some aromatic molecules are very large. because the most common heteroatoms are nitrogen. A simplified notation for drawing these molecules permits us to represent the double-bond system by a circle within the ring.Organic Chemistry . Examples are ethene (C2H4) . By hydrogenation ethene thus reacts to form ethane. and cyclohexene (C6H10). of which some are biogenic and others are formed during diagenesis. highly aromatic materials of
. these compounds are called alkenes. the majority contain oxygen. Heterocompounds are also called NSO compounds. bitumen. they are free to move throughout the cyclic system instead of being held between two particular carbon atoms. In the laboratory they are readily converted to alkanes by the addition of hydrogen in the presence of a catalyst. and kerogen are called heteroatoms. Among the most important NSO compounds are the asphaltenes. the structures of which are shown below. The extreme case is graphite. At first glance aromatics appear to be nothing more than cyclic alkenes containing several double bonds. nitrogen. these compounds are quite different trom the majority of the organic molecules found in living organisms. propene (C3H6). that is.15
bonds. sulfur. and oxygen. Many of the heterocompounds present in organisms are converted to hydrocarbons during diagenesis and catagenesis. The hydrocarbons present in petroleum are mostly the end products of extensive degradation of biogenic molecules. Polycyclic aromatic hydrocarbons having fused ring structures are quite common. converts alkenes to alkanes and cyclic compounds during diagenesis.
Because alkenes are highly reactive. sulfur. they do not long persist in geologic environments. or other elements. The hydrocarbons we discussed so far are relatively simple molecules. some complex hydrocarbons that are found in fossil organic material can be related directly to individual biological precursors. Aromatics possess a system of alternating single and double bonds within a cyclic structure.
Amino acids are the building blocks of proteins. It is a polymer consisting of many repetitions and combinations of three basic aromatic subunits. where small amounts of preserved amino acids can be used to date specimens)
. Lignin and cellulose are major constituents of humic coals. They have many characteristics in common with kerogen. however. Like lignin. They are rapidly metabolized by virtually all organisms. Lignin is an important component of wood. and thus tends to become concentrated as other organic matter is decomposed. and thus are seldom preserved in sediments (exceptions occur in shell material and in bones. providing much of the structural support for large land plants. sugars. most carbohydrates are attacked readily by microorganisms. and amino acids. Many nonhydrocarbon molecules common to living organisms are also present in sediments. Upon decomposition lignin forms phenolic compounds. which are aromatics having a hydroxyl group (OH) attached. Lignin monomers are linked topether to form molecules having molecular weights from 3000 to 10. Carbohydrates include starch. it is an important constituent of terrestrial organic matter.Organic Chemistry . and cellulose. Among these are lignin. but asphaltene molecules are smaller and more aromatic than most kerogens. the latter is the most abundant organic compound in the biosphere.16
varying structure. Because phenols are potent bactericides.000 atomic mass units. carbohydrates. Although cellulose is quite resistant to decomposition under some conditions. lignin is rather resistant to degradation.
because it has patchwork structures formed by the random combination of many small molecular fragments. The term kerogen was originally coined to describe the organic matter in oil shales that yielded oil upon retorting. Humic coals are best thought of as kerogens formed mainly from landplant material without codeposition of much mineral matter. The residual kerogens also undergo important changes. the geopolymers become larger. large molecules that have no regular or biologically defined structure. have more mineral matter than algal coals. and still larger ones. as well as the nature of the organic matter from which it was formed. Kerogen is of great interest to us because it is the source of most of the oil and some of the gas that we exploit as fossil fuels. The 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. and the individual component parts are either destroyed or used to construct new geopolymers. The soluble portion. humic acids. for example) are partially or completely dismantled.17
4 . slightly larger ones. Diagenesis results mainly in loss of water. which have molecular weights of several thousand or more. humins. and natural gas. Subsurface heating causes chemical reactions that break off small fragments of the kerogen as oil or gas molecules. in contrast. will be discussed in a following chapter. Large organic biopolymers of highly regular structure (proteins and carbohydrates. with some of the inorganic matrix often being contributed by the algae themselves. whether these hydrocarbons are mainly oil or gas. Diagenetic and catagenetic histories of a kerogen. develop after tens or hundreds of meters of burial. carbon dioxide. The detailed chemistry of kerogen formation need not concern us greatly. True kerogens. A basic understanding of how kerogen is formed and transformed in the subsurface is therefore important in understanding how and where hydrocarbons are generated. and less regular in structure. oil. strongly influence the ability of the kerogen to generate oil and gas. If anaerobic sulfate
. The amount of organic matter tied up in the form of kerogen in sediment is far greater than that in living organisms or in economically exploitable accumulations of coal.Kerogen
Kerogen is normally defined as that portion of the organic matter present in sedimentary rocks that is insoluble in ordinary organic solvents. Lack of solubility is a direct result of the large size of kerogen molecules. called bitumen. and ammonia from the original geopolymers.
The process of kerogen formation actually begins during senescence of organisms. having very high molecular weights. and sediments. Today it is used to describe the insoluble organic material in both coals and oil shales.Kerogen . These geopolymers are the precursors for kerogen but are not yet true kerogens. Algal (boghead) coals are formed in environments where the source phytoplankton lack both calcareous and siliceous skeletal components. Oil shales. more complex. Coals are a subcategory of kerogen. The smallest of these geopolymers are usually called fulvic acids. as well as dispersed organic matter in sedimentary rocks. soils. when the chemical and biological destruction and transformation of organic tissues begin. Kerogen composition is also affected by thermal maturation processes (catagenesis and metagenesis) that alter the original kerogen. which are reflected in their chemical and physical properties. Each kerogen molecule is unique. During the course of diagenesis in the water column. Coals and oil shales should therefore be viewed merely as sedimentary rocks containing special types of kerogens in very high concentrations. and how much oil or gas can be expected.
contain mainly the most resistant types of biogenic molecules that were ignored by microorganisms during diagenesis. which are highly reactive. Most organic oxidation in sedimentary environments is microbially mediated. What is within our reach. and their organic precursors
Transformation of organic material in sediments and sedimentary rocks. the macerals that they are composed of. Subsequent investigations have identified Type IV kerogen as well. Kerogen formation competes with the destruction of organic matter by oxidative processes. and III) and have studied the chemical characteristics and the nature of the organisms from which all types of kerogens were derived. Microorganisms prefer to attack small molecules that are biogenic. The amount of sulfur contributed by the original organic matter itself is very small. is developing a general method of describing gross kerogen composition and relating it to hydrocarbon-generative capacity. II.
. They identified three main types of kerogen (called Types I. and ultimately of much greater practical value. the subdued level of bacterial activity allows more time for the formation of geopolymers and.
Because each kerogen molecule is unique. In a low-oxygen (reducing) environment. Kerogens formed under reducing conditions will be composed of fragments of many kinds of biogenic molecules. better organic preservation. and if the sediments are depleted in heavy-metal ions (which is often the case in nonclastic sediments but is seldom true in shales). therefore. One way that we can begin is by classifying kerogens into a few general types. because the bacterial enzyme systems do not know how to attack them. large amounts of sulfur may become incorporated into the kerogen structure. Even if such a description were possible. Carboncarbon double bonds.Kerogen . About a decade ago workers at the French Petroleum Institute developed a useful scheme for describing kerogens that is still the standard today. in contrast.18
reduction is occurring in the sediments. In an oxidizing environment many of the small biogenic molecules will be attacked by bacteria before they can form geopolymers. or at least look very much like biogenic molecules. Those kerogens formed under oxidizing conditions. Geopolymers are more or less immune to bacterial degradation. in contrast.
The four types of kerogen. it is somewhat fruitless to attempt a detailed discussion of the chemical composition of kerogens. are converted into saturated or cyclic structures. it would not be of great and direct significance to exploration geologists.
successively. They are generally considered to have essentially no hydrocarbon-source potential. and carbohydrates. The various Type II kerogens are grouped together. despite their very disparate origins. catagenesis. Type II (liptinitic) kerogens are also high in hydrogen. leaf waxes.
Van Krevelen diagram showing maturation pathways for Types 1 to IV kerogens as traced by changes in atomic HIC and OIC ratios. and Colorado. contain far less oxygen because they were formed from oxygen-poor lipid materials. have lower hydrogen contents because they contain extensive aromatic systems.19
Type I kerogen is quite rare because it is derived principally from lacustrine algae. Type III (humic) kerogens. 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. because they all have great capacities to generate liquid hydrocarbons. pollen and spores. from Wyoming. The best-known example is the Green River Shale. including marine algae. unless they have small inclusions of Type II material. and metagenesis. of middle Eocene age. in contrast. Type IV kerogens contain mainly reworked organic debris and highly oxidized material of various origins. phenols. in contrast. Type IV kerogens are highly oxidized and therefore contain large amounts of oxygen. have the lowest hydrogen contents.
. In the immature state. The shaded areas approximately represent diagenesis. Cellulose and lignin are major contributors. Type I and Type II kerogens. Heteroatom contents of kerogens also vary with kerogen type. cellulose. Occurrences of Type I kerogens are limited to anoxic lakes and to a few unusual marine environments. Type II kerogens arise from several very different sources.Kerogen . They also include contributions from bacterial-cell lipids. Type IV kerogens. Most Type II kerogens are found in marine sediments deposited under reducing conditions. Type III kerogens have much lower hydrocarbon-generative capacities than do Type II kerogens and. Type III kerogens have high oxygen contents because they are formed from lignin. and fossil resin. Type III kerogens are composed of terrestrial organic material that is lacking in fatty or waxy components. Type I kerogens have high generative capacities for liquid hydrocarbons. Utah. which mainly contain polycyclic aromatic systems. Hydrogen contents of immature kerogens (expressed as atomic H/C ratios) correlate with kerogen type. Type I (algal) kerogens have the highest hydrogen contents because they have few rings or aromatic structures. are normally considered to generate mainly gas.
called catagenesis and metagenesis. The different types of kerogen particles are called macerals. interrelated. is derived mainly from sulfate that was reduced by anaerobic bacteria. whereas hydrocarbon generation focuses on the production of hydrocarbon molecules. In many cases the original cellular structure is still recognizable. but they really represent different aspects of the same process. forcing us to make assumptions about the source organisms. Nitrogen is derived mainly from proteinaceous material. anoxic. Catagenesis refers to transformations of kerogen molecules. In this text we shall use the terms somewhat interchangeably. Kerogen types are defined by the morphologies of the kerogen particles. they represent fundamentally different perspectives. The correspondence is not perfect. Macerals are essentially organic minerals. High-sulfur kerogens (and coals) are almost always associated with marine deposition. however. which is destroyed rapidly during diagenesis. Although the terms catagenesis and oil generation are often used synonymously. called maturation. most terrestrially influenced kerogens are low in nitrogen. metagenesis is not equivalent to "metamorphism. wherever possible. Because lignins and carbohydrates contain little nitrogen. they are to kerogen what minerals are to a rock. 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. which occurs after catagenesis. however. In others the original fabric has disappeared completely. Kerogen sulfur. in some cases. a term taken trom coal petrology. Most high-nitrogen kerogens were therefore deposited under anoxic conditions where diagenesis was severely limited. Microscopic organic analysis has reached a fairly high level of refinement and is often capable of assessing kerogen type with good accuracy. The biggest problem comes in identifying Type III kerogen. especially when we are discussing both aspects simultaneously. 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. A list of the most common macerals and their precursors is given in the table presented earlier in this chapter. The small molecules eventually become petroleum and natural gas. In principle. nonclastic sediments). occur when a kerogen is subjected to high temperatures over long periods of time. Maceral names were developed by coal petrologists to describe. because fresh waters are usually low in sulfate. Thermal decomposition reactions. proving the origin of the particle.
KEROGEN MATURATION INTRODUCTION
Very important changes. Thus few kerogens consist of a single maceral type. but it also continues through the metamorphic stage." Metagenesis begins long before true rock metamorphism.Kerogen . Sulfur is only incorporated into kerogens in large quantities where sulfate reduction is extensive and where Fe +2 ions are absent (organic-rich.
. marine. Many high-sulfur kerogens are also high in nitrogen. because there is not a perfect biological separation of the various types of living organic matter. the materials from which a maceral was derived.20
Sulfur and nitrogen contents of kerogens are also variable and. in contrast. 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. represents drygas generation. Metagenesis. Despite its name. Catagenesis and hydrocarbon generation occur concurrently. they are not precisely equivalent. It is possible to make a reasonably good correlation between kerogen type based on chemical characteristics and kerogen type based on visual appearance. By convention the term catagenesis usually refers to the stages of kerogen decomposition during which oil and wet gas are produced.
Kerogen maturation is not a reversible process-any more than baking a cake is reversible. is to monitor hydrocarbon generation. the more hydrocarbons it can yield during cracking. There is therefore no necessary cause-and-effect relationship
. Types I.
EFFECTS OF MATURATION ON KEROGENS
Kerogen undergoes important and detectable changes during catagenesis and metagenesis. Kerogen particles become darker during catagenesis and metagenesis. II. Some of these changes can be measured quantitatively. simply because the longer time available compensates for lower temperatures. Furthermore. The most important implication of these chemical changes is that the remaining hydrocarbongenerative capacity of a kerogen decreases during catagenesis and metagenesis. the cracking of any organic molecule requires hydrogen. much as a cookie browns during baking. the rates of catagenesis are generally not important at temperatures below about 70° C. This complex interplay between the effects of time and temperature on maturity is discussed in a later chapter. it is also true that other changes in kerogen properties have little or nothing to do with it. Nitrogen loss occurs primarily during late catagenesis or metagenesis. possessing essentially no remaining hydrocarbon generative capacity. including the Miocene Monterey Formation of southern California. and gas) will be discussed in a following chapter. the residual kerogen gradually becomes more aromatic and hydrogen poor as catagenesis proceeds. however. For practical purposes. There is a steady color progression yellow-goldenorange-light brown-dark brownblack as a result of polymerization and aromatization reactions. It is impossible to set precise and universal temperature limits for catagenesis. All kerogens become increasingly aromatic and depleted in hydrogen and oxygen during thermal maturation. As we saw earlier. as evidenced by low maturity. Old rocks will often generate hydrocarbons at significantly lower temperatures than young rocks. Furthermore. These reactions are intimately related to important changes in the chemical structure of kerogen. after hydrogen loss is well advanced. Nitrogen and sulfur are also lost from kerogens during catagenesis. Thus the steady decrease in hydrogen content of a kerogen (usually measured as the atomic hydrogen/carbon ratio) during heating can be used as an indicator of both kerogen catagenesis and hydrocarbon generation.Kerogen . Although it is obvious that many measurable changes in kerogens are related to hydrocarbon generation. Chemical reaction-rate theory requires that the rates of reactions decrease as temperature decreases. but they are not necessarily identical with hydrocarbon generation. The composition of the products (bitumen. much of the sulfur is lost in the earliest stages of catagenesis. In contrast. high-sulfur oils found in a number of areas. The real reason for following kerogen catagenesis. but it also states that at any temperature above absolute zero reactions will be occurring at some definable rate. because time also plays a role. provided that the hydrogen content of the kerogen was known prior to the onset of catagenesis. in most cases decreases of temperature in excess of about 20°-30° C due to subsurface events or erosional removal will cause the rates of catagenesis to decrease so much that it becomes negligible for practical purposes. Because many of the light product molecules are rich in hydrogen. The more hydrogen a kerogen contains. of course. In the late stages of maturity. thus allowing us to judge the extent to which kerogen maturation has proceeded. and III kerogens will therefore be very similar chemically. the chemical process of maturation never stops completely.21
This chapter will focus on those changes in the residual kerogen that accompany catagenesis. even if drastic decreases in temperature occur. oil. 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. and thus are not necessarily valid indicators of hydrocarbon generation.
A general name tor these molecules is bitumen. contain large numbers of unpaired electrons. The more random a kerogen's structure. 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. the more an incident light beam will be scattered. The concentration of free radicals in a given kerogen has been found to increase with increasing maturity. is the ability of kerogen particles to reflect incident light coherently. especially highly aromatic ones.
As kerogen catagenesis occurs. Because coal rank is merely a measure of coal maturity. there would be a large and continuous build-up of bitumen in the rock as a result of catagenetic decomposition of kerogen. For example.Kerogen . the visual appearance of kerogen also does not change during catagenesis: kerogen types are generally recognizable until the particles become black and opaque. resulting in lower bitumen contents in the source. called vitrinite reflectance. Cracking often produces free radicals. which are unpaired electrons not yet involved in chemical honds. and which can be used to gauge the extent of molecular reorganization. is that some of the bitumen is expelled from the source rock or cracked to gas. Some of these are hydrocarbons. Bitumen generation occurs mainly during catagenesis. The difference between the two curves represents bitumen expelled from the rock or cracked to light hydrocarbons. somewhat beyond the oil-generation window. If neither expulsion from the source rock nor cracking of bitumen occurred. Kerogens.
Plot of bitumen generation as a function of maturity (dashed fine) compared to bitumen remaining in rock (solid line).22
between kerogen darkening and hydrocarbon generation. during metagenesis the chief product is methane. has been widely and successfully applied in assessing kerogen maturity. while others are small heterocompounds. Kerogens often fluoresce when irradiated. One property that is strongly affected. These small compounds are much more mobile than the kerogen molecules and are the direct precursors of oil and gas. These structural reorganizations bring about changes in physical properties of kerogens. and because vitrinite particles also occur in kerogens. and the less it will be reflected. Free-radical concentrations can be measured by electron-spin resonance. and no guarantee that a particular kerogen color always heralds the onset of oil generation. the technique. Both curves are highly
. Some properties of kerogen change very little during catagenesis. What actually occurs. carbon-isotopic compositions of kerogens are affected little by maturation. As kerogen matures and becomes more aromatic. its structure becomes more ordered. small molecules are broken off the kerogen matrix. The intensity and wavelength of the fluorescente are functions of kerogen maturity. because the flat aromatic sheets can stack neatly. Except for darkening. however.
residual kerogen as well as small molecules that are the direct precursors for petroleum and natural gas. Resinite and sulfur-rich kerogens are able to generate liquid hydrocarbons earlier than other kerogens because of the particular chemical reactions occurring in those two materials. Candidates for early expulsion would be very organic rich rocks and those containing resinite or high-sulfur kerogens. this result is hardly surprising. Sulfur-rich kerogens decompose easily because carbon-sulfur hbonds are weaker than any bonds in sulfur-poor kerogens. Given the significant chemical differences among the various types of kerogens. It has become apparent in recent years that not all kerogens generate hydrocarbons at the same catagenetic levels.23
Kerogen begins to form during early diagenesis. as measured by parameters such as vitrinite reflectance. although we know that oil generation does occur during the phase we call catagenesis. which in turn is partly attributed to hydrocarbon generation itself. Many workers now believe that microfracturing of source rocks is very important tor hydrocarbon expulsion. Several methods exist for estimating the extent to which hydrocarbon generation has occurred in a given kerogen. Thus. whereas those kerogens that contain few lipids will generate mainly gas. Microfracturing is related to overpressuring. those rocks that generate few hydrocarbons may not expel them until they have been cracked to gas. Effective generation of hydrocarbons requires that the generated products be expelled from the source-rock matrix and migrated to a trap. Other kerogens usually follow a more traditional model. because natural variations among samples cause much scatter in experimental data. however. Kerogens formed from resinite will generate condensates or light oils quite early. we cannot always define the limits of hydrocarbon generation with great confidence. when large geopolymers are created from biological molecules. The chemical composition and morphology of kerogen macerals depend both on the type of original organic matter and on diagenetic transformations. Timing and efficiency of expulsion depend on a number of factors. but none of these measurements is closely linked to the actual process of hydrocarbon generation. Kerogens formed from lipid-rich organic material are likely to generate liquid hydrocarbons. Resinite consists of polymerized terpanes (ten-carbon isoprenoids) that can decompose easily by reversing the polymerization process. 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. We shall consider the latter briefly here. Source rocks that generate large amounts of hydrocarbons early are likely to expel those hydrocarbons early. Numerous methods exist for tracing the history of a kerogen and determining its original chemical and physical characteristics. In such cases the expelled products will be mainly gas. high-sulfur oils at low levels of maturity. Conversely.Kerogen . High-sulfur kerogens generate heavy. hydrogen-poor. In very lean rocks expulsion may occur so late that cracking of the generated bitumen is competitive with expulsion.
. Rich rocks will become overpressured earlier than lean ones and thus will also expel hydrocarbons earlier. Catagenesis of kerogen produces a more aromatic.
Bitumen and petroleum compositions can also be used as tools in correlating samples with each other. A second fraction consists of aromatic hydrocarbons and some light sulfur-containing compounds. n-alkanes. The final fraction contains very large. Light aromatic hydrocarbons. and how much is due to physical separation of chemical compounds having very different properties. Asphaltenes tend to aggregate into stacks because of their planarity. The influence of the lithologies of source and reservoir rocks on these compositional changes is poorly understood. variously called polars. Saturated hydrocarbons are the most thoroughly studied of the components of petroleum and bitumen because they are the easiest to work with analytically. but these compounds are lost from bitumens during evaporation of the solvent used in extracting the bitumen from the rock. have been studied in petroleums. Heavier aromatic and naphthenoaromatic hydrocarbons. however.24
Bitumen. Major compositional changes occur in going from bitumen to petroleum. This chapter will compare and contrast bitumen and petroleum compositions and examine the factors responsible for the observed differences. Each of the fractions contains certain types of chemical compounds. and Natural Gas
Petroleum obtained from reservoir rocks and bitumen extracted from fine-grained rocks have many similarities.Bitumen. and form complexes with molecular weights of perhaps 50. Much of this variety is related to source-rock facies and the composition of the kerogens that generated the bitumens. The lighter of these fractions. Maturity also exerts control over bitumen and petroleum composition. In order to investigate the individual compounds present. many unanswered questions remain about the processes that transform bitumen into petroleum. and steranes.000. particularly those derived from diterpanes. However. Reservoir transformations in some cases greatly affect oil composition and properties. and Natural Gas -
COMPOUNDS PRESENT IN BITUMEN AND PETROLEUM GENERAL CLASSES OF COMPOUNDS
Both bitumen and petroleum contain a very large number of different chemical compounds. Some of these are present in relatively large quantities. but they also exhibit many important differences. like benzene and toluene. Petroleum. branched hydrocarbons (including isoprenoids). We also do not know how much of the change involves chemical reactions. In order to understand bitumen and petroleum compositions and to use them for exploration. The large sizes of asphaltene units render
. triterpanes. Few of these heterocompounds have been studied carefully. indeed. NSOs. 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. Petroleum. bitumen is almost universally accepted as the direct precursor for petroleum. but we are not certain whether they occur mainly within the source rock or during migration through the reservoir rock. we first separate a crude oil or a bitumen into several fractions having distinct properties. Most of the NSO compounds appear in the remaining two fractions. are more commonly studied. Both bitumens and petroleums exhibit a wide range of compositions. There is no doubt that they are related. One fraction consists mainly of saturated hydrocarbons. Such correlations can be particularly useful in establishing genetic relationships among samples. and cyclics. and resins. while others are only trace contributors. highly aromatic asphaltene molecules that are often rich in heteroatoms. contains a wide variety of small and medium-sized molecules with one or more heteroatoms.
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). asphaltene molecules have not been studied in detail. or CPI.) Even-carbon preferences occur principally in evaporitic and carbonate sediments. The most useful biomarkers serve as indicators of the organisms from which the bitumen or petroleum was derived. whereas in other instances we may be able to limit the possible precursors to only a few species. The distributions are quite sharp. we are unable to use it as an "index fossil" for specific organisms. of biological origin. For the most part n-alkanes present in terrestrial plants have odd numbers of carbon atoms. and by their catagenetic formation from long-chain compounds such as fatty acids and alcohols. CPI values can therefore
. or members of the n-alkane series. marine algae produce n-alkanes that have a maximum in their distribution at C-17 or C22. or of the diagenetic conditions under which the organic matter was buried. If odd-carbon homologs predominate. and no preference for either odd. because the concentration of n-alkanes often decreases with increasing carbon number. but their sources are simply no longer recognizable due to diagenetic and catagenetic transformations. although we know for certain that the biomarker molecule is biogenic. Their n-alkane distributions reflect this mix. If the number of odd. and 31 atoms. 25. even-carbon homologs predominate as strongly as do the oddcarbon homologs among the n-alkanes. the CPI is 1. the lower-carbon homologs are given more weight in the calculation. which are derived from biogenic precursor molecules. In contrast. 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.
FACTORS AFFECTING COMPOSITION OF BITUMEN AND PETROLEUM SOURCE AND DIAGENESIS
Biomarkers n-Alkanes were among the first biomarkers to be studied extensively. Because of their molecular complexity and heterogeneity. of course. Asphaltenes can thus be removed from oils or bitumens in the laboratory or refinery by adding a light hydrocarbon. Carbon Preference Index. and Natural Gas .or even-carbon homologs is evident. receive contributions of n-alkanes from both terrestrial and marine sources. 27. Sediments are also known that exhibit a strong preference for n-alkanes having an even number of carbon atoms. an abbreviation for biological markers. However. such as pentane or propane. however. The average of two ranges is taken to minimize bias produced by the generally decreasing n-alkane concentrations with increasing number of carbon atoms.25
them insoluble in light solvents. however. (Among the acids and alcohols present in living organisms.0.Bitumen. Petroleum. These compounds.0. Another important indication of the origin of n-alkanes is the distribution of individual homologs. especially 23. 29. are essentially molecular fossils. In a few cases specific precursor organisms or molecules can be identified. Many of the compounds and classes of compounds that we find in crude oils and bitumens are called biomarkers.
Biomarkers. Many sediments. In most cases. Other compounds. These n-alkanes are believed to be formed by hydrogenation (reduction) of longchain fatty acids and alcohols having even numbers of carbon atoms.and even-carbon members is equal. They are. depending upon the species present. the CPI is greater than 1. Their high concentration in bitumens and oils is best explained by their existence in plant and algal lipids. where input of terrestrial n-alkanes is minimal and diagenetic conditions are highly reducing.
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.
Bitumen, Petroleum, and Natural Gas -
Natural gas contains many different compounds, although most of them are present only in trace quantities. The principal components with which we shall be concerned are light hydrocarbons (methane through butanes), C02, H2S, and N2. Carbon dioxide and N2 are generally associated with very hot reservoirs. C02 is derived either by oxidation of oil or gas or by decomposition of carbonates. The origin of the C02 can be determined easily by carbon-isotope measurements: the very different isotopic compositions of organic-carbon species and carbonates are carried over into any C02 derived from these materials. Nitrogen is thought to be an indicator of high levels of maturity formed primarily by metagenetic transformation of organic nitrogen and ammonia bound to clay minerals. Hydrogen sulfide is usually derived from high-sulfur kerogens or oils. These in turn are formed most readily in carbonates. Thus sour gas is most common in carbonate reservoirs or in places where the source rock was a carbonate. H2S could also be formed by the reaction of hydrocarbons with sulfate in reservoirs, especially carbonates containing anhydrite. Biogenic gas, most of which occurs at shallow depths, but which can apparently form (or at least persist) at depths of a few thousand meters, is very dry, containing only trace amounts of hydrocarbons heavier than methane. In contrast, the first gas produced during catagenesis is quite wet. With increasing maturity, gas again becomes progressively drier as a result of cracking of the heavier hydrocarbons to methane.
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.
where they can be preserved over long periods of time. Primary migration is the first phase of the migration process. Each of these steps is quite distinct from the others. Many cycles of pressure buildup. and overpressuring commences anew. Momper (1978) suggested that in most cases no microfracturing or expulsion could occur until a threshold amount of bitumen had been generated in the source rock. Secondary migration is the movement of oil and gas within this carrier bed. Traps are the means by which migration is stopped and accumulation occurs. it involves expulsion of hydrocarbons from their fine-grained. Accumulation is the concentration of migrated hydrocarbons in a relatively immobile configuration. The hydrocarbons within the pores then become isolated again because of the impermeability of the waterwet source rocks to hydrocarbons. we must look at each of these steps separately.Migration . any contribution by diffusion will be overwhelmed by that from other expulsion mechanisms. Based on empirical evidence. The main problem with diffusion as an important mechanism of migration is that diffusion is by definition a dispersive force. expulsion. Diffusion has been shown to be active on at least a minor scale and over short distances in carefully studied cores. Today there are only three mechanisms of primary migration that are given serious consideration by most petroleum geochemists: diffusion. This chapter wi11 not go into the physics and chemistry of migration in detail. oil-phase expulsion. Once the internal pressure has returned to normal.29
6 . it is probably most effective in immature rocks. An important implication of the microfracturing model is that expulsion cannot take place until the strength of the source rock has been exceeded. Momper's value has been widely accepted as a reasonable average. By far the most popular mechanism invoked today to explain primary migration is expulsion of hydrocarbons in a hydrophobic (oily) phase. There appear to be three distinct ways in which oilphase expulsion can occur. particularly along lines of weakness such as bedding planes. whereas accumulation of hydrocarbons requires concentration. When the internal pressures exceed the strength of the rock.
PRIMARY MIGRATION MECHANISMS
Many theories about primary migration (expulsion) have been popular at various times. Laminated source rocks may therefore expel hydrocarbons with greater efficiency than massive rocks. and pressure release can be repeated. where pre-existing light hydrocarbons bleed out of the rocks prior to the onset of significant generation and expulsion. Its importance is probably limited to the edges of thick units or to thin source beds. the microfractures heal.Migration
Migration is the movement of oil and gas within the subsurface. and solution in gas. Furthermore. Diffusion would therefore have to be coupled with a powerful concentrating force to yield accumulations of appreciable size. In order to understand the complex sequence of events that we call migration. During intense hydrocarbon generation. but will describe the most widely held views on the dominant mechanisms of primary and secondary migration and accumulation.
. but those that have been discounted will not be discussed here. One occurs most commonly as a result of microfracturing induced by overpressuring during hydrocarbon generation. microfracturing. lowpermeability source rock into a carrier bed having much greater permeability. Although the exact threshold value must vary considerably as a function of rock lithology and other factors. microfracturing occurs.
Expulsion of hydrocarbons is facilitated because water-mineral and water-water interactions no longer need be overcome. Sand stringers within shale units can provide secondary migration conduits for hydrocarbons sourced in the shales." We can only estimate the fraction of the bitumen left in the source rock during microfractureinduced expulsion. A second way in which oil-phase expulsion can occur is from very organic-rich rocks prior to the onset of strong hydrocarbon generation. By comparing the average hydrocarbon compositions of bitumen and crude oil.30
Once the threshold has been exceeded. expulsion of oil dissolved in gas. Finally. but it does give some idea of the efficiency of expulsion.
. and assuming that expulsion of hydrocarbons is ten times as efficient as expulsion of NSO compounds. but a large proportion of NSO compounds and heavier hydrocarbons are left behind. Primary migration is difficult and slow. requires that there be a separate gas phase. This type of expulsion is probably only operative in very rich source rocks during the main phase of oil generation. upward. expulsion can be lateral. but the mechanism by which overpressuring is achieved is not understood. depending upon the carrier-bed characteristics of the surrounding rocks. therefore. we conclude that solution in gas is a minor mechanism for oil expulsion. Of course. In most cases the distances of primary migration are probably between 10 centimetres and 100 m. the migrating fluids will take them. primary migration may be of poor efficiency. hydrocarbons will be expelled in any direction that offers a lower pressure than that in the source rock. The organic matter expelled consists mainly of lipids that were present in the sediment during deposition and diagenesis. Because neither case is of great general significance for petroleum formation. Fracture and joint systems. oil-phase expulsion can take place when bitumen forms a continuous network that replaces water as the wetting agent in the source rock. Primary migration is unquestionably the most difficult part of the entire migration process. Massive. but also an "exit tax. most of the hydrocarbons are expelled. Because the source rock is overpressured. Thus a source rock lying between two sands will expel hydrocarbons into both carrier beds. In most cases hydrocarbons are generated within short distances of viable secondary-migration conduits. where they do exist. it would be expected only in the late stages of catagenesis or in source rocks capable of generating mainly gas. also make excellent secondary-migration pathways. we can estimate that once the expulsion threshold is reached the expulsion efficiency for bitumen is about 50%. This expulsion process probably releases internal pressures in the rock. or downward. Therefore the threshold must represent not only a hurdle to be cleared by the bitumen before it can leave the source rock. particularly in brittle carbonate and opal-chert source rocks. because petroleum is being forced through rocks having low matrix permeabilities. unfractured source-rock units are relatively rare. Because the driving force for microfracture-induced primary migration is pressure release. Thus inefficiency of expulsion is responsible for much of the difference in composition of bitumen and petroleum that we noted earlier. As soon as easier paths become available. Such a phase could only exist where the amount of gas far exceeds the amount of liquid hydrocarbons.
DISTANCE AND DIRECTION
The distances traversed by hydrocarbons during primary migration are short. Thus primary migration ends whenever a permeable conduit for secondary migration is reached. this early expulsion mechanism seems to be limited to rocks having very high original contents of lipids. Therefore. The third mechanism.Migration . this approach is rather approximate.
and becomes stuck until either the buoyant force or the capillary entry pressure changes. the more deformation is required.31
SECONDARY MIGRATION MECHANISM
Once hydrocarbons are expelled from the source rock in a separate hydrocarbon phase into a secondary-migration conduit. These modifications to the overall scheme are probably minor. migration may have to proceed at an oblique angle to structural contours. If. The upward buoyant force is partly or completely opposed by the capillary-entry pressure. Thus movement within a confined migration conduit will be updip perpendicular to structural contours whenever possible. Coalescence of globules of hydrocarbons after expulsion from the source rock therefore increases their ability to move upward through water-wet rocks. 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. if bulk water movement opposes the direction of buoyant movement. whereas capillary-entry pressure retards or stops it. then the rate of hydrocarbon movement should be enhanced somewhat. Within massive sandstone. and therefore are more buoyant. Structural contours on the top of the carrier bed will
. subsequent movement of the hydrocarbons will be driven by buoyancy. the force required to deform the oil globule enough to enter the pore throat.Migration .
Retardatin of buoyant movement as an oil globule (X) is deformed to fit in to a narrow pore throat (Y). Where faulting or facies changes create impassable barriers (capillary-entry pressure exceeds buoyant force). Hydrocarbons are almost all less dense than formation waters.
DISTANCE AND DIRECTION
Secondary migration occurs preferentially in the direction that offers the greatest buoyant advantage. the globule will squeeze into the pore throat and continue moving upward. A third force-namely. That is. the globule must deform to squeeze into the pore. then the rate of hydrocarbon transport will be retarded. The smaller the pore throat. If water is flowing in the subsurface in the same direction as hydrocarbons are moving by buoyancy. the pore throat is very tiny or if the buoyant force is small. This model is very simple. Buoyancy promotes migration. This fact has important implications for tracing migration pathways through a thick conduit. we say that accumulation has occurred.
Opposing the buoyancy is capillary-entry pressure. can modify hydrocarbon movement. Hydrocarbons are thus capable of displacing water downward and moving upward themselves. secondary migration will cease until either the capillary-entry pressure is reduced or the buoyant force is increased. Whenever a pore throat narrower than the globule is encountered. In contrast. however. secondary migration will occur both laterally and vertically. requiring only the existence of two forces. which is resistance to entry of the hydrocarbon globule or stringer into pore throats. hydrocarbons entering the land from an underlying source rock will move toward the top of the sand even as they migrate laterally updip. the globule cannot enter. If the capillary-entry pressure exceeds the buoyant force. hydrodynamic flow. If the upward force of buoyancy is large enough. When hydrocarbons cease moving. but it is not essential and does not change our basic model.
at which time they suddenly became immiscible with the water and formed a separate hydrocarbon phase. The question of long-distance migration has been much discussed and disputed. The absence of both tectonic and stratigraphic barriers permits long-distance migration. Cap rocks having low
. This model greatly simplifies the problem of accumulation.Migration . leading to smaller fault-bounded accumulations and vertical migration. Unconformities also can juxtapose migration conduits. Vertical migration across stratigraphic boundaries is more difficult. not only because they often juxtapose carrier beds from different stratigraphic horizons. large drainage areas and chances for very large accumulations. as a result of both tectonic disruption and facies changes related to tectonic events. for example. because final control on migration direction will be exerted by the upper part of the bed (assuming that no laterally continuous shale breaks divide the carrier bed into two or more separate systems). Drainage area is one of the most important factors influencing the size of hydrocarbon accumulations. Hydrocarbons had to remain in solution until they reached the trap. the heavy oils in the Orinoco Belt of Venezuela. thus providing a potentially very effective system for combined vertical and lateral migration. and the Saudi Arabian crude oils. and has provided as carrier beds continuous blankets of sand juxtaposed with these source rocks. Indeed. because now accumulation can occur where the buoyancy-driven movement of the hydrocarbon phase is stopped or even strongly impeded. although it should be remembered that there are two fundamentally different types of vertical migration.32
in general be more useful than contours on its base. otherwise it is impossible to account for the incredible volumes of hydrocarbons in place today. are basins in which lateral migration distances do not exceed a few tens of kilometers. Vertical migration distances can also be considerable. Lateral migration is therefore often stymied. Migration updip within a single stratum can accomplish a large amount of "vertical" migration rather painlessly. However. It is possible to have lateral migrations of as much as a few hundred kilometers in exceptional circumstances. by definition. There is no a priori reason why secondary migration cannot be a very-long-distance phenomenon. Much more common. however. Lack of long-distance migration opportunities implies that supergiant and giant accumulations are far less likely and that exploration targets will be smaller. when migration was thought to occur mainly in water solution. Various mechanisms for exsolution were proposed to explain how all this was supposed to happen. The problem in discussing long-distance migration is that such cases are rare.
In the old days. but also because an active fault or the brecciated zone adjacent to a fault may itself have high permeability. the process of hydrocarbon accumulation was somewhat mystical. Faults may play an important role in vertical migration. Long-distance migration implies. can offer possible pathways (although sometimes rather tortuous ones) for vertical migration. distances of several thousand feet are not unheard of. Most basins. Nevertheless. Today we believe that hydrocarbons migrate as a separate phase. 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. are broken up tectonically and have poor lateral continuity of carrier beds. Vertical migration can also occur across formations. however. all must have migrated long distances. the largest hydrocarbon deposits known. Stacked sands in a paleodelta. including the Athabasca Tar Sands of western Canada.
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. 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. The low permeability sand thus creates a bottleneck to gas migration. The seal prevents vertical migration from the reservoir rock into overlying strata. Because the high permeability sand updip allows gas to migrate rapidly through. Thus the Elmworth Field exhibits a water-over-gas contact. The simple principle behind a kinetic trap is that hydrocarbons are supplied to the trap faster than they can leak away. Gas generated in the late stages of kerogen catagenesis in the Alberta Deep Basin is trapped in a sandstone bed having lower permeability than the overlying sand. and will be covered separately. Because gas generation is very rapid.
Most hydrocarbon traps are either structural or stratigraphic. The Elmworth Field in the Alberta Deep Basin of Canada is the prototype for kinetic gas accumulations.Migration .
Cross section across the Rhine Graben of West Germany showing the discontinuity of strata as a result of extensional tectonism endemic to rift basins. Accumulations are small because drainage areas are small. This model requires. No traditional seal exists.
. of course. Lateral migration is of necessity short distance.33
permeabilities to hydrocarbons provide barriers to migration: that is. rocks whose capillary-entry pressures are high enough to overcome hydrocarbon buoyancy. it remains water wet.
CLASSICAL TRAPS. Seals in the traditional sense of the word may not exist. a fractured shale that is both source and reservoir. The much smaller Antelope Field produces from the Mississippian Bakken Formation. Gas production is actually from the low-permeability sand rather than from the high-permeability sand updip and downdip.
Kinetic traps represent a fundamentally new concept in trapping mechanisms for hydrocarbons. Classical traps are well understood. the low-permeability sands become filled with gas. while the structure or lithologic change prevents lateral updip migration. Fracturing associated with high races of oil generation in the Green River Shale has created a supergiant accumulation at Altamont. and vertical migration becomes important.
The polar molecules once again interact most strongly with interstitial water and mineral surfaces.
EFFECTS ON OIL AND GAS COMPOSITION
It has already been suggested that most of the compositional changes seen between bitumens and normal crude oils occur during expulsion (primary migration) from the source rock. Once expulsion has occurred.
Formation of crystalline hydrates of natural gas provides an extremely efficient trapping mechanism for natural gas. A second characteristic is that gas hydrates form effective seals against vertical hydrocarbon migration. and thus get left behind as the oil globule or stringer moves upward. The base of the gas hydrate zone forms a pronounced seismic reflector that often simulates bottom contours and cuts across bedding planes. and would be incapable of sealing accumulations for long geologic periods. there may be a chromatographic effect during secondary migration. These gas hydrates consist of a rigid lattice of water molecules that form a cage within which a single molecule of gas is trapped. unconsolidated sediments that would have no other means of retaining the methane. The polar (NSO) compounds interact most strongly with both mineral surfaces and water molecules. but in the future gas-hydrate accumulations may be of great economic significance.Migration . however. 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. but it may also include some heavier hydrocarbons dissolved in the gas. Methane is by far the most commonly trapped gas molecule. Phase changes occur as a result of decreases in pressure and temperature during migration. One important feature of methane hydrates is that they are much more efficient at storing methane than is liquid pore water. because the same conditions that created the tar mat persist in the subsurface. and thus are not expelled as efficiently with the oil phase.34
Many of the accumulations in Pliocene reservoirs in southern California are also kinetic accumulations in a slightly different sense. but hydrates large enough to accommodate butane molecules are known. these changes in temperature and pressure can cause separation of the original phase into a liquid phase and a gas phase. contain mainly light components. Because hydrate zones are often hundreds of meters thick. tar-mat traps are worth discussing because they include the largest hydrocarbon accumulations known: those of the Athabasca Tar Sands and the Orinoco heavy-oil belt. The technology necessary for producing these hydrocarbons has not yet been developed. Formation of hydrates thus provides an important trapping mechanism. tar mats may provide the only possible means for retaining any hydrocarbons.
Tar mats produced by biodegradation can create excellent seals. As soon as two immiscible phases are formed. large accumulations have formed despite high rates of leakage. It will therefore migrate much faster and
. When the original hydrocarbon phase contains large amounts of light components. of course. Accumulations beneath tar-mat seals are generally biodegraded themselves. the quantities of gas in such accumulations are huge. 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. because much of the methane trapped is biogenic and was formed in young. The gas phase will. the lighter (gas) phase will be far more buoyant than the liquid phase. Despite the rarity of tar-mat seals. and in zones of permafrost. Because intense oil generation is going on now. Cap-rocks in those fields are often poor. In cases where no other structural or stratigraphic trapping mechanism exists. especially methane.
the efficiency of expulsion. In using our understanding of secondary migration for exploration. and how far they moved.35
will also assume the structurally high position in any reservoirs containing both phases. Proximity to effective source rocks and their permeabilities to hydrocarbons determine conduits. leading to an enrichment of hydrocarbons in the expelled liquid. We have already stated that oil is expelled primarily as a liquid phase.
SIGNIFICANCE FOR EXPLORATION
Explorationists who are reading about migration will surely ask. we want to determine the main pathways and conduite through which migration occurs. gas is presumably expelled as a gas phase.
. When separation of a single hydrocarbon phase into two phases occurs. Efficiency of expulsion of liquids has already been estimated to be in the neighbourhood of 50% after the expulsion threshold has been reached. Lateralmigration distances are strongly influenced by tectonic and depositional histories of basins. we will also have determined the timing of expulsion. by faulting. both new phases will have compositions that differ drastically from the original phase. In summary. depending upon stacking of reservoirs. Many light oils (often called condensates) probably have such an origin
Proposed separation of petroleum components during secondary migration as a result of chromatographic effects. Pathways. as we have seen. and the vertical and horizontal distances involved. vertical faulting. in what direction they moved. We need to know when hydrocarbons moved. and expulsion occurs concurrently with generation to relieve generation-induced overpressuring. Efficiency of expulsion for hydrocarbons is apparently much higher than for NSO compounds. Vertical-migration distances can be considerable. and the possibilities of combined vertical and lateral migration. by decreases in permeability as a result of facies changes. We already know two important facts about timing from our previous discussion: expulsion based on microfracturing cannot occur before generation. Thus if we can determine the timing of generation. Unstable basins seldom have depositional or tectonic continuities necessary for longdistance lateral migration to occur. Tectonically stable basins have the best potential for long-distance migration and supergiant accumulations. and the timing of expulsion. are determined by structural contours on the top of the carrier beds. Polar compounds interact more strongly with water and rock minerals and thus move more slowly than hydrocarbons. Timing of expulsion must be dealt with in a different way. Barriers can be created by folding. the barriers that modify die direction of migration and eventually stop it. "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). as explorationists we have very pragmatic interests in migration. or by the presence of tars.Migration .
we need a few definitions. To complement the structure contour map. 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. but there must also be some sort of blockage to prevent further migration. The highest point of the reservoir. but it is often convenient to exaggerate the vertical to show the individual beds more clearly. If then we are to find any of it still preserved. is the spill-point: this is where oil. The top of a reservoir formation. These are illustrated using a simple anticline as an example. Such a configuration of the reservoir is known as a trap. by displacing the water already there in the porosity. before we reached our modern understanding of the geology of petroleum. they should properly be drawn with the same scale for both the vertical and the horizontal.Petroleum Traps
We have seen petroleum generated in and expelled from the source rock formation into an overlying or underlying reservoir. is mapped by contours showing depth below sealevel. Any oil getting there will be unable to migrate further and so it starts to accumulate. A structure contour map resembles an ordinary topographic contour map.Petroleum Traps . is known as the crest of the trap. Note that we commonly highlight petroleum accumulations by shading or colouring the reservoir formations where they contain oil or gas. If it can. The location of a trap in the subsurface is often the first objective of an exploration program. The lowest point. Faults will be marked by jumps of the contours. exploration used to consist largely of finding a trap. up towards the ground surface. which may give a misleading impression of `lakes' of
petroleum under the ground!
Structure contour maps. The contours are in feet below mean sea-level. if more continues to migrate up into the trap than can be
. one or more cross-sections may be drawn. they can be mapped by means of contours drawn on the top of the reservoir formation. Nowadays we can do better. (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. First. where it is lost. the ticks are on the downthrown sides of the faults. except that the contours are in depth below sealevel. To give a true representation. This may be caused either by the reservoir itself dying out or by an interruption of its upwards continuity to the surface.(2-18)
Before we go further.36
7 . Indeed. it will escape to surface as a seepage. and hoping for the best. as the beds on one side are dropped down relative to the other. so that the highest points on the map have the lowest values. (a) A simple hypothetical anticline. drilling a well into it.
THE REPRESENTATION OF TRAPS
Traps are commonly depicted in two ways. 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). which may refer either to its depth or to the spot under the ground where it lies.
which are rare and are mentioned mainly for completeness. Oil being lighter than water.e. i. separates out on top within the pore-spaces of the reservoir. or in their layering. using a cross-section of a simple anticline as example (2-19).37
accommodated. they are embraced by the familiar terms oilfield or gasfield. however. They are normally classified under four headings (2-21):
1. and the same term is used loosely to refer to the area of the trap above the level of the spill-point. 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. 2. Combination traps. in which the trap is formed by changes in the nature of the rocks themselves. being lighter still. Structural. Where there is more than one such pool in the same or overlapping areas. 3. When referring to a single well. either by folding or faulting. Let us remember. Stratigraphic. so that we can recognize a generally horizontal oil-water contact. perhaps if more than one reservoir is present. there are various types of
. the only structural effect being a tilt to allow the oil to migrate through the reservoir. If there is no oil.(or gas-) column. will spill out (under) and migrate on.
Some terms used to define a trap. However. Similarly gas.
The best known type of trap is the anticline: on reaching the crest. but not entirely due to either.
Now we can start to consider the types of trap whose discovery may await us. which have porosities and permeabilities too low for them to contribute oil to production. the informal term pay is often used. will occur as a gas cap above a gas-oil contact. 4. Just a couple more terms. The vertical height between the spill-point and the crest is referred to as the closure. that most reservoir formations include some tight intervals. formed partly by structural and partly by stratigraphic effects.Petroleum Traps . The trap is due to water flowing through the reservoir and holding the oil in places where it would not otherwise be trapped. petroleum migrating up along a reservoir can go no further and it accumulates there as a pool. Hydrodynamic traps. A single accumulation of oil or gas is called a pool. where the trap has been produced by deformation of the beds after they were deposited. The vertical height of the oil (or gas) between the crest of the trap and the water contact is the oil. then we may see a gas-water contact.
we have to know its depth to know where best to locate the well. therefore in order to drill into a reservoir near its highest point (where we would expect the oil to be). on the other hand. but an understanding of the shape and size of a prospect is clearly critical to programming an exploration well. many structures have forms in-between the two extremes. Seismic may help. To test the crest at depth. we can find the trap present at all levels down to the basement. This can only happen if there is an apparent thickening of some beds over the crest of the fold. Compressive structures have a range of shapes between the purely concentric or parallel anticline and the similar fold. with one flank steeper than the other. the anticline is asymmetrical. This leads us into the next problem. In this case. Below this point we have just too much rock to fit into the anticline. Other types of anticline can be formed without any lateral compression at all: an important one is the drape or drape-compaction structure. (a) The dips are the same on both flanks and the crest is beneath the same locality at all depths. (b) The anticline is asymmetrical and the crest shifts with increasing depth. In this type of structure. in cross-section. maintains its shape constant down to depth. but we commonly have to undertake some form of geometrical construction to interpret what is happening at depth. These compressive structures pose one problem right from the start. Anticlines. then the position of the crest will shift with increasing depth.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. If. Traps can also be formed against faults if a chopped-off reservoir is thrown against a shale or other impervious rock. We will describe in a little detail the most important types of anticline. Let us see what the implications are for exploration. so that the beds become intensely crushed and thrust together: we may no longer even have an anticline at all. so that the beds maintain a constant thickness throughout. a well would have to be located off-crest at surface. noting the differences in shape and prospectivity that we have to try to interpret. There is a definite limit to the depths to which we should drill. we can thus expect to find only smaller and smaller accumulations of petroleum down to the centre of curvature. This is a very different kettle of fish from the concentric anticline. and the blanket bulges upwards with an anticlinal shape. Imagine an old-fashioned stone hot-water bottle in a bed with a blanket over it: we can still see the form of the hot-water bottle. and we may be able to continue exploration down to depths where we have to stop for other reasons. The general principles of this are straightforward.
. depending on the nature and strength of the rock layers being folded.(2-22)
In the concentric fold the tops and bottoms of all the layers remain strictly parallel to each other.
Cross-sections of trap-forming anticlines. beyond which there may be no trap left to explore as the consequence of decoupling of layers. and we may no longer be able to see where the bottle is.Petroleum Traps . In practice. The similar anticline. Cover it with a few more blankets and a duvet or two. These conditions mean that the anticline becomes smaller and tighter at deeper levels until we reach a common `centre of curvature'.
bending downwards into the hole. higher beds will gradually mute and suppress the structure until it is no longer present at shallow levels. showing the variety of traps that may be associated with them. it is also liable to fracture the overlying and surrounding beds creating fault traps. The effect of salt diapirism will be initially to bulge up the overlying sediments as an anticline. can be a perfect seal to any underlying accumulations. does not like empty holes. In case anyone should think that this is unimportant. and several others. a salt pillow or a salt dome. note that the largest oilfield in the world. Nature. is in one such trap. Another is the Forties field in the North Sea. where the beds are draped over the eroded stumps of an old Jurassic volcano. and hence the combined name. Not only may an anticline be pushed up over the plug.Petroleum Traps . it is not always easy to separate out the two effects. the Middle East. Ghawar in Saudi Arabia. Note that the anticline dies out upwards towards the surface. it may bend up and seal off the strata it cuts through. 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. it may extend up to the surface of the ground or only part way if the supply of salt is limited. A second effect comes into play here: because there is a greater thickness of beds off the structure than over the top. much of the west coast and continental shelf of Africa. All of these possible traps may contain hydrocarbons.(2-26)
A wide variety of traps can be associated with salt plugs. the beds being draped over an upfaulted block (horst) of basement rocks. Note also that salt. then they will blanket the hill as an anticline. The last type of anticline that we should be aware of is the roll-over anticline. if the first sediments in a basin were deposited over a hilly surface. This occurs alongside a normal fault that is curved. and finally a residual bulge may be left between two nearby plugs: a turtle or turtle-back structure. and the beds on the downthrown side above the curving fault collapse to fill the gap. so that it is steep near the surface and flattens with depth. the Gulf Coast of the USA. the Canadian Arctic Islands. This compaction enhances the anticline formed by the drape. but also
. Note a characteristic of these anticlines: not only do they `grow' with depth. In effect the downthrown side is being pulled away from the upthrown side which would tend to create an open fissure along the fault. being plastic. however. or over an upfaulted block or horst. which contains more than four times as much oil as the whole of the North Sea put together.
Diagrammatic section through two salt plugs. Extensive salt deposits and plugs with associated traps occur in many parts of the world: the southern North Sea and northern Germany. This creates a rollover anticline. and then to burst through them in the form of a salt plug or salt wall.(2-25)
A drape-compaction anticline.
The sealing capacity of faults is a major difficulty confronting us. trapped against faults to the south. Tertiary. It adds further uncertainties to our predictions of the subsurface occurrence of oil and gas. or have acted in the past. a fault can provide a seal. Lower Cretaceous.Petroleum Traps . we still do not fully understand what the difference is due to. down towards the deep ocean.
. The reader may care to think through the various situations sketched as bits of cross-sections in the following figure in which the faults themselves are non-sealing. to locate an exploration well in the right place. therefore. whether the fault is normal or reverse.
Tr. BS+MJ+O. The proviso is that we also have lateral closure: this may be provided by further faulting. Upper Jurassic. Lower Jurassic. The oil is in two reservoirs.40
they are asymmetrical. we have to know whereabouts in the succession our prospective reservoir lies. UK.
Cross-section through the Wytch Farm oilfield. these predated the deposition of the Upper Cretaceous. and in understanding them. but we also know that sometimes faults are pathways for migrating petroleum and non-sealing at all. setting it against something impermeable. We know that sometimes.
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. Whether or not there is a trap. Upper Cretaceous.. The large Wytch Farm oilfield of southern England offers a splendid example. T. will depend on the dip of the reservoir as compared with that of the fault. the position of the crest is displaced with depth and that accumulations in successive reservoirs will not underlie the same surface position. Kim+P. although there are many problems in trying to locate them in the subsurface. Fault traps We indicated above that a trap may be formed where a dipping reservoir is cut off up-dip by a fault. Much of the oil under the Niger and Mississippi Deltas is in such roll-over anticlines. Middle Jurassic. Again. at deeper levels the crest will shift away from the position of the fault at surface. as at Wytch Farm. and naturally we have some ideas on the subject. in both ways. It also depends on whether the fault itself is sealing or non-sealing. and how big it is. Occasionally indeed. in both cases. All very puzzling! Although attempts have been made to investigate the problem in Nigeria and elsewhere. thus causing sand against sand to permit migration and sand against shale to be sealing.
Roll-over anticlines: (A) a simple roll-over into a normal fault. Triassic. southern England. L. W. (2-28)
We do not propose to discuss fault traps in detail. whether or not the reservoir is completely or only partially offset. it seems that one and the same fault may act. Note that. and it will depend on the amount of displacement on the fault. or by opposing dips. and its depth. or slumping as a sort of land-slide. (B) a roll-over complicated by subsidiary faulting near the crest.
We mention just three examples. fan sands provide one of the prime present-day exploration
. A lot of oil has been found in recent years in this sort of trap in the North Sea. Non-unconformity traps are even more diverse. A dipping reservoir. depending on whether the fault is normal or reverse. strongly weathered basement rock (granites. will spread out as a fan over the ocean floor. to provide a trap when later covered with. First. so we will mention a few to convey the general idea. possibly through a submarine canyon.(2-29)
Petroleum may be trapped where the reservoir itself is cut off up-dip. if terminated updip as not infrequently happens. say. but are generally classified as stratigraphic traps. on the direction of dip of the beds relative to the fault plane. the beach sands will spread progressively over the land surface. let us note that a number of traps. to a large extent reflecting the restricted environments in which the reservoir rocks were deposited. Unconformity traps can also be found above the break.Petroleum Traps . a hill on the old land surface may be formed of permeable rock. if drowned by shales. Consider the sea gradually encroaching over the land as sea level rises. and on the amount of displacement of the reservoir. More esoterically. A sand deposited in a river channel will be confined by the banks and. may serve as an isolated stratigraphic trap. however. thus preventing further migration. and leave the reader to speculate on other possibilities. A flood of sand washed off the shallow continental shelf into the deeper ocean. they differ somewhat in principle from the others. A coral reef overwhelmed by muds. becoming younger as time goes on. gneisses) under an unconformity serve as reservoirs in China and North Africa.41
Six trapping and two non-trapping configurations against a fault. is the biggest in the USA outside Alaska. no structural control is needed. its edges will provide an example of a reservoir dying out laterally. for example. In this manner. the porosity could be preserved beneath the unconformity. cut across by erosion and later covered above the unconformity by impermeable sediments. until perhaps the supply of sand runs out. are formed by unconformities. some of them very important. provides the classic case: the East Texas field. claystone. In fact. It is presumed that petroleum cannot escape up the fault plane. but nevertheless known. The variety in size and shape of such traps is enormous. It would be pointless to list all of the possible types of stratigraphic trap that can exist. We would be left with a sandstone reservoir dying out above the unconformity. we have an isolated trapping situation.
has most of its oil and gas trapped in a Carboniferous to Jurassic sequence which includes more than one reservoir. and truncated by erosion. The difference is believed to be due to clay being smeared into the fault plane. A couple of examples may give the idea. although such prospects are not easy to locate and may require a lot of sophisticated seismic. tilted westwards.(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. where the reservoirs overlie overpressured shales.
An investigation into the sealing qualities of faults affecting roll-over anticlines in the Niger Delta. it is presumed that the fault is non-sealing. these beds were folded into a faulted east-west anticline. We may note here one most important consideration. as the fault moved. The oil is held in the reservoirs by younger shales overlying the erosion surface (Fig.(230)
A number of fields.42
targets. The reservoir beds were folded into an anticline. there always seems to be something new as a challenge. where there is enough of it in the section. that the trap must be shown to have been there before the oil migrated.). some of them large. elsewhere it appears to form a trap.
A block representation of the trap at the Prudhoe Bay field in northern Alaska. which was tilted west and eroded before deposition of the overlying beds now dipping east. neither completely controls the trap. The oil in these fields can only have migrated there after the traps were sealed by the higher sequences. This combination trap is partly structural (the anticline) and partly stratigraphic (beneath the unconformity). occur in traps formed by a combination of structural and stratigraphic circumstances. Where a reservoir is full to spillpoint against a fault. the biggest field in the USA.Petroleum Traps . or the oil would have been lost. This vital factor. Both the faulting and the unconformity control the traps. possibly even before it
. and where an oil-water contact is continuous across a fault. As the more easily found structural traps are running out in much of the world. The Prudhoe Bay field in northern Alaska. Again the range of possibilities is almost infinite. which were eroded and unconformably overlain by Cretaceous shales.
was generated. Oil. The timing of trap formation versus oil migration has not always worked out favorably. We would recognize this from residual traces of oil in a water-bearing reservoir. they are known in a number of parts of the world. only for as long as the water keeps coming: dry up the supply of water. in say ordinary anticlinal traps. cases are known where flowing water has apparently been able totally to flush oil out of an anticlinal trap. The number of structural field of this size may partly reflect the fact that structural traps are easier to find than the others. It is therefore always important to get a handle on the hydrodynamic regime in a reservoir for both exploration and oilfield development purposes. It is totally dependent on the flow of water and is effective. The trouble. There is no structural or stratigraphic closure. The oil-water contact in such a hydrodynamic trap is normally tilted in the direction of water flow. we would have to be careful where we locate and drill our oil production wells. are the more obscure and generally smaller prospects. traps in both number and size. up in the hills and percolating downwards towards a spring. geologically speaking. Furthermore. it may find itself caught against an unevenness of the reservoir surface where there is no conventional trap at all. attempting to escape to surface up a reservoir.
Imagine surface water. a regime of water flow cannot normally be expected to remain constant for long.
. as we do not want to waste the money drilling wells that would miss the oil altogether. therefore. are not all that rare.Petroleum Traps .
A hydrodynamic trap. from our present-day point of view. but the oil reserves they contain show clearly that generally they are also bigger. Oil has found its way into the reservoir and is battling to migrate upwards to the surface against the flow of water. and the oil will be free to move again. What our efforts are increasingly directed towards. is that in most parts of the world the larger anticlines have now been drilled. Note that the oil-water contact is tilted down in the direction of water flow. of course. entering a reservoir formation. perhaps from rain. essentially anticlinal. or aquifer. Depending on the balance of forces acting on the oil. In this sort of situation. Such tilted contacts. is held against an unevenness of its upper surface by water flowing in the opposite direction.(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 is what has been described as a hydrodynamic trap. This may be one of the reasons why oil accumulations trapped hydrodynamically are rare. indicating the former presence of an oil accumulation now lost. is yet another aspect of the petroleum geology that we have to assess in proposing exploration drilling.
The logs show SP (Self Potential or Spontaneous Potential) on the left and R (Resistivity) on the right.45
EXERCISES EXERCISE 1: The following well logs have been hung on a structural datum.
.Make the interpretations from easy (A) to more difficult. multi-interpretable (D). Interpret the geological relationships shown in each by drawing a
structural cross-section through the logs.Petroleum Traps .
produces from Onondaga Limestone and/or Oriskany Sandstone.Petroleum Traps . Wyckoff Reef Gas Field WellElevation
CORNELL DIBBLE GUILD CHASE BANKS RICHARDS 2257' 2098' 2037' 2206' 2182' 2066'
EXERCISE PetroleumTraps 2 The Wyckoff Gas Field. showing the interval from top of Onondaga to bottom of Oriskany. Oriskany production is from a small anticline on the upthrown side of the fault. N. Elevations and marked logs are provided for 6 wells in the Wyckoff Field.. The Onondaga forms a thick biohermal reef over part of the field. A deep-seated downto-the-southwest fault extends upward along the southwest flank of the reef.Y. located in Steuben County. Only the porous core facies is productive in the reef section (see map on next page). Use this information to construct a northeastsouthwest structural cross section from the Richards well to the Dibble well.
Petroleum Traps .47
Petroleum Traps .48
in which case virtually all the initial
DEFINITION OF SOURCE ROCK
Much of modern petroleum geochemistry depends upon accurate assessment of the hydrocarbonsource capabilities of sedimentary rocks. but if the rocks contain abundant organic matter. quick. instead it must be estimated by measuring G for a similar sample that is still immature. Although the term source rock is frequently used generically to describe fine-grained sedimentary rocks. The quantity actually measured in the laboratory is always G. but which may have generated and expelled hydrocarbons. The difference between Go and G represents the hydrocarbons already generated in the effective source rock. For better communication.. if G is very low. much smaller amounts can be analyzed.49
8 . However. a possible source rock in a nearby unstudied region. 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. Go can only be measured directly for immature source rocks.
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 following distinctions can be made: Effective source rock: any sedimentary rock that has already generated and expelled hydrocarbons. the Phosphoria Formation of Wyoming and Idaho belongs to each of these classifications in different areas. we actually measure its remaining (or untapped) source capacity at the present day. is it because the rock never had a high initial source capacity. This simple. It follows from these definitions that a particular stratum could be an effective source rock in one place. a potential source rock in a less-mature area. and inexpensive analysis serves as the first and most important screening technique in source-rock analysis. the remaining source capacity and not the original capacity (Go). The term "effective source rock" obviously encompasses a wide range of generative histories from earliest maturity to overmaturity. 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.
MATURITY OF ORGANIC MATERIAL
Knowing a rock's remaining source capacity G solves only one part of the puzzle. For example. For example. we cannot measure G directly for a sample that has already begun to generate hydrocarbons. Analysis normally requires about one gram of rock. overmature. that usage is a bit too broad and loose. This quantity.e. is most meaningful if we can compare it to the rock's original source capacity. Go. Possible source rock: any sedimentary rock whose source potential has not yet been evaluated. or is it because the rock is "burned out" (i. which we can call G.Source Rock Evaluation . where G and Go are identical.
in fact. In all cases it is worthwhile to supplement vitrinite with other measures of maturity. Vitrinite reflectance (Ro). leading to frequent difficulties in establishing which vitrinite population is indigenous. and then embedding the kerogen particles in an epoxy plug. All the methods have strengths and weaknesses. and pyrolysis temperature. the reflectance value of vitrinite increases. its maturity is not related to that of the rock in which it is found. 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. whenever possible. All the techniques discussed are useful and probably reasonably accurate if the analytical work is carefully done. the plot is a straight line.50
hydrocarbon-source capacity has already been used up)? The exploration implications of these two scenarios are. of course. where the o indicates that the measurements were made with the plug immersed in oil. unless surrounding samples help us determine the indigenous vitrinite population. The most commonly used maturity parameters today are spore color (Thermal Alteration Index. In many areas it is easy to use and valuable.
. far more common in shales than in coals. The method is based on the fact that with increasing thermal stress. The darkening of kerogen particles with increasing thermal maturity can be used as an indicator of maturity. Thermal Alteration Index (TAI). TAI measurements are carried out on bisaccate pollen grains whenever possible. In many rocks vitrinite is rare or absent. in some cases it is essential. along with a statistical analysis of the data.Source Rock Evaluation . vitrinite reflectance is the most popular technique today for estimating kerogen maturity. Despite its weaknesses. Less commonly used are fluorescence and conodont color (CAI). misidentification of macerals can cause problems. however. Vitrinite-reflectance measurements begin by isolating the kerogen with HCl and HF. 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. If a log scale is used for the reflectance. A few of these parameters will briefly be discussed. Because what is present is often reworked. the microscopist shines light on an individual vitrinite particle. or TAI). even for experienced workers. Results are reported as Ro values. TAI values are estimated. If enough vitrinite particles can be found. Reworked vitrinite is. If no pollen can be found. in obtaining more than one maturity parameter. Because each maceral type increases in reflectance in a slightly different way as thermal stress increases. The fraction of the incident beam that is reflected coherently is measured and recorded and stored automatically on a computer. from amorphous kerogen. In order to minimize differences in color caused by changes in the type or thickness of the kerogen particles. between 50 and 100 measurements will be taken. There are many problems with vitrinite reflectance as applied to kerogens. A substantial number of techniques for measuring or estimating kerogen maturity have been developed over the years. with lower confidence. Vitrinite-reflectance techniques were developed for measuring the rank of coals. very different. Such histograms are quite often difficult or impossible to interpret. The ideal histogram of reflectance values is therefore rather rare. and none can be applied in all cases. TAI measurements are made on the same slides prepared for microscopic kerogen-type analysis. The feeling of most workers today is that there is no single maturity indicator that tells the whole story unerringly all the rime. Other macerals or solidified bitumens can often be misidentified as vitrinite. in which the vitrinite maceral is usually very common. vitrinite reflectance. After the plug is polished. Reflectance values are normally plotted versus depth in a well. In other rocks. The key to using maturity parameters effectively lies in evaluating the measured data carefully (and sometimes with skepticism) and.
changes in conodont color are apparently due to carbonization of inclusions of small amounts of organic matter during catagenesis and metagenesis.
Conodont Alteration Index (CAI). The first maturity indicator applied to sediments was the Carbon Preference Index. and thus are of no value in many areas. Although TAI determinations are subjective. and thus helps expand the range over which maturities can be measured. A careful worker can reproduce earlier work with excellent precision. leading to an inaccurate assessment of kerogen maturity. Early investigations showed that immature rocks often had high CPI
Each laboratory has reference slides so that microscopists can continually compare the color determinations they are now making with those they and their colleagues made in the past. where most of the interest is. use of careful standards and the same type of palynomorph in each analysis greatly aid reproducibility. Carbon Preference Index (CPI). TAI values estimated from amorphous material are always suspect and should be corroborated by other analyses. they offer a means of measuring maturity in rocks that do not contain pollen grains or vitrinite. CAI is only an indirect indicator of hydrocarbon maturity. Conodonts are isolated. CAI is inexpensive and easy to measure and. the absence of spores and pollen in the samples. When palynomorphs are absent. Although conodonts are composed of carbonate apatite. Conodonts do not occur in rocks younger than the Triassic. most commonly from fossiliferous carbonates. One disadvantage of CAI measurements is that CAI values can be dramatically increased in the presence of hot brines. Other disadvantages overlap with some of the advantages. TAI measurements are therefore often quite accurate and correlate very well with results from other techniques. Finally. Thirdly. 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. The chief problems arise with inexperienced workers. because the organic metamorphism displayed by conodonts is not related to hydrocarbon generation or destruction. Colors of the specimens thus obtained are determined under a binocular microscope and compared with standards.Source Rock Evaluation . One advantage of CAI over other maturity parameters is that because conodonts existed as early as the Cambrian. lack of proper standardization. TAI values must be estimated from amorphous debris. or most commonly. Furthermore. with the help of color charts can be carried out by inexperienced personnel. conodonts are plentiful in carbonate rocks. where pollen and vitrinite are often absent. The technique is simple and quick and can be done even by inexperienced workers. Finally. by removing the mineral matrix with acetic or formic acid. which can vary greatly in its chemical and physical properties. Conodonts are not very sensitive indicators of maturity within the oil generation window.
It breaks down at high maturity levels. 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. atomic H/C ratios measure the present day status of the kerogen rather than its original chemical composition. Hydrocarbon contamination is rare except in the immediate vicinity of production or where vehicles are used. and lignite from lignosulfonates. Like pyrolysis. This method works fairly well if the kerogen is still within the oil-generation window. therefore. and therefore should be easy to avoid. Contaminants of particular notoriety are diesel fuel. of course.5%. fewer CPI determinations are made now. Drilling-fluid additives have been a severe headache for petroleum geochemists for a long time. it can lead to an overly optimistic assessment of the organic richness of the section. The exception to this rule is with amorphous material. whereas those of oils were almost always below 1. which affect only the kerogen portion of the sample. Furthermore. strongly affected by maturity. As long as kerogen particles are not completely black. As a result. in which the input of terrestrial lipids was very limited. it is impossible to determine which maturation path brought it to that point. palynological analysis can usually detect the presence of lignosulfonates because of the unique pollen assemblages present in the lignite. Caving is not a problem for conventional or sidewall cores. rocks deposited in pelagic environments. Problems with living organic matter are easily avoided by physically removing tiny plant roots and other recognizable debris. In many cases. they can usually be identified with reasonable confidence. Atomic H/C ratios must therefore be corrected for the effects of
. Walnut hulls and other organic debris are also easy to detect microscopically.The main causes of contamination among samples obtained from wells are caving and adulteration by drilling-fluid additives. because of their friability. vitrinite reflectance measurements offer the best means of recognizing caving. where the fluorescence that enables us to distinguish between oil-prone and non-oil-prone disappears toward the end of the oil-generation window. however. only microscopic analysis is relatively unaffected by maturity. Later it was realized that the decrease in CPI with increasing maturity depends upon the type of organic matter originally present as well as on maturity. In particular. of course.52
values (> 1. Fortunately. walnut hulls and other solid debris. diesel fuel affects both kerogen and bitumen. in the last decade kerogen analyses have replaced bitumen analyses as the routine procedure in source-rock evaluation. Caving is a particular problem for coals. Mold or other surface growth may also be present. This discovery led to the use of CPI as an indicator of maturity. have low CPI values even when immature. but it can be devastating in cuttings samples.Source Rock Evaluation .5). In contrast to solid additives.
ESTIMATION OF ORIGINAL SOURCE CAPACITY
Of the three major methods of determining kerogen type. Without additional information. Well Samples .2. Careful picking of lithologies and comparison with up-hole samples can often recognize caved materials. however. 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. It is capable of impregnating sidewall and conventional cores as well as cuttings. and can be removed prior to beginning the analytical sequence.
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. Pyrolysis yields are. because all kerogens have low pyrolysis yields.
cutinite. TOC values above 2% often indicate highly reducing environments with excellent source potential. yielding
. has dissented from this pessimistic view. Thus high TOC values are a necessary but not sufficient criterion for good source rocks. Because the density of organic matter is about one-half that of clays and carbonates.5% and 1. which ones might be of slight interest (TOC between 0. and inert. Gas-generative kerogen is mainly vitrinite. Smyth (1983). however. The oil-generative macerals are those of Type I and Type II kerogens: alginite.53
maturation by using a van Krevelen diagram. and thus of limited source potential. Rocks containing more than 1% TOC often have substantial source potential. These raw data are then normalized for the organic-carbon content of the sample. Those rocks containing less than 0.5% and 1. have little oil-source potential. the direct evidence for such a statement is rather meager.5%). Raw data (S1. exinite.5% TOC are considered to have negligible hydrocarbon-source potential.
INTERPRETATION OF SOURCE-ROCK DATA QUANTITY OF ORGANIC MATERIAL
Almost all measurements of the amount of organic matter present in a rock are expressed as TOC values in weight percent of the dry rock. that at least some Australian inertinites can generate significant amounts of oil.5% TOC.Source Rock Evaluation . claiming. Pyrolysis results are normally reported in two ways.0% TOC are marginal. resinite. Inertinite is considered by most workers to have no hydrocarbon-source capacity. Interpretation of TOC values therefore does not simply focus on the quantity of organic matter present. because the kerogens they contain are woody or highly oxidized. and which are definitely worthy of further consideration (TOC > 1. The amount of hydrocarbons generated in such rocks is so small that expulsion simply cannot occur.0%). etc. Rocks containing between 0. Kerogens in rocks containing less than 1% TOC are generally oxidized. the kerogen in such lean rocks is almost always highly oxidized and thus of low source potential. however. but they may expel small quantities of hydrocarbons and thus should not be discounted completely. In some rocks TOC values between 1% and 2% are associated with depositional environments intermediate between oxidizing and reducing. In interpreting these observations we normally divide these macerals into oil-generative. because the type of kerogen preserved in rich rocks is often more oil-prone than in lean rocks. Furthermore. S2. and S3) are expressed in milligrams of hydrocarbon or carbon dioxide per gram of rock sample. These immature H/C ratios can then be used to calculate Go. fluorescing amorphous kerogen. As such these quantities are a measure of the total capacity of a rock to release or generate hydrocarbons or carbon dioxide. gas-generative. We therefore use TOC values as screens to indicate which rocks are of no interest to us (TOC < 0. Nevertheless.
TYPE OF ORGANIC MATTER
Microscopic kerogen-type analysis describes the proportions of the various macerals present in a sample. We must still determine whether the kerogen present is in fact of good hydrocarbon-source quality. A rock containing 3% TOC is likely to have much more than six times as much source capacity as a rock containing 0.0%). on the basis of deductive reasoning. They will not function as highly effective source rocks. where preservation of lipid-rich organic matter with source potential for oil can occur. Many rocks with high TOC values. the actual volume percent occupied by the organic material is about twice the TOC percentage.
The ultimate limit of oil stability is not known for certain. Peak generation is reached near 0. less common application is to decide whether oil will be stable in a given reservoir. Determination of the oil-generation window in a particular section is the objective of most maturity analyses performed on possible source rocks. but in most cases is probably not much above 1.
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. this generalization has two fallacies: most of the coalfields originally studied were of Paleozoic age. Thus. respectively. and the end of liquid-hydrocarbon generation is thought to be at about 1. The correlations among maturity parameters have been fairly well established. Although Tmax values are determined objectively. and the coals were of bituminous to anthracite rank. but there are still some minor variations from one laboratory to another. Some laboratories put the onset of maturity at 435° C. CAI can actually measure high-grade metamorphism. exinite) or from marine algal material. The limits of the oil generation window vary considerably depending upon the type of organic matter being transformed.5% Ro. because during the Paleozoic the biota was quite different than during the Cenozoic.35% Ro. Kerogens with hydrogen indices above 600 usually consist of nearly pure Type I or Type II kerogens. others use 440°.9% Ro. a unified scale for comparing them with Ro values has not been adopted.54
values in milligrams per gram of TOC. some Cenozoic coals should have better potential for generating liquid hydrocarbons. Kerogens with hydrogen indices above about 300 contain substantial amounts of Type II macerals. Measured hydrogen indices must be corrected for maturity effects by using a modified van Krevelen diagram as outlined above. Age of coals is important. because they vary with kerogen type as well as maturity. 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. most other maturation parameters are related to Ro values.Source Rock Evaluation . Because some Cenozoic land plants are richer in resins and waxes than Paleozoic plants. However. Interpretation of hydrogen indices for immature kerogens is straightforward. for most kerogens the onset of oil-generation is taken to be near 0. They have excellent potential to generate liquid hydrocarbons. Because variations in TOC have been removed in the normalizing calculation.
. if you are using TAI determinations determined by an analytical laboratory. 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. The normalized S2 and S3 values are called the hydrogen index and the oxygen index. make sure that you have a copy of their equivalency between TAI and Ro. Because vitrinite reflectance is the most popular method of determining maturity.6% Ro. Those between 150 and 300 contain more Type III kerogen than Type II and therefore have marginal to fair potential for liquids. either from terrestrial macerals (cutinite. the hydrogen index serves as an indicator of kerogen type. A second. Conodont Alteration Index (CAI) values ranging from 1 to 5 were tied loosely to vitrinite reflectance and fixed carbon content of coals. and thus are considered to have good source potential for liquid hydrocarbons.
Kerogen Parameters. Hydrogen indices above 150 reflect increasing amounts of lipid-rich material. Nevertheless. resinite.
8 3.2 3.0 4.50 2.0 3.00 3. therefore.0 Pyrolysis Tmax (°C) 420 430 440 450 460 465 470 480 500 500 + 500 + Conodont Alteration Index (CAI) 1 1 1 1. To do this intelligently we must have the ability to develop regional models of organic facies and thermal maturity.Source Rock Evaluation .8 4. With increasing experience one can also learn to derive important information on thermal histories. we should not rely on a single analytical technique.35 1. rather. Interpretation of source-rock data on a basic level is quite simple. Whenever possible.0 2. In some areas one technique may fail completely or may be only partially successful.5 3. and organic facies.50 0. and maturity of the organic matter present in the rocks? Satisfactory methods are available in most cases to answer all these questions.20 1.80 1.60 0.4 3.55
Any source-rock evaluation should attempt to answer three questions: What are the quantity.00 Thermal Alteration Index (TAI) 2.3 2.
Vitrinite Reflectance (%Ro) 0.00 1. unconformities and erosional events.5 2 2 2 3 4 4 5
Correlation of various kerogen-maturity parameters with vitrinite-reflectance (Ro) values
. type.6 2. We should always attempt to extrapolate our measured data over as large an area as possible.00 4. we should attempt to corroborate the measured data by other analyses.40 0.
7 1.1 2.77 0.41 0.15 0. To use the H /C data.5 2. one must first convert the measured. as shown in Figure B (derived from Figure A).Source Rock Evaluation .98 0. 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." To do this.72 0.7 2.9 3.5 2.3 0.5 2.27 1.05 0. This can be done easily by plotting H/C versus TAI.0 2-2.5 0.5 1. presenting the kerogen quality factor as a
. refer to the graph on next page. quality (H /C and %Alginite + Exinite).6 0.2 3. and then tracing the H/C ratio back to its immature value.65 0.6 2.0 3.07 1. however.5 2-2.2 Atomic H/C 1.66 0.1 3.8 0.7 2.
Both the immature H / C ratios and the maceral analysis data need to be scaled to calculate "Total Oil.7 1.8 % Alginite + Exinite 75 80 80 75 80 90 85 75 70 50 45 60 45 40 ? ?
Data are available on quantity (%Corg). and maturity (TAI). The calculated immature H/C ratios are listed in the table on next page." Two independent quality measurements have been made.5 0.2 2.86 0.56
Worked out example: Perform a source-rock analysis on the Mauve Well.75 0.5 2-2.6 2. and both should be utilized and examined for possible discrepancies.5 1.81 1.33 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) .22 1.38 TAI 2. so "Total Oil" can be plotted against "Oil Already Generated.7 3.3 1.0 0. present-day H/C ratios to the ones that the kerogens had when they were thermally immature.6 2.2 1. B) H/C versus TAI for Mauve Well samples.
65 0.65 0.72 0.6 1. In each case.33 1.22 1.05 0. The prudent interpreter might now ask that some of the H/C ratios be rerun.90 0.60 ? ? * * * * * 1.43 1.5 1. In likewise manner (not illustrated here) the quality factor can be determined from maceral analysis data. 1750. The most important point being made here is that these discrepanties must be taken seriously by the interpreter.30 1. and not
.5 1. the H/C ratio gives the lower quality factor.5 1.41 0.85 1.15 0.35 1.05 1. and would certainly request that the slides made for maceral analysis be reviewed.98 0.
Kerogen quality factor as a function of H/C ratio of the immature kerogen.9 0.00 0.6 1.4 1.8 ? ?
* Indicates discrepancy between quality factors calculated from H /C and from maceral analysis.50 1.75 0.66 0.07 1.0 0.05 1.70 1.38 Immature H/C 1.90 ? ? Quality Factor Quality Factor (from H/ C) (from 1.27 1.8 1. The scaled quality factors are given for each parameter in the table on next page.2 0. and 4500 meters all show differences in the quality factors calculated from the two types of data.77 0. If these attempts produced no resolution of the problem. 2300.86 0.05 0.90 0. to check for analytical error.81 1.35 0. so some systematic error is likely.77 0.60 0.35 0. such as pyrolysis.90 0. it is impossible to pinpoint the error.6 1. Without more knowledge.Source Rock Evaluation .
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.
It is apparent that there are serious discrepanties between the H/C and maceral analysis results for several of the samples. the interpreter might then decide to try a third technique.81 1. 1500. 4000. The samples at 1000.07 1.57
function of H/C ratio of the immature kerogen in order to determine the quality factor from H/C.17 0.20 1.7 1.05 0.60 0.9 1.22 1. however. 2000.90 0.
The only sample where the discrepancy is significant is that from 2000 meters.
"Total Oil" and "Oil Already Generated" profiles tor the Mauve Well. The rest of the section shows a good correspondente between the two parameters. More samples between 3000 and 3500 meters should be obtained to define better the zone of high "Total Oil" values.58
be overlooked or swept under the rug.
"Total Oil" and "Oil Already Generated" profiles are plotted in above figure. These two kerogens are highly mature and quite black. although the section between 2000 and 3500 meters shows fairly good potential. therefore. "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. It may be necessary occasionally to offer two alternative interpretations without choosing between them. "Total Oil" values are generally unexciting. In fact.
. and the H/C ratios are not helpful because the maceral types cannot be ascertained from such low H/C values. because sourcerock potential is not good for most of the section. Future exploratory activity could include an attempt to find such a section. Let us take this last approach to this problem.Source Rock Evaluation . except for the two deepest samples. Most of the discrepanties among the different quality factors turn out to be unimportant. Finally. about the oil-source history of the section below 4600 meters. The relative organic richness of the blackened samples below 4600 meters makes them interesting for further investigation. 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. One can say little. no maceral analysis was possible here.
07 1.0-2.90 0.5 2.60 0.9 1.49 0.5-3 2.
EXERCISE Source Rock 2 Perform a source-rock evaluation of the section penetrated in the Turquoise Well.09 0.02 Atomic H/C 0.33? 1.06 0.5 3-3.91 1.65 0.08 0.3 Bit/TOC 0.66 0.5-3 2.0 0.17 0.03 0.63 0.99 1.11 0.2 0.06 0.02 0.46 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 2.8 0.12
*TAI and Ro are interconverted according to the correlation table at the end of chapter 7.0 2.5 2.25 1.3 2.5-3 2.5 2.0-2.25 0.6 0.17 0.49 0.5 2.51 0.0 2.5 2.7 0.02 0.21 1.5
TOC = Total Organic Carbon Bit/TOC = Bitumen/Total organic carbon ? indicates a poor histogram
TAI = Thermal Alteration Index Ro = Vitrinite reflectance
.52 0.0 2.67 0.21 0.3 2.22 0.59 0. Source-rock data tor the Turquoise Well
Depth (ft) 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500 8000 8500 9000 9500 10.5 2.2 2.7 0.44 0.21 1.08 0.5 2.27 0.8 1. Explain how you resolved any apparent discrepancies.0 3-3.03 0.09 0.18 0.4 0.5 2.61 0.1 2.05 0.03 0.88 0.51 0.07 0.5 3.5-3 3.1 0.5 3.91 0.Source Rock Evaluation .5-3.85 0.6 4.60 0.41? 1.000 Type of Sample Cuttings Cuttings TOC 1.66 0.27 1.59
EXERCISE Source Rock 1 Combine the data from the Blue Well to give a coherent picture of thermal maturity in the section drilled.91 1.6 2.3 2.0 2.00 1.08 0.59 0.55 0.0 2.08 0.51 0.5 2.5 0.07 0.05 0.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10
2-2.06 0.10 0.01 0.42 0.86 1.5 2.26? 1.5-3 2.0 2.48 Ro 0.5 2.65 0.71 0.3 1.60 0.5-3 2.0-2.
especially if the seismic reflectors can be tied to well data. Furthermore. estimates can be made. maturity measurements can only tell us about present-day maturity levels.60
9 . In some areas there are no well samples available. a time stratigraphy can sometimes be constructed using seismic data. for it is in keeping with the predictions of chemical-kinetic theory. nor do we know at what depth or temperature it occurred. Part of this problem is a consequence of the limitations we face in attempting to obtain reliable maturity measurements. in frontier basins there may not be a single well within tens or hundreds of kilometers. 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.
CONSTRUCTION OF THE GEOLOGICAL MODEL
One of the advantages of Lopatin's method is that the required input data are very simple and easy to obtain.Predicting Thermal Maturity
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. 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. If our measurements indicate that a rock has already passed through the oil-generation window. 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. 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. He developed a "Time-Temperature Index" of maturity (TTI) to quantify his method. however. perhaps from thicknesses of exposed sections nearby. and migration with timing of structure development or trap formation. however. Time-stratigraphic data are usually available as formation tops and ages obtained by routine biostratigraphic analysis of well cuttings. In order to circumvent these difficulties. 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. These considerations are important when we want to compare timing of generation. In this chapter you will learn how to carry out maturity calculations using Lopatin's method and how to use Lopatin's method in exploration. methods have been developed for calculating maturity levels where measurements are not available. It has even been suggested that maturity models are more accurate than measured data for determining the extent of petroleum generation. we still have no clue as to when oil generation occurred. measured maturity data are of limited value in exploration. Even in maturely explored basins the samples available for analysis often do not give a representative picture of maturity in the basin. Nevertheless. In most cases. expulsion. If no well data are available. This assumption is a logical and defensible one.Predicting Thermal Maturity . If no subsurface data are available.
. In 1971. indeed. We need data that will enable us to construct a time stratigraphy for the location of interest and to specify its temperature history.
The next step is to locate the first control point from the time-stratigraphic data on the input table.61
Implementation of Lopatin's method begins with the construction of a burial-history curve for the oldest rock layer of interest. Nevertheless. by 80 Ma the sediment had been buried to a depth of 900 m (point C). 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. we can construct the temperature grid with equally spaced isotherms parallel to the earth's surface. that the Tiger well was logged. burial-history curves represent our best understanding of the geological history of an area.(9-2)
All of the shallower and younger horizons will have burial-history curves whose segments are parallel to those of the oldest horizon. In cases where biostratigraphic data are available and deposition has been reasonably continuous. In cases where biostratigraphic data are lacking or where the sediments have had complex tectonic histories.
. In the Tiger well. representing the initial deposition of the sediment (point A) and its position today (point B). it is easy to construct burial-history curves with a high level of confidence. Today the rock is at a depth of 3700 m. Using these present-day data and extrapolating them into the past. a burial-history curve may represent only a rather uncertain guess. Using the other control points from the input table. are marked on the age-depth plot. which was constructed from the time stratigraphy for the Tiger well. we can construct the complete figure. and that a corrected bottom-hole temperature of 133° C was obtained at 3800 m.
The next step is to provide a temperature history to accompany our burial-history curve. An example is shown in the following figure. This geometry is a direct consequence of ignoring compaction effects.Predicting Thermal Maturity . The burial-history curve was constructed in the following way: two points. if constructed as carefully as the data permit. Burial-history curves are based on the best information available to the geologist. The simplest way to do this is to compute the present-day geothermal gradient and assume that both the gradient and surface temperature have remained constant throughout the rock's history. sediment has accumulated continuously but at varying rates since deposition of the oldest rock 100 million years ago (Ma). Connecting the six dots completes the burial-history curve. for example. Neglecting compaction effects. Suppose.
In most cases.
SPECIAL CONSIDERATIONS ABOUT BURIAL-HISTORY CURVES
The most common complicating factor in constructing burial-history curves is erosional removal. 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. two separate diagrams should be used for the sake of clarity. In many poorly explored areas. If deposition resumes later. Erosion is indicated in a burial-history curve by an upward movement of the curve. burial-history curves for both hanging wall and footwall can be represented on a single diagram. the data necessary for highly sophisticated temperature reconstructions are simply not available. some part of the section is repeated as a result of thrusting. temperature profiles will be based largely on guesswork. Given adequate data or an appropriate model on which to base complex temperature reconstructions. If thrusting is rapid compared to the rate of thermal equilibration between thrust sheets.62
Where measured bottom-hole temperatures are not available. There are numerous other variations that can be employed in creating temperature grids. but the geothermal gradient varies in response to heating or cooling events. the resultant thinning of the section must be represented in the entire family of burial-history curves. If. Whenever erosional removal occurs. however. the movement of hot rocks from the bottom of the overthrusted slab over cool rocks at the top of the underthrusted slab will affect
. There is no theoretical limit to the complexity that can be introduced into our temperature histories. If part of the section is missing as a result of faulting. the burial-history curve again begins to trend downward. More complicated temperature histories account for changes in thermal conductivities caused by variations in lithology.
In other cases the surface temperature remains constant. Causes for such events could include global warming and cooling or local climatic variations resulting from continental drift or elevation changes. The effects of thrusting on thermal maturity are not well understood. maps of regional geothermal gradients can be useful in estimating the gradient at a particular location. The individual segments of each of the burial-history curves in a family will remain parallel. For example (9-7). we are limited only by our own creativity.Predicting Thermal Maturity . Faulting can be dealt with by considering the hanging wall and footwall as separate units having distinct burial histories. however. we can change surface temperatures through time without altering the geothermal gradient.
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. Now we can carry out the maturity calculations. Lopatin defined each time factor simply as the length of time.
Loss of 1000 m of section by erosion during an uplift event lasting from 70 Ma to 60 Ma. The temperature factor.Predicting Thermal Maturity . expressed in millions of years. we need to define both a time factor and a temperature factor for each temperature interval.63
organic maturation by causing important perturbations in subsurface temperatures. Total maturity is calculated by summing the incremental maturity added in each succeeding temperature interval. A Time interval is the length of time that the rock has spent in a particular temperature interval. but the distance between the two lines which bracket the erosion. we must paste them together. Temperature intervals are defined by successive isotherms spaced 10° C apart. Lopatin chose the 100°-110° C interval as his base and assigned to it an index value n = 0. Intersections of the burial-history curve with each isotherm are marked with dots. Because the rate of maturation was assumed to increase by a factor of two for every 10° C rise in temperature. Lopatin (1971) assumed that the rate of maturation followed this doubling rule. spent by the rock in each temperature interval.400 cal/mol will approximately double with every 10° C increase in reaction temperature. This intervalTTI value represents the maturity acquired by the rock in that temperature interval during the time
. In order to carry out maturity calculations conveniently. Studies in the Overthrust Belt of Wyoming indicate that a slow-equilibration model is superior to a simple model invoking rapid thermal equilibration. However. Individual burial-history curves remain parallel.(9-12)
CALCULATION OF MATURITY
Once the burial-history curves and temperature grids have been constructed. respectively. Multiplying the time factor for any temperature interval by the appropriate temperature-factor for that interval gives a product called the Time-Temperature Index of maturity (TTI). in contrast. more work is required before we will understand fully how thrusting influences hydrocarbon generation and destruction. Testing of his model and the successful application of Lopatin's method in numerous published examples have confirmed the general validity of this assumption. for any temperature interval the temperature factor (?) was given by: ? = 2n The temperature-factor thus reflects the exponential dependence of maturity on temperature. increases exponentially with increasing temperature. decreases by 1000 m. Index values increase or decrease regularly at higher or lower temperatures intervals. These dots define the time and temperature intervals that we shall use in our calculations.
It is also possible to determine the total-TTI value at any time in the past simply by stopping the calculation at that time. If we put a cake in a cold oven and turn the oven on. In A the rock was buried at a constant rate for its entire 80-my history. finally. To obtain total maturity. where the time factors and yfactors for each temperature interval are shown on the burial-history curve. Furthermore. In B burial was very slow during the first 70 Ma of the rock's existence. A good analogy can be drawn between oil generation and baking.64
given. followed by a nonerosional depositional hiatus for the last 50 Ma. but quite rapid in the last 10 my. In D 40 Ma of rapid burial to a depth of 4000 m was followed by a hiatus lasting 30 Ma and. In the adjoining table interval-TTI values and total-TTI values up to the present day are calculated. TTI values differ appreciably among these four scenarios. baking will continue. if we forget about the cake when the oven is hot and let it burn. we cannot "unburn" it. On the other hand. maturity continues to increase (albeit at a slower rate) because y is always greater than zero.
. as the oven cools down.
FACTORS AFFECTING THERMAL MATURITY
Because maturity is affected by both baking time and baking temperature. although at increasingly slower rates. by 10 Ma of uplift and erosion. we simply sum all the interval-TTI values for the rock. Four of the many paths by which an 80-Ma-old rock could have reached a present burial depth of 3000 m is indicated in the figure (9-21).Predicting Thermal Maturity . it can never go backward because interval-TTI values are never negative. Figure C shows rapid burial during the first 20 Ma. The first step in calculating TTI is illustrated in the following figure. the specific burial history of a rock can strongly affect its maturity. even if a rock cools down. If we turn off the oven but leave the cake inside. the cake will bake slowly at first but will bake faster and faster as the temperature rises. no matter how much or how rapidly we cool it down. Maturity always increases.
Wyoming. 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. In actuality. First. Temperature. the dependence of maturity on time is linear.(9-29)
Furthermore. and can be even better in Cenozoic rocks. showing the evolution of the oilgeneration window through time. but there is no guarantee of their accuracy in any particular case. time data are seldom a problem.
Family of burial-history curves for a well in the Big Horn Basin.Predicting Thermal Maturity . Secondly. we usually have excellent control on rock ages through micropaleontology. in contrast. Present-day subsurface temperatures are difficult to measure accurately. Most logged temperatures are too low and require correction.
. might we anticipate possible problems with time. is the single most important cause of uncertainty and error in maturity calculations. Km = Lance-Meeteetse formations. so even a rather large error in baking time will not produce a catastrophic change in maturity. The model includes an extensive nonerosional depositional hiatus. Tfu = Fort Union Formation. Various methods have been developed for this purpose. B) Revised burial-history model for Well #1 based on the poor correlation with measured maturity data. Tu = undifferentiated Tertiary. 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. our uncertainties about the true values of subsurface temperatures are much greater than about time. Only in cases where micropaleontological dating was not or could not be carried out. Kc = Cody-Frontier formations.65
A) Initial proposed burialhistory model for Well #1.
52 0.25 1.5-3 2.85 0.5 3.7 0.48 Ro 0.8 0. Base Pleistocene 2 Ma Base Pliocene 5 Base Upper Miocene 11 Base Middle Miocene 50 Ma
.88 0.5 2.3 Bit/TOC 0. however.27 1. Construct a family of burial-history curves for the well and calculate the present-day TTI at total depth.49 0.91 1. particularly where Paleozoic rocks are involved.
EXERCISE Thermal Maturity 1 Perform a source-rock evaluation of the section penetrated in the Turquoise Well. A plausible average surface temperature is 20° C.17 0.51 0.21 1.0 0.06 0.000 ft of Upper Miocene before being abandoned at 16. 3500 ft of Pliocene. 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.67 0.66
Even if we could measure present-day subsurface temperatures with perfect accuracy.03 0.41? 1.21 1.91 1.1 0. Despite experimental evidence indicating that different kerogens decompose to yield hydrocarbons at different levels of maturity models.5-3 3.22 0.5-3 2.5-3 2.5-3 2.5-3 2.59 0.4 0.5
TOC = Total Organic Carbon Bit/TOC = Bitumen/Total organic carbon ? indicates a poor histogram
TAI = Thermal Alteration Index Ro = Vitrinite reflectance
EXERCISE Thermal Maturity 2 The Black Well was drilled off the Louisiana Gulf Coast.66 0.5 2. and 11. A question of some concern comes from the previously mentioned fact that most of the maturity models treat all types of kerogen identically.0 3-3.60 0.6 4. where presentday temperatures are maximum paleotemperatures.02 0.26? 1. we still would have to extrapolate the present somehow into the past. however.8 1.08 0.07 1.3 1. Source-rock data tor the Turquoise Well
Depth (ft) 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500 8000 8500 9000 9500 10.05 0.5 2.91 0. even an inaccurate extrapolation into the past may not cause significant problems.86 1. In many cases.08 0.9 1.000 Type of Sample Cuttings Cuttings TOC 1.65 0. In other cases.7 0.99 1.08 0.5 0.150 ft in the Middle Miocene.1 2.2 0.33? 1.65 0.5 3-3. The corrected bottom-hole temperature was 270° F. do not utilize different kinetic parameters for the various kerogen types.03 0. an accurate interpretation of the ancient geothermal history may be critical.71 0.5 2.00 1.Predicting Thermal Maturity .51 0.02 Atomic H/C 0.01 0.5 3.90 0.06 0.27 0.5-3.18 0. It penetrated 1000 ft of Pleistocene sediments.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10
Total depth is reached at 6120 ft in Middle Jurassic rocks.67
EXERCISE Thermal Maturity 3 Calculate present-day TTI at 3000 m in the Red Well.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. Corrected BHT (4200 m): Estimated surface temp.5 base Turonian base Cenomanian base Cretaceous top Kimmeridgian base Kimmeridgian 91 Ma 97 144 150 156 Ma
. Find when the rock at 3000 m began to generate oil (TTI = 10).5 88. At a depth of 1500 ft. micropaleontology indicates the rocks to be of Maestrichtian age. draw a burial-history curve for the section penetrated and calculate maturity for the Kimmeridgian shale. 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. Determine when each of the strata began to generate oil. Total original thickness of the Kimmeridgian is thought to be 1500 ft. Assuming a surface temperature of 10° C and a geothermal gradient of 2° F/100 ft. assuming a constant geothermal gradient through time. It is also believed that 500 ft of Lower Cretaceous sediments were deposited before uplift and erosion began. Evidence from related sections indicates that the Paleocene was originally about 3000 ft thick and that no other Cenozoic sediments were ever deposited. Age data
top Paleocene base Paleocene base Maastrichtian base Campanian base Santonian base Coniacian 55 Ma 65 73 83 87.end Cretaceous: 15° C 141° C 25° C
EXERCISE Thermal Maturity 4 The Ultraviolet Well is spudded in Paleocene sediments.
000 18. From 40 Ma to the present about 500m of additional burial occurred.500 27."
Utilizing the principles of hydrocarbon generation and preservation. and the surface temperature today is about 15° C. oil-prone source rock at about 4300m depth near the prospect.500
EXERCISE Thermal Maturity 6 You have been asked to evaluate an undrilled prospect in a remote area that is available in an expensive farm-in deal. Time-stratigraphic data are given in the following table.000 25. Because of the high operations cost. The geothermal gradient was found to be 1.
. The basin filled at a generally uniform rate from about 300 Ma to 100 Ma. Carboniferous '' '' '' '' E. they are in turn overlain at 2750m by a sandstone of excellent reservoir quality. Your responsibility is to make a recommendation regarding the nature of hydrocarbons that might be present in die prospect. The reservoir is sealed by a thick salt layer.68
EXERCISE Thermal Maturity 5 Analyze the timing of oil generation in the Pink Well. No other reservoirs are anticipated. evaluate the prospect.
"A regional study of the area suggests the probable presence of a thin. The following geological summary is available to you.000 13. The source rock is thought to be about 300 Ma old.0° F/100 ft.000 8. Carboniferous '' Ordovician '' Depth (ft) 7. Erosional removal since the Permian probably totals about 2000 ft.65°C/100 m and a surface intercept of 15°C are reasonable for the area. upper management has decided that gas and condensate are not economical. rich.000 11.
Top of Permian Virgil Missouri Des Moines Atoka Morrow Mississippian Kinderhook Sylvan Arbuckle Age (Ma) 230 280 288 296 304 309 320 340 425 470 Period Permian 0 L.000 23. 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. At that time nearby orogenic activity caused the first traps to be formed during a gradual 1200m uplift lasting until 40 Ma. No other source rocks were noted. No unconformities are recognized within the Paleozoic. Highly fractured carbonates overlie the source rock.500 21. Nearby well control indicates that a geothermal gradient of 3.Predicting Thermal Maturity .
10 . located at surface near the well-head. Because anyway there is uncertainty about this amount. Now we must see how we can apply our knowledge of the geology to assessing the amounts of petroleum that we have found. is liable to change between our information points. companies tend to use `proven' for those reserves that are believed to be present with an 85 or maybe 90 per cent degree of
. Recoverable reserves: The volume of oil that can actually be produced to surface from an accumulation. it is desirable to be able to express our degree of confidence in it. Proven reserves: Here we start to enter a minefield! Different companies have different definitions of what is proven. 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. Increasingly these days. and oil may be produced directly into it. This section is included to give an idea of what is involved. and tertiary reserves using more exotic techniques. How do we handle these problems? Before we get into this. First.Quantitative Assessment
So far we have been talking in rather generalized terms. even within oil companies. We have to try to understand. we have to remember that we are dealing with a resource and that we are very concerned with the quantities involved. but the same considerations. Similarly. or hope to find. which can be produced using assisted or enhanced recovery techniques. You may see the engineers using the term STOOIP: stock tank oil originally in place. since we are never able to recover all of the oil that is down there in the reservoir. half a mile or whatever. once a discovery is made. and terms can be used equally for gas. We may distinguish between primary reserves that can be produced without any artificial assistance other than pumping. What they think is beyond that in the accumulation. in the case of small fields.
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. 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. We will refer to oil. of a well. however. Note. just what these changes amount to. However. unless we can be more specific about how we are going to produce them. This may be done via a standard deviation or by a statistical probability (see below). or predict. We cannot regard these quantities as `reserves'.Quantitative Assessment . A bald figure for `recoverable reserves' is somewhat meaningless. which controls the amounts of oil in the reservoir. and therefore without any dissolved gas of significance. measured in barrels or other units that is present in an accumulation under the ground. we are involved with a greater or less degree of uncertainty about quantities. So. And yet oil companies need to know what to expect. there is no way that we can know precisely how much we have found: the geology. The stock tank is. let alone how much. of the following terms:
OIL IN PLACE
This is the total volume of oil. let us again emphasize that we are dealing all the time with uncertainties. Some might use the term to refer to the amount of recoverable oil that is believed to lie within a given radius. methods. they might designate as `probable'. secondary reserves. we have to clear a good deal of misunderstanding and misuse. It usually refers to what was there originally. until actually all of the oil has been produced. 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. before we started to take any of it out.
It may well be that it is best to avoid the terms `proven'. the higher will be the water saturation. 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. – Fill is the `fill factor'. even when we have information from a lot of wells. like `proven'. but what happens between and beyond our well control? – Sw is the water saturation. We have to discount those parts of it that are useless and just consider the net reservoir thickness. This reflects the fact that oil under the ground in the reservoir occupies more space than it does when we get it up to the surface. meaning that we have to try to interpret in detail the environments that the sediments were deposited in. This can be pretty subjective. if we do. BV will be determined from seismic and well data. in this case 50 per cent. Probable reserves: Equally dodgy! One definition was given above: the term may be used.Quantitative Assessment . Sometimes `possible' is also seen. or rather the average porosity of the net reservoir across the entire accumulation. This will be controlled by variations in the nature of the sediments that comprise the reservoir. – FVF is the formation volume factor. We then eliminate progressively everything from this volume that is not oil. it shrinks because gas bubbles out of it as its pressure is eased during production. the volume of the gas cap and the water-bearing rock below the oil-water contact being discounted. including the adequacy of the source rock to provide enough oil to the trap. `probable'. What this means and how we arrive at the figure. to refer to a degree of confidence or probability. then we can go straight to the bulk reservoir volume containing the oil. It is affected by many factors. – N/G is the net to gross ratio. the percentage of the porosity that is occupied by the immovable water. Not all of a reservoir formation is going to be sufficiently porous and permeable to contribute oil to production. and what is still there for the taking at a given date. Recoverable reserves = [BV * Fill * N/G * ? * (1 . and regional and local geological interpretation. 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. 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. faulting. We have not only all the problems of average porosity but remember that the size of the pores comes in here as well: the finer the sand. and `possible' altogether.
. – ? is the porosity.70
confidence or statistical probability. we shall see shortly. The shape of the trap. if we hear simply about `reserves'. Usually. that are meant. What anyway should we regard as net reservoir? A rather arbitrary porosity cut-off value is often used. to cover the reserves that have only a 15 or 10 per cent chance of being present. which is the percentage of the bulk volume that actually contains the oil. then this factor may be little more than a guess. Again we need an average value for the field. We do our best from measurements on core samples and from wireline log interpretation. They refer respectively to what was there and recoverable before we started producing.
Once a discovery of oil has been made. and the thickness of the reservoir govern it. and the quality and strength of the cap rock.Sw)] * RF * Constant FVF where: – BV is the volume of the reservoir formation within the closure of the trap above the spill-point. it is the remaining reserves. So we multiply the bulk volume of the reservoir in the trap by those factors that represent the non-oil. If we do not know where the gas-oil and oil-water contacts are.
the proportion of the oil in the reservoir that we can actually recover and produce. Alternatively one may plot the frequencies as percentages of the total number of answers: the statistical probabilities. and we also specify the total range.. Most commonly these days. The computer does the sum using these values. we shall find that the bulk of them tend to cluster round the middle (Fig. since it is about this that the standard deviation can be calculated.
Diagrammatic plots of the outputs from two Monte Carlo simulations. any one of which could be the real value.. Then we get a computer to pick a value for each factor at random from the range we have given. Note that the preferred answer that is usually used is the mean value. The list is put into order from the smallest to the largest. What we are doing. we have to multiply the figure we calculate by 7758. If we are working entirely in the metric system. and then analysed statistically. In a sandstone reservoir. we give as our preferred figure the average of all the answers (the mean). and governments must have numbers that they can use for planning purposes. The one that has the most answers in (= the modal class of the distribution) we can regard as the most probable value -in other words. we can work out the standard deviation (the ±) which will give an idea of our confidence in our answer.71
RF is the recovery factor. then.
. If we plot out the answers on our list falling within successive size ranges (in barrels of oil).
It will be clear to anyone that. then we don't have to worry. To get an answer to our sum in barrels of oil. So we have a whole list of answers. even though they may be well aware that any such figures will eventually turn out to be wrong. doubtful estimates by doubtful estimates. but it may be a good deal less from carbonates. A constant is needed to adjust the units. until we begin to wonder whether our answer has any reality or meaning at all.). Who is right? Whose answer should we use? Can we indeed believe any of them? Unfortunately we cannot escape from the problem. having regard to all of the geology. is to multiply uncertainties by uncertainties. and again. More commonly.Quantitative Assessment . this is commonly about 50-60 per cent. from minimum possible to maximum possible. and to try to be as honest and objective as possible. for this average value. known as a Monte Carlo simulation. The number of answers in successive reserve ranges is plotted against the size ranges themselves. and arrive at perhaps wildly different answers. however.This is because. maybe 500 or 1000 times. and again. Then we ask it to do the same thing again. It is a figure that we cannot know exactly until we have finished producing. companies. 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. there must be considerable uncertainty to say the least. So we usually have to base our estimate on prior experience elsewhere. the problem is tackled through a statistical technique. but biassing its pick towards our best estimate. somewhere within which the `true' figure must be. our best estimate. for each of the factors we work out our best estimate. in producing figures for all of these factors. Different geologists will certainly come up with different values for at least some of the input factors.
The risk factor. We try to assess the probability that each factor will be satisfied. say.
. the 90. It cannot be worked out completely objectively. turn out to be totally dry-lacking in hydrocarbons. This is what is used to determine those reserves that may be called proven. but also the chance of there in fact being any oil at all. that is exactly what it is. the curve represents the chance (probability) that the reserves are a certain size or greater. we have to go a stage further. combined with the estimate of how much. and honest as can be in assessing exploration risk. you may say. then no oil. and ensures that all possibilities are considered. for geological reasons. and 10 per cent levels of probability respectively. and possible at. probable. When it comes down to risk. 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.
This is all very well. Incidently. Of course we try to be as scientific. Indeed it does not! When we are looking at exploration of the unknown. It will give a graph which shows the probability that the reserves will be of a certain size or more. objective. different geologists will arrive at different figures for the probability of success. By plotting the answers from the 100 per cent probability downwards. but rather it is the number an individual geologist might produce to reflect his/her personal interpretation of the geology. there really is no such thing as the risk factor. and then merely combine the probabilities to give an overall probability .Quantitative Assessment . We have to give not only our best estimate of how much petroleum there might be.
Most usefully. but it assumes that we have already discovered oil. perhaps. to give the chance of discovering certain reserves or more including the 50 per cent chance that we may find nothing at all. So this type of graph has now become one of the standard key tools in exploration/development decision. now gives a more complete picture of the viability of an undrilled prospect .). 50. of our confidence that there will be at least some oil. This chance (probability) is known as the risk factor: it is an expression. it doesn't take any account of the fact that our exploration well may. For example. It is this sort of thing that helps to make the oil exploration business so competitive. It is also used to assist management in making their exploration/development decisions. we can read off from the graph the chances of our field containing that much oil or more. as opposed to assessing what we already know to be there. if the engineers say that a field of so many million barrels is going to be needed to justify development and production costs. And if all this sounds like a gambling game. 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. we can plot out the percentages of answers in successive size ranges cumulatively as we work down the list (Fig.at least until we start also considering the costs and economics. in numbers. management can then decide whether or not to take the gamble on developing the field at those odds. the same values are discounted by a 50 per cent risk factor.72
The output from a Monte Carlo simulation with the percentages plotted cumulatively. In the lower plot.the risk factor. if any one of them fails or is lacking.
This kind of plot can be used also for individual basins or for the whole world. the expected reserve estimates from our Monte Carlo simulation multiplied (discounted) by the risk factor (Fig. is a hypothetical figure. it is a pretty wild sort of plot. 3. however. Should we. The obvious thing to do is to add together the risked reserves estimates of all the remaining prospects. we have to assume that today we can identify and assess all of the prospects that ever will be found in the basin.). for example. 5. 1. Delphi was the place in ancient Greece where one went to consult the oracle about one's future. all of them are very dodgy
.Quantitative Assessment . remains to be found. In a similar vein the amount of oil found world-wide each year from the beginning of the century can be plotted. We might look at explored and known parts of the basin. the two elements of size and chance of success. knowing how rich it is.
So far we have been talking about a single oil accumulation or a single prospect. then use these figures for the unexplored parts of the basin. for our `best estimate'. and a number of techniques have been employed. or underlying each square mile of surface area. If we have a reasonable amount of information and control. This starts with the volume of mature source rock in the basin and then. we can. merely use the average of the figures they produce. on average. But we have to admit that. we are said to be consulting the oracles! All of the above techniques have been used. the built-in risk factor takes care of this. Some of these will be successful. however. the amount of oil generated. if we draw a smooth line through it to even out the peaks and the troughs. We could make comparisons between known and unknown basins. However. This figure is extremely imprecise and may be not much more than a guess. and the area under that bit will represent what. 4. This is known as the Delphi technique. We could adopt what is known as a `geochemical material balance' approach. 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. go for a large but very risky prospect. expelled. unless we really have a lot of information (we never have enough!). Use past statistics (number of barrels of oil found on average for each 100m of exploration drilling?) and extrapolate to future drilling. or would our money be better spent on drilling a smaller but safer one? The risked reserves. otherwise we may be doing little more than guessing. This combines in a single estimate. and use the figures for the known also for the unknown ones. then the area under it represents the total volume of oil found to date. sometimes in combination. 2. However. and made available for entrapment (the `charge') can be calculated. get a number of experts to make their forecasts by whatever technique they prefer and. and 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. to believe that we can do this would be the height of conceit. on this tack. but some will be dry. and calculate average quantities of oil per cubic mile of sediment. let us note a number known as the risked reserves. Let us look at the more important ones. Undiscovered are thus what we hope to find in a prospect area or sedimentary basin in the future.73
Lastly. and as such can be very useful in planning an exploration program. There are lots of uncertainties in this but the calculation would be amenable to a Monte Carlo type of simulation. Forcing these experts to agree a figure amongst them might refine the approach. Many `experts' have scratched their heads over the estimation of undiscovered reserves. qualify it by a statistical probability. Extrapolate this smoothing line out into the future. and some may be more appropriate in given circumstances than the others. 6. Adding this to the original reserves will give us what is sometimes called the `ultimate reserves'-a grand total for the basin. this technique may bring us into the right ball-park. If all else fails.