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
porosity and permeability decrease. called catagenesis. Although the transformation process is very complex. In the early stages of catagenesis most of the molecules produced from kerogen are still relatively large. thermal reactions become increasingly important. are chemically distinct from each other. In the late stages of catagenesis and in the final transformation stage. and are called bitumen . Certain microorganisms. Most of this organic matter is transformed during diagenesis info very large molecules. Migration through these conduits often leads to traps. 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. As temperature rises. Formation of biogenic methane has been recognized for a long time. these are the precursors for petroleum. and were formed as dead organic matter was converted to microbial tissues. These play a key role as the precursors for oil and much natural gas. As burial depth increases.
. These changes lead to a gradual cessation of microbial activity. the largest of which are called kerogen. but only within the last few years have we realized that in many areas a large portion of the natura!-gas reserves are biogenic. it is known that organic debris derived from plants and algae is best preserved in fine-grained sediments deposited in the absence of oxygen.Organic Facies . The earliest stage of hydrocarbon generation occurs during diagenesis. the principal products consist of smaller gas molecules. During this second transformation phase. Once formed. where hydrocarbon movement ceases and accumulation occurs. called methanogens.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. and temperature increases. with many details still poorly understood. These differences can have a significant effect on hydrocarbon generation. oil and gas molecules can be expelled from the source rock into more permeable carrier beds or conduits. more mobile molecules. and thus eventually bring organic diagenesis to a halt. or under different diagenetic conditions. Many of the chemical compounds present in sediments are in fact derived from bacteria. called metagenesis. convert some of the organic debris to biogenic methane. kerogen begins to decompose into smaller.5
1 . however. Low-temperature chemical and biological reactions (called diagenesis) that occur during transport to and early burial in the depositional environment modify this organic matter.
Oxidative decay of dead organic matter is a highly efficient process mediated largely by microorganisms. Some of the organic material in sediments consists of fragments of plants or algae that derived their energy from the sun. the yearly productivity of both groups is about equal. as a consequence of the much more rapid reproduction of simple aquatic organisms. A large fraction. Zooplankton and higher animals contribute relatively little organic matter to sediments. Because of
. 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. Preservation of organic material is actually a rare event.Organic Facies
THE CARBON CYCLE
Because oil and gas are generated from organic matter in sedimentary rocks. less than 1% of the annual photosynthetic production escapes from the carbon cycle and is preserved in sediments. however.Organic Facies . Most organic carbon is returned to the atmosphere through the carbon cycle. Despite the great imbalance in biomass between terrestrial plants (450 billion metric tons [t]) and aquatic phytoplankton (5 billion t). Preservation of organic matter begins with photosynthesis.6
2 . we need to understand how this organic matter came to be preserved in the rocks. comprises microbial tissue formed within the sediments by the bacterial transformation of plant and algal debris.
In the modern world there are zones of intense seasonal upwelling off the west coasts of California.000 billion t. Depth could interfere with microbial diagenesis when compaction reduces pore sizes and nutrient fluxes in interstitial waters. The three primary factors influencing the amount of organic matter in a sedimentary rock are productivity. Total Organic Carbon (TOC) values decrease monotonically through the first 300 meters of burial before levelling out at about 0. and Northwest Africa that result from the movement of surface waters away from these coasts. In relatively unrestricted marine environments. There is another zone of seasonal upwelling off the Horn of Africa in the Indian Ocean as a result of
. one of the critical parameters governing productivity. and general water chemistry. and recycling by organic decay. paleoclimate. Nutrients dissolved in waters below the photic zone therefore go unutilized. When we consider inefficiencies in discovery and recovery. Upwelling occurs where bulk movement of surface water away from a particular area allows deeper water to ascend to replace it. are therefore much more productive than the open ocean. predators. If this deeper water is enriched in nutrients. On the other hand. Productivity is the logical place to begin our analysis. significant amounts of organic matter must be deposited and protected from diagenetic destruction. and dilution. because without adequate productivity. a great deal of the oxidation of organic matter occurs within the sediments themselves.Organic Facies . high photosynthetic productivity will occur at the site of upwelling. carbonate supply. and that the microbes have given up trying to digest it. Peru. because under normal circumstances they cannot move upward into the zone of photosynthesis. Although some destruction of organic material occurs during transport to the depositional environment. where there is local recycling of nutrients from decaying organisms and influx of fresh nutrients from terrestrial sources.7
extensive oxidation of land-plant debris in soils.
A partial listing of the many factors influencing productivity would include nutrient availability.000 billion t) dispersed in fine-grained sedimentary rocks. Namibia. orogeny and erosion. suggesting that either depth or organiccarbon content eventually limits diagenesis. preservation. Only a small fraction of this (10. Only where there is upwelling of subsurface waters can these nutrients return to the photic zone. in fact. light intensity.05%) occurs in economic deposits of fossil fuels. the low TOC values could indicate that the remaining organic matter has no more nutritional value. volcanism.000. or about 0. For example.1%. nutrient availability would depend on such factors as water circulation patterns. temperature. with a preference for horizontal water movement within each density layer. Each factor may be dominant under different conditions. Bodies of water naturally develop density stratification. Although oxidative decay destroys most of the yearly production. Nutrient availability is. only one molecule out of about every one million successfully negotiates the journey from living organism to the gasoline pump. Each of these categories could in turn be further subdivided. however. accumulation of organic-rich sediments cannot occur. watercirculation patterns are particularly important for supplying nutrients and thus controlling productivity. Shallowmarine environments.
FACTORS INFLUENCING ORGANIC RICHNESS
In order for organic-rich rocks to be formed. over vast amounts of geologic time the small fraction that escaped the carbon cycle has built up extremely large quantities of organic matter (20. much of the terrestrial organic material is already highly oxidized when it arrives in the sediments.
Anoxic sediments always contain elevated TOC values (generally above 2% and always above 1% ).Organic Facies . Such models are interesting. wind and water circulation patterns. if on the average only 1% of organic matter is preserved. After all.
The principal control on organic richness is the efficiency of preservation of organic matter in sedimentary environments. and we could coin the term dysoxic to describe the zone itself.8
monsoonal winds that drive surface waters away from the coast.2 mL/L. diagenesis is restricted to anaerobic processes.5 milliliters (mL) per liter (L)). ANOXIA. Anoxia is of tremendous importance in the preservation of organic matter in sediments. There are. However. microorganisms that utilize materials like sulfate or nitrate ions instead of molecular oxygen as electron acceptors in their metabolic processes. There are many more organic-rich facies resulting from excellent preservation than from extremely high productivity. and all the other factors that influence upwelling loci is severely limited. respectively. especially of woody origin. productivity is probably not as important a factor as preservation. soils. many species disappear. TOC values alone must therefore be used with caution. The term dysaerobic has been used to describe processes occurring in the transitional zone (0. All large organisms require oxygen in order to live. because marine organic matter is consumed preferentially by organisms. Secondly. some problems associated with their application. the simplest way to limit oxidation is to limit the supply of oxygen. because when the availability of oxygen is limited.2 mL/L. Thus if anoxia can develop. however. Three factors affect the preservation (or destruction) of organic matter: the concentration and nature of oxidizing agents.2 mL/L is called the anoxic zone. All these areas exhibit high productivity when upwelling occurs. its use in practice has been expanded to include very low oxygen levels as well. Anoxic sediments are not always easy to recognize. essentially the only viable organisms are those that we call anaerobes. and may in fact prove useful in future exploration efforts. and are usually limited in scope by the availability of sulfate or nitrate. and sediments is biological. the zone where oxygen falls below 0. First. the type of organic matter deposited. preservation of organic matter will be much enhanced. Of these. paleoclimatic conditions. landmasses. and the sediment-accumulation rate. Theoretical models have been developed to predict upwelling (and consequent productivity) in ancient seas from input data on continental configurations. At lower levels of dissolved oxygen. oxidizing agents are probably the most crucial factor. the remaining individuals often become dwarfed in an effort to survive in a hostile environment. although some species can tolerate extremely low oxygen levels (0. Its presence in
. At dissolved oxygen levels below about 0. and because most biological oxidation processes require molecular oxygen.2-0. and paleoclimates. These anaerobic processes are inefficient compared with aerobic diagenesis.5 mL/L). increasing preservation rates is a very efficient way to increase organic richness. Because most of the oxidation occurring in the water column. The presence of undegraded marine organic material is a strong indication of anoxia. Processes that occur in these two zones are called aerobic and anaerobic. especially in the Palaeozoic. the accuracy with which we can reconstruct continental positions. because some of the commonly used indicators of anoxia may be misleading. much oxic sediment also contains large amounts of organic matter." hut because of the radical change in biota that occurs at about 0. We call the zone in which oxygen contents are high the oxic zone. The term "anoxic" literally means "having no oxygen.
then permanent density stratification will arise as a result of temperature differences within the water column. It therefore behoves us to understand the conditions under which anoxia develops. the Elko Formation (Eocene/Oligocene. STAGNANT BASINS. although stunted burrows can be used as evidence of dysoxia. The ultimate implications of anoxia for petroleum exploration are great. denser waters remain at the bottom. This oxygen minimum develops when the rate of consumption of oxygen within that layer exceeds the rate of influx of oxygen to it. Color should be used mainly as a negative criterion: If a rock is not very. it is instructive to consider complete stagnation. 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. the presence of bioturbation indicates that the bottom waters were not anoxic. Lake deposits associated with continental rifting. anoxic sediments show preserved depositional laminae on a millimeter or submillimeter scale.9
rocks therefore indicates that diagenesis was stopped prematurely. Nevertheless. The cooler. that most of the world's oil was generated from source beds deposited under anoxic conditions. it may well have developed after burial. The laminae prove that burrowing fauna were absent. there is no guarantee that anoxia was present at the sea floor. anoxic sediments. Lack of communication between the layers prohibits replenishment of oxygen in the bottom layer.2 mL/L. very dark. Finally. most likely by absence of oxygen. it has been estimated. but limnic environments often are. Therefore. however. in fact. All anoxic sediments will be very dark gray or black when deposited. Depths in excess of 200 m are required to prevent mixing during storms. If an isolated body of water is deep enough. where photosynthesis and turbulence can no longer contribute oxygen to the water. Furthermore. and therefore that dissolved-oxygen levels were below 0. and both the waters in the bottom layer and the underlying sediments will become anoxic. OXYGEN-MINIMUM LAYER (OML). Truly stagnant basins are actually quite rare. once the original oxygen has been consumed in oxidizing organic matter. 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. and if the climate is subtropical or tropical. Many black rocks. are not rich in organic carbon. anoxia can be very local. it cannot represent an anoxic facies.Organic Facies . Although pyrite does indeed form under anoxic conditions. Among the ancient lake beds thought to have been deposited in permanently stratified waters are the well-known Green River Shale (middle Eocene. Lakes in failed rifts can also contain organic-rich. Marine basins are seldom isolated enough to fit well into the stagnant-basin model. and strata from several basins in China. especially during the Triassic along the margins of the developing Atlantic Ocean. Lakes of the Rift Valley of East Africa are excellent modern analogs receiving much attention from both researchers and explorationists at the present time. The supply of fresh oxygen is therefore limited to horizontal
. slow circulation or turnover of the water column occurs almost everywhere. Nevada). leading to the eventual development of a pycnocline (density interface) which prevents interchange between the two layers. Consumption of oxygen results from decay of dead organisms that have sunk from the photic zone above. and warm climates are necessary to avoid overturn caused by freeze-thaw cycles. are anoxic in some of the places where they have been penetrated. Conversely. and its presence indicates that the anaerobic reduction of sulfate ion did occur. they often owe their dark color to finely divided pyrite or to particular chert phases. The oxygen minimum layer usually begins immediately below the photic zone. Color is not a reliable indicator. Wyoming). no more oxygen can enter. The presence of pyrite itself can also be deceptive. particularly in understanding lacustrine beds.
its intensity varies greatly. high influxes of organic matter. and diminished bacterial activity. because of their connection with the open-marine realm. Coal Swamps. if the basin is deep enough. This depletion was probably the result of the complex interplay of several factors. because these horizontally moving waters also lie within the oxygen minimum layer. since most organic matter was destroyed within the overlying OML. Furthermore. which could be excellent hydrocarbon source rocks. Settings in which circulation is restricted are much more common than stagnant basins. Where the sill is shallow. in areas of poor circulation. mid-Cretaceous.. the shallowness of the swamps prevents the waters themselves from becoming anoxic. the oxygen they can contribute is limited. permanent density stratification will develop. High productivity reduces oxygen levels. In actuality there is a lazy turnover of the bottom waters. Wherever an intensely developed OML intersects the sediment-water interface. In an evaporitic environment (Karabogaz in the Caspian Sea) there is a net flow of water into the basin. as a result of diminished oxygen demand. Although circulation in coal swamps is generally sluggish. Anoxia
. and high hydrogen-sulfide concentrations create conditions poisonous to predators. but it is too slow to disturb the anoxia which develops in the bottom layer. The result is often deposition of organic-rich laminae within evaporites. when a major transgression had greatly increased the continental shelf area. Although an oxygen-minimum layer exists virtually everywhere in the ocean. 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. or as lateral facies equivalente thereof. Coal swamps can develop under a variety of conditions in both marine and non-marine environments. There are other ancient and modern examples of organic-rich rocks deposited under anoxic or near-anoxic conditions associated with OMLs. 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. Nutrients are concentrated by evaporation. Intensely developed OMLs occur in areas of high productivity and. whereas in a fluvially dominated system (Black Sea) the net flow of surface water is out over the sill. Below the OML oxygen levels again increase. It has been proposed that at certain times in the past (e. However. Shallow Silling. and grazers and predatory organism are eliminated by the high salinities.10
movement of oxygen-bearing waters. Large amounts of organic material are preserved in coal swamps as a result of the combined effects of poor water circulation. Late jurassic.g. the point of connection between the restricted area and the open-marine environment. It is not coincidental that these were times of deposition of large amounts of organic-rich rocks in many parts of the world. an upward expansion of the OML led to a tremendous increase in the surface area covered by anoxic bottom waters. In times like the mid-Cretaceous. sediments will be deposited under low-oxygen conditions. those environments can also incorporate the features of an oxygen-minimum-layer model. In contrast. including paleoclimate and water circulation. to a lesser extent. In either case.Organic Facies . During those times the OML expanded both upward and downward because of poor supply of oxygen to subsurface waters. Any organic matter arriving in those sediments will have an excellent chance to escape oxidation. Circulation is often restricted by the presence of a sill. Evaporitic environments combine the opportunity for abundant growth of algae with ideal conditions for preservation. RESTRICTED CIRCULATION. the waters entering or leaving the basin are near surface. foreset beds within the same system are leaner in organic matter because they are deposited above the OML. Shallowly silled basins often yield evaporites. with the bottom layer almost isolated from the open-marine waters. Late Devonian) the world oceans were severely depleted in dissolved oxygen.
as a result of more rapid removal of organic material from the zone of microbial diagenesis. Rapid settling of organic debris through the water column is also important. and low productivity in the overlying pelagic realm. and other oxidative processes. with their high concentrations of organic matter. Near-shore oxidizing facies sometimes have high TOC values. but it does spread that organic material through a larger volume of rock. lignitic. It may also contain very resistent organic debris derived from erosion of ancient rocks. Any extensive organic diagenesis is therefore likely to eliminate algal organic matter first. TYPE OF ORGANIC MATTER. at very high accumulation rate dilution may become a more important factor than increased preservation. because extensive decomposition occurs during its fall to the ocean floor. renders it of little nutritional value. much of the organic material that does reach the bottom in deep waters arrives in relatively large fecal pellets. Nitrogen and phosphorus are in particular demand. 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. Organic matter of algal (phytoplanktonic) origin is consumed more readily by organisms than are other types of organic material. TOC values increase as sediment-accumulation rates increase. and therefore wi11 contain primarily oxidized organic matter. Furthermore. and may include woody. or resinous material. because its chemical components are digestible and provide precisely the nutrients required by scavengers and predators. Dilution does not reduce the total amount of organic matter preserved. Coals are important source rocks for gas accumulations. Coals also accumulate very rapidly and. especially in structural (woody) material. Phenolic bactericides derived from lignin hinder bacterial decay in the water and throughout the sediment column. provide an ideal means of maintaining low-oxygen conditions. Rapid deposition of inorganic detritus is common in turbidites and in prodelta shales. That material which remains is dominantly of terrestrial origin.Organic Facies . Most depositional settings not specifically catalogued above will be more or less well oxygenated. Rapid burial is accomplished by a high influx of inorganic detritus. Oxic Settings. cuticular. thus preventing extensive diagenesis of such material. but their supposedly low potential for generating oil is to be reconsidered. The net result is a reduction in TOC values. Rapid sedimentation and burial con also enhance preservation. In fact.11
develops within the sediments rather than in the water column. Abyssal sediments are notoriously low in organic carbon as the result of the combined effects of high oxygen levels in abyssal waters. cellulosic. 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. all of which are chemically quite distinct from each other. biogenic inorganic sediment. forest fires. The hydrocarbon-source potential of all of these oxidizing facies is low. their virtual absence in much terrestrial organic material. or organic material. very slow sedimentation rates. and more favorable for gas than for oil.
Although high sediment-accumulation rates enhance preservation of organic matter. which settle several orders of magnitude faster than individual phytoplankton. RAPID SEDIMENTATION AND BURIAL.
It is important to be able to distinguish local anoxia or anoxia developed deep within sediments from anoxia induced by anoxic bottom waters. however. such models are not yet of much practical value for the distant past. dilution effects may lead to lower TOC values in spite of enhanced preservation rates.Organic Facies . Of these. Although certain periods undeniably contain more than their share of anoxic rocks. anoxia in bottom waters is a phenomenon whose effects we should learn to recognize in ancient rocks. As in the modern oceans. a strongly developed oxygen-minimum layer. such events were often interrupted for long periods before anoxia was reinduced. however. are not as strongly affected by dilution.
There are three principal factors that affect the amount of organic matter in sedimentary rocks: primary photosynthetic productivity. Productivity can be predicted by locating ancient sites of marine upwellings. The most reliable criteria for bottom-water anoxia are the preservation of fine depositional laminae. To derive maximum value from our analyses. where sediment-accumulation rates are directly proportional to organic-carbon-accumulation rates. including stagnancy or near-stagnancy. Models that integrate the concepts of organic richness with depositional cycles and facies analysis will be valuable tools for understanding hydrocarbon systems in basins. we should always strive to place the organic rich rocks in the larger context of basin evolution through time and space. Our ability to make accurate predictions is limited. Direct control of the anoxia was thus probably local.and atmospheric-circulation patterns. preservation is generally the most important. in contrast. Consequently. as a result of high productivity or sluggish circulation. and a very imperfect understanding of oceanic. Preservation is best accomplished where oxygen is excluded from bottom waters. Shales. however. anoxic sediments were deposited discontinuously through time and space. Facies changes from carbonates to shales may create large dilution effects that can be wrongly interpreted as indicating changes in oxygen levels. There are a number of mechanisms by which oxygen depletion may be fostered and maintained. lack of knowledge of seawater chemistry and nutrient availability at those times. Anoxic events in the past were probably not as large in scale or as long lasting as some workers have suggested. in contrast. Because of its role in creating rocks with excellent hydrocarbon-source potential. and dilution by inorganic material. Biogenic sediments. by uncertainties about exact continental positions and configurations in the past. in which the organic and inorganic materials arrive together. In biogenic sediments or coals.12
Dilution effects depend upon rock lithology. dilution is far less marked. If the rapidly accumulating sediment is mainly clastic. and rapid burial. effectiveness of preservation. It is often very difficult to separate the influences of these various factors in a particular depositional environment. show strong dilution effects when accumulation rates are very high. and the presence of high TOC values coupled with the occurrence of undegraded marine organic matter. Some of the commonly applied criteria are apt to be misleading. Rapid accumulation of sediment shortens the residence time of organic matter in the zone of diagenesis and thus promotes preservation.
Writing the detailed structure of a simple molecule like methane is no problem. Organic chemistry is thus the study of carboncontaining compounds. ethane. oxygen. two bonds. Carbon atoms like to form bonds with each other.
. This unique property of carbon is responsible for the existence of literally millions of different organic compounds. creating long chains and ring structures.
NAMES AND STRUCTURES HYDROCARBONS
In chemical terms a hydrocarbon is a compound containing only the elements carbon and hydrogen. One common convention is to represent all the hydrogen atoms attached to a given carbon atom by a single H. and indeed in every carbon compound (except a few highly unstable ones created only in laboratories). carbonates.13
3 . and cyclohexane. elsewhere in this text usage will vary. especially if one has to do it only occasionally. We can make other logical simplifications for longer carbon chains. sulfur. three bonds. If one wants to draw large molecules. and organic geochemistry the study of organic compounds present in geological environments. This usage is historical and does not imply that all such compounds are necessarily derived from living organisms. are termed organic. trace metals. Similarly.Organic Chemistry
Anyone who uses petroleum geochemistry must be familiar with basic chemical terminology. in which one must also learn all the reactions of many classes of compounds. the explicit inclusion of every atom and every bond becomes extremely tedious. Petroleum and natural gas are themselves often referred to as "hydrocarbons. The chemical reactions of interest to us are very few and are discussed only briefly. oxygen and sulfer. The structures of methane and ethane are thus represented by CH4 and CH3CH3 respectively.Organic Chemistry . using a subscript on the H to denote the total number of hydrogens around that atom. This objective is very different trom that of a normal course in organic chemistry. All compounds containing carbon atoms. The following representations of n-pentane are equivalent: CH3CH2CH2CH2CH3 or CH3(CH2)3CH3.
Examples of hydrocarbons are methane. In each of these compounds. except carbon dioxide. Several different types of shorthand have therefore developed to facilitate drawing organic molecules. every carbon atom forms four bonds. hydrogen always forms one bond. In this chapter we restrict the usage of the term hydrocarbon to the standard chemical one." but that usage is incorrect trom the chemist's point of view because those materials often contain substantial amounts of nitrogen. whose structures are shown below. and metal carbides. however. and nitrogen. as it does in the real world. 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. and other elements.
We have also seen that carbon atoms can be arranged in rings. and carbon-carbon bonds are shown as lines connecting those points. Hydrogen atoms and bonds to hydrogen atoms are not shown at all. Isoprenoids ranging in length from six to forty carbon atoms have been found in petroleum and rocks. but the prefixes denoting the number of carbon atoms in the other alkanes are derived from Greek numbers. Each carbon atom is represented by a point. is the adjectival form of the word methane. We have ahready encountered n-pentane. giving rise to a vast number of possible structures.Organic Chemistry . Many unsaturated compounds have carbon-carbon double
. Note that the name of each compound ends in -ane. That is. a CH3 (methyl) group is attached to the second carbon atom." The first four names are irregular. Branching can occur.14
An even quicker shorthand that uses no letters at all has evolved. Another important group of hydrocarbons is the unsaturates. The letter n stands for normal. Because we know that each carbon atom forms four bonds and each hydrogen atom forms one bond. Other adjectival forms are made by dropping the -ane ending and adding yl (for example. ethyl and propyl). In the case of 2methylhexane (C7H16) the basic structure is hexane. The term methyl. which. as in "alkane. Regular isoprenoids consist of a straight chain of carbon atoms with a methyl branch on every fourth carbon. are able to combine with additional hydrogen. 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. in contrast. The zigzag configuration illustrated for n-pentane is adopted to show clearly each carbon atom. because they are saturated with respect to hydrogen. no more hydrogen can be incorporated into the molecule without breaking it apart. For example. All the compounds mentioned above are called saturated hydrocarbons or saturates. The simplest series of hydrocarbons has linear structures. These cyclic compounds (called naphthenes) are named by counting the number of carbon atoms in the ring and attaching the prefix cyclo. simple inspection shows how mant' hydrogen atoms each carbon atom must have. these molecules are called n-alkanes or nparains. n-pentane and cyclohexane are represented by the line structures shown below. and indicates that there is no branching in the carbon chain. Among the most important branched hydrocarbons in organic geochemistry are the isoprenoids. the names of the other nine simplest n-alkanes are given in the following table. which we used earlier.
Among the most important NSO compounds are the asphaltenes. Polycyclic aromatic hydrocarbons having fused ring structures are quite common. the compounds in which they occur are called heterocompounds. these compounds are quite different trom the majority of the organic molecules found in living organisms. which are large. of which some are biogenic and others are formed during diagenesis. The hydrocarbons present in petroleum are mostly the end products of extensive degradation of biogenic molecules.Organic Chemistry . They are named in a similar manner to the alkanes.15
bonds. some complex hydrocarbons that are found in fossil organic material can be related directly to individual biological precursors. because the most common heteroatoms are nitrogen. A variety of reactions. propene (C3H6). except that the ending -ene indicates the presence of a double bond. Some aromatic molecules are very large. Although they are very important constituents of petroleum. they do not long persist in geologic environments. Many of the heterocompounds present in organisms are converted to hydrocarbons during diagenesis and catagenesis. Aromatics possess a system of alternating single and double bonds within a cyclic structure. they do not add hydrogen easily. Aromatics form an extremely important class of unsaturated hydrocarbons. Many common NSO compounds are not directly related to biogenic precursors. including hydrogenafion. converts alkenes to alkanes and cyclic compounds during diagenesis. At first glance aromatics appear to be nothing more than cyclic alkenes containing several double bonds. In the laboratory they are readily converted to alkanes by the addition of hydrogen in the presence of a catalyst. The circle indicates that the electrons in the double bonds are delocalized. The hydrocarbons we discussed so far are relatively simple molecules. and oxygen. Examples are ethene (C2H4) . the structures of which are shown below. By hydrogenation ethene thus reacts to form ethane. bitumen. In fact. and cyclohexene (C6H10). highly aromatic materials of
. which is an almost-endless sheet of aromatic rings. or other elements.
Because alkenes are highly reactive. It is this delocalization of electrons which makes aromatic compounds very stable. and kerogen are called heteroatoms. Most biological molecules are larger and more complex than the simple hydrocarbons. The extreme case is graphite. A simplified notation for drawing these molecules permits us to represent the double-bond system by a circle within the ring. that is. they are free to move throughout the cyclic system instead of being held between two particular carbon atoms. sulfur. nitrogen. Their stability permits aromatics to be important constituents of oils and sediments. Although they are unsaturated. Heterocompounds are also called NSO compounds.
Atoms other than hydrogen and carbon that occur in petroleum. the majority contain oxygen. these compounds are called alkenes. Fossil organic matter often contains a vide variety of heterocompounds. sulfur. phosphorus. but they actually have completely different chemical properties from alkenes and are unusually stable.
They have many characteristics in common with kerogen. sugars. It is a polymer consisting of many repetitions and combinations of three basic aromatic subunits. it is an important constituent of terrestrial organic matter. and cellulose. Many nonhydrocarbon molecules common to living organisms are also present in sediments. Lignin is an important component of wood. most carbohydrates are attacked readily by microorganisms. Like lignin. the latter is the most abundant organic compound in the biosphere.Organic Chemistry .000 atomic mass units. Carbohydrates include starch. and thus are seldom preserved in sediments (exceptions occur in shell material and in bones.16
varying structure. lignin is rather resistant to degradation. Upon decomposition lignin forms phenolic compounds. but asphaltene molecules are smaller and more aromatic than most kerogens. providing much of the structural support for large land plants. carbohydrates. Because phenols are potent bactericides. Lignin and cellulose are major constituents of humic coals. which are aromatics having a hydroxyl group (OH) attached. and amino acids. where small amounts of preserved amino acids can be used to date specimens)
. Lignin monomers are linked topether to form molecules having molecular weights from 3000 to 10. however. Among these are lignin. and thus tends to become concentrated as other organic matter is decomposed. They are rapidly metabolized by virtually all organisms. Amino acids are the building blocks of proteins. Although cellulose is quite resistant to decomposition under some conditions.
when the chemical and biological destruction and transformation of organic tissues begin. Subsurface heating causes chemical reactions that break off small fragments of the kerogen as oil or gas molecules. Humic coals are best thought of as kerogens formed mainly from landplant material without codeposition of much mineral matter.Kerogen . A basic understanding of how kerogen is formed and transformed in the subsurface is therefore important in understanding how and where hydrocarbons are generated. will be discussed in a following chapter. 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. develop after tens or hundreds of meters of burial. Kerogen composition is also affected by thermal maturation processes (catagenesis and metagenesis) that alter the original kerogen. whether these hydrocarbons are mainly oil or gas. soils.
The process of kerogen formation actually begins during senescence of organisms. The term kerogen was originally coined to describe the organic matter in oil shales that yielded oil upon retorting. Algal (boghead) coals are formed in environments where the source phytoplankton lack both calcareous and siliceous skeletal components. Diagenetic and catagenetic histories of a kerogen. These geopolymers are the precursors for kerogen but are not yet true kerogens. Each kerogen molecule is unique.17
4 . Lack of solubility is a direct result of the large size of kerogen molecules. Coals are a subcategory of kerogen. and sediments. Oil shales. and natural gas. strongly influence the ability of the kerogen to generate oil and gas. oil. The smallest of these geopolymers are usually called fulvic acids. Coals and oil shales should therefore be viewed merely as sedimentary rocks containing special types of kerogens in very high concentrations. humic acids. which have molecular weights of several thousand or more. and still larger ones. as well as the nature of the organic matter from which it was formed. and how much oil or gas can be expected. in contrast. having very high molecular weights. because it has patchwork structures formed by the random combination of many small molecular fragments. Large organic biopolymers of highly regular structure (proteins and carbohydrates. as well as dispersed organic matter in sedimentary rocks. with some of the inorganic matrix often being contributed by the algae themselves. carbon dioxide. the geopolymers become larger. humins. Today it is used to describe the insoluble organic material in both coals and oil shales. During the course of diagenesis in the water column. and the individual component parts are either destroyed or used to construct new geopolymers. have more mineral matter than algal coals. The detailed chemistry of kerogen formation need not concern us greatly. Diagenesis results mainly in loss of water. and ammonia from the original geopolymers. for example) are partially or completely dismantled. more complex. The residual kerogens also undergo important changes. 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. If anaerobic sulfate
. which are reflected in their chemical and physical properties. slightly larger ones. 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. and less regular in structure. The soluble portion. large molecules that have no regular or biologically defined structure. True kerogens.Kerogen
Kerogen is normally defined as that portion of the organic matter present in sedimentary rocks that is insoluble in ordinary organic solvents. called bitumen.
In a low-oxygen (reducing) environment. Microorganisms prefer to attack small molecules that are biogenic. or at least look very much like biogenic molecules. which are highly reactive. In an oxidizing environment many of the small biogenic molecules will be attacked by bacteria before they can form geopolymers. One way that we can begin is by classifying kerogens into a few general types. and if the sediments are depleted in heavy-metal ions (which is often the case in nonclastic sediments but is seldom true in shales). Carboncarbon double bonds. Geopolymers are more or less immune to bacterial degradation. Those kerogens formed under oxidizing conditions. are converted into saturated or cyclic structures. They identified three main types of kerogen (called Types I. large amounts of sulfur may become incorporated into the kerogen structure.Kerogen . What is within our reach. in contrast. and their organic precursors
Transformation of organic material in sediments and sedimentary rocks. Most organic oxidation in sedimentary environments is microbially mediated.18
reduction is occurring in the sediments. Kerogen formation competes with the destruction of organic matter by oxidative processes. About a decade ago workers at the French Petroleum Institute developed a useful scheme for describing kerogens that is still the standard today.
Because each kerogen molecule is unique. because the bacterial enzyme systems do not know how to attack them. the macerals that they are composed of. II. 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. it would not be of great and direct significance to exploration geologists. Even if such a description were possible. Subsequent investigations have identified Type IV kerogen as well. and III) and have studied the chemical characteristics and the nature of the organisms from which all types of kerogens were derived.
. therefore. and ultimately of much greater practical value. contain mainly the most resistant types of biogenic molecules that were ignored by microorganisms during diagenesis. in contrast. Kerogens formed under reducing conditions will be composed of fragments of many kinds of biogenic molecules. it is somewhat fruitless to attempt a detailed discussion of the chemical composition of kerogens. better organic preservation.
The four types of kerogen. the subdued level of bacterial activity allows more time for the formation of geopolymers and.
They also include contributions from bacterial-cell lipids. Cellulose and lignin are major contributors. Type III kerogens are composed of terrestrial organic material that is lacking in fatty or waxy components. successively. leaf waxes. Type I (algal) kerogens have the highest hydrogen contents because they have few rings or aromatic structures. and Colorado. Utah. Extensive interest in those oilshale deposits has led to many investigations of the Green River Shale kerogens and has given Type I kerogens much more publicity than their general geological importance warrants. Type IV kerogens. pollen and spores. in contrast.
. contain far less oxygen because they were formed from oxygen-poor lipid materials. are normally considered to generate mainly gas. Type III (humic) kerogens. catagenesis. and fossil resin. of middle Eocene age. Most Type II kerogens are found in marine sediments deposited under reducing conditions. in contrast. because they all have great capacities to generate liquid hydrocarbons. despite their very disparate origins. from Wyoming. Occurrences of Type I kerogens are limited to anoxic lakes and to a few unusual marine environments. Type I kerogens have high generative capacities for liquid hydrocarbons. The shaded areas approximately represent diagenesis. and metagenesis. Hydrogen contents of immature kerogens (expressed as atomic H/C ratios) correlate with kerogen type. unless they have small inclusions of Type II material. Type IV kerogens contain mainly reworked organic debris and highly oxidized material of various origins. have lower hydrogen contents because they contain extensive aromatic systems. Type II (liptinitic) kerogens are also high in hydrogen. The best-known example is the Green River Shale. including marine algae. phenols. The various Type II kerogens are grouped together. and carbohydrates. Type III kerogens have high oxygen contents because they are formed from lignin. Type III kerogens have much lower hydrocarbon-generative capacities than do Type II kerogens and. Type IV kerogens are highly oxidized and therefore contain large amounts of oxygen. Heteroatom contents of kerogens also vary with kerogen type. Type II kerogens arise from several very different sources.Kerogen . have the lowest hydrogen contents.19
Type I kerogen is quite rare because it is derived principally from lacustrine algae.
Van Krevelen diagram showing maturation pathways for Types 1 to IV kerogens as traced by changes in atomic HIC and OIC ratios. Type I and Type II kerogens. In the immature state. They are generally considered to have essentially no hydrocarbon-source potential. which mainly contain polycyclic aromatic systems. cellulose.
especially when we are discussing both aspects simultaneously. forcing us to make assumptions about the source organisms. but they really represent different aspects of the same process. In many cases the original cellular structure is still recognizable. they are to kerogen what minerals are to a rock. because fresh waters are usually low in sulfate. represents drygas generation. Kerogen sulfur. It is possible to make a reasonably good correlation between kerogen type based on chemical characteristics and kerogen type based on visual appearance. called catagenesis and metagenesis.
. in some cases. they are not precisely equivalent. Although the terms catagenesis and oil generation are often used synonymously. but it also continues through the metamorphic stage.20
Sulfur and nitrogen contents of kerogens are also variable and. The small molecules eventually become petroleum and natural gas. Most high-nitrogen kerogens were therefore deposited under anoxic conditions where diagenesis was severely limited. metagenesis is not equivalent to "metamorphism. Despite its name. is derived mainly from sulfate that was reduced by anaerobic bacteria.
KEROGEN MATURATION INTRODUCTION
Very important changes. because there is not a perfect biological separation of the various types of living organic matter. Catagenesis and hydrocarbon generation occur concurrently. The kerogen in a given sedimentary rock includes many individual particles that are often derived from a variety of sources. in contrast. The different types of kerogen particles are called macerals.Kerogen . In principle. which is destroyed rapidly during diagenesis. most terrestrially influenced kerogens are low in nitrogen. break off small molecules and leave behind a more resistant kerogen residue. High-sulfur kerogens (and coals) are almost always associated with marine deposition. a term taken trom coal petrology. Thermal decomposition reactions. anoxic. the materials from which a maceral was derived. Metagenesis. In this text we shall use the terms somewhat interchangeably. Microscopic organic analysis has reached a fairly high level of refinement and is often capable of assessing kerogen type with good accuracy. Because lignins and carbohydrates contain little nitrogen. The biggest problem comes in identifying Type III kerogen. Catagenesis refers to transformations of kerogen molecules. marine. Thus few kerogens consist of a single maceral type. wherever possible. occur when a kerogen is subjected to high temperatures over long periods of time. In others the original fabric has disappeared completely. The correspondence is not perfect. however. Maceral names were developed by coal petrologists to describe. Nitrogen is derived mainly from proteinaceous material. proving the origin of the particle. whereas hydrocarbon generation focuses on the production of hydrocarbon molecules. Macerals are essentially organic minerals. 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. Many high-sulfur kerogens are also high in nitrogen. A list of the most common macerals and their precursors is given in the table presented earlier in this chapter. which occurs after catagenesis. Kerogen types are defined by the morphologies of the kerogen particles. they represent fundamentally different perspectives. called maturation. interrelated. however. By convention the term catagenesis usually refers to the stages of kerogen decomposition during which oil and wet gas are produced. nonclastic sediments)." Metagenesis begins long before true rock metamorphism. Sulfur is only incorporated into kerogens in large quantities where sulfate reduction is extensive and where Fe +2 ions are absent (organic-rich. 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.
Kerogen particles become darker during catagenesis and metagenesis. It is impossible to set precise and universal temperature limits for catagenesis. as evidenced by low maturity. Because many of the light product molecules are rich in hydrogen. after hydrogen loss is well advanced. The composition of the products (bitumen. but it also states that at any temperature above absolute zero reactions will be occurring at some definable rate. As we saw earlier. the residual kerogen gradually becomes more aromatic and hydrogen poor as catagenesis proceeds. The most important implication of these chemical changes is that the remaining hydrocarbongenerative capacity of a kerogen decreases during catagenesis and metagenesis. In the late stages of maturity. Types I. Nitrogen loss occurs primarily during late catagenesis or metagenesis. oil. and thus are not necessarily valid indicators of hydrocarbon generation. thus allowing us to judge the extent to which kerogen maturation has proceeded.
EFFECTS OF MATURATION ON KEROGENS
Kerogen undergoes important and detectable changes during catagenesis and metagenesis. Although it is obvious that many measurable changes in kerogens are related to hydrocarbon generation. Old rocks will often generate hydrocarbons at significantly lower temperatures than young rocks. Furthermore. II. These reactions are intimately related to important changes in the chemical structure of kerogen. possessing essentially no remaining hydrocarbon generative capacity. simply because the longer time available compensates for lower temperatures. There is therefore no necessary cause-and-effect relationship
. including the Miocene Monterey Formation of southern California. is to monitor hydrocarbon generation. 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. however. provided that the hydrogen content of the kerogen was known prior to the onset of catagenesis. even if drastic decreases in temperature occur. high-sulfur oils found in a number of areas. the rates of catagenesis are generally not important at temperatures below about 70° C. and III kerogens will therefore be very similar chemically. Some of these changes can be measured quantitatively. 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. All kerogens become increasingly aromatic and depleted in hydrogen and oxygen during thermal maturation. of course. much of the sulfur is lost in the earliest stages of catagenesis. The real reason for following kerogen catagenesis.Kerogen . the cracking of any organic molecule requires hydrogen. much as a cookie browns during baking. but they are not necessarily identical with hydrocarbon generation. Furthermore. Nitrogen and sulfur are also lost from kerogens during catagenesis. Kerogen maturation is not a reversible process-any more than baking a cake is reversible.21
This chapter will focus on those changes in the residual kerogen that accompany catagenesis. 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. the more hydrocarbons it can yield during cracking. There is a steady color progression yellow-goldenorange-light brown-dark brownblack as a result of polymerization and aromatization reactions. and gas) will be discussed in a following chapter. In contrast. For practical purposes. the chemical process of maturation never stops completely. it is also true that other changes in kerogen properties have little or nothing to do with it. This complex interplay between the effects of time and temperature on maturity is discussed in a later chapter. Chemical reaction-rate theory requires that the rates of reactions decrease as temperature decreases. The more hydrogen a kerogen contains. because time also plays a role.
The intensity and wavelength of the fluorescente are functions of kerogen maturity. Both curves are highly
. small molecules are broken off the kerogen matrix. its structure becomes more ordered. As kerogen matures and becomes more aromatic. Some of these are hydrocarbons. because the flat aromatic sheets can stack neatly. Except for darkening. and which can be used to gauge the extent of molecular reorganization. Some properties of kerogen change very little during catagenesis. The more random a kerogen's structure.
As kerogen catagenesis occurs. during metagenesis the chief product is methane. One property that is strongly affected. Free-radical concentrations can be measured by electron-spin resonance. there would be a large and continuous build-up of bitumen in the rock as a result of catagenetic decomposition of kerogen. which are unpaired electrons not yet involved in chemical honds. Kerogens often fluoresce when irradiated.
Plot of bitumen generation as a function of maturity (dashed fine) compared to bitumen remaining in rock (solid line). Kerogens. resulting in lower bitumen contents in the source. These small compounds are much more mobile than the kerogen molecules and are the direct precursors of oil and gas. Cracking often produces free radicals. What actually occurs. Because coal rank is merely a measure of coal maturity.22
between kerogen darkening and hydrocarbon generation. called vitrinite reflectance. somewhat beyond the oil-generation window. has been widely and successfully applied in assessing kerogen maturity. the technique. especially highly aromatic ones. A general name tor these molecules is bitumen. is that some of the bitumen is expelled from the source rock or cracked to gas. carbon-isotopic compositions of kerogens are affected little by maturation. If neither expulsion from the source rock nor cracking of bitumen occurred. while others are small heterocompounds. however. and because vitrinite particles also occur in kerogens. contain large numbers of unpaired electrons. and the less it will be reflected.Kerogen . For example. Bitumen generation occurs mainly during catagenesis. and no guarantee that a particular kerogen color always heralds the onset of oil generation. the more an incident light beam will be scattered. is the ability of kerogen particles to reflect incident light coherently. the visual appearance of kerogen also does not change during catagenesis: kerogen types are generally recognizable until the particles become black and opaque. The difference between the two curves represents bitumen expelled from the rock or cracked to light hydrocarbons. 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 concentration of free radicals in a given kerogen has been found to increase with increasing maturity. These structural reorganizations bring about changes in physical properties of kerogens.
Rich rocks will become overpressured earlier than lean ones and thus will also expel hydrocarbons earlier. Many workers now believe that microfracturing of source rocks is very important tor hydrocarbon expulsion. Sulfur-rich kerogens decompose easily because carbon-sulfur hbonds are weaker than any bonds in sulfur-poor kerogens. including rock physics and organic-geochemical considerations. The chemical composition and morphology of kerogen macerals depend both on the type of original organic matter and on diagenetic transformations. we cannot always define the limits of hydrocarbon generation with great confidence. Given the significant chemical differences among the various types of kerogens.23
idealized. Numerous methods exist for tracing the history of a kerogen and determining its original chemical and physical characteristics. Thus. although we know that oil generation does occur during the phase we call catagenesis. hydrogen-poor. Resinite consists of polymerized terpanes (ten-carbon isoprenoids) that can decompose easily by reversing the polymerization process. The chemical composition of a kerogen controls the timing of hydrocarbon generation and the type of products obtained. but none of these measurements is closely linked to the actual process of hydrocarbon generation. In very lean rocks expulsion may occur so late that cracking of the generated bitumen is competitive with expulsion. because natural variations among samples cause much scatter in experimental data. when large geopolymers are created from biological molecules. Resinite and sulfur-rich kerogens are able to generate liquid hydrocarbons earlier than other kerogens because of the particular chemical reactions occurring in those two materials. Catagenesis of kerogen produces a more aromatic. whereas those kerogens that contain few lipids will generate mainly gas.
. as measured by parameters such as vitrinite reflectance. high-sulfur oils at low levels of maturity. Kerogens formed from lipid-rich organic material are likely to generate liquid hydrocarbons. Conversely. this result is hardly surprising. Microfracturing is related to overpressuring.
Kerogen begins to form during early diagenesis. Other kerogens usually follow a more traditional model. which in turn is partly attributed to hydrocarbon generation itself. those rocks that generate few hydrocarbons may not expel them until they have been cracked to gas. We shall consider the latter briefly here. however. High-sulfur kerogens generate heavy. Several methods exist for estimating the extent to which hydrocarbon generation has occurred in a given kerogen. residual kerogen as well as small molecules that are the direct precursors for petroleum and natural gas.Kerogen . In such cases the expelled products will be mainly gas. Kerogens formed from resinite will generate condensates or light oils quite early. Effective generation of hydrocarbons requires that the generated products be expelled from the source-rock matrix and migrated to a trap. It has become apparent in recent years that not all kerogens generate hydrocarbons at the same catagenetic levels. Candidates for early expulsion would be very organic rich rocks and those containing resinite or high-sulfur kerogens. Source rocks that generate large amounts of hydrocarbons early are likely to expel those hydrocarbons early. Timing and efficiency of expulsion depend on a number of factors.
There is no doubt that they are related. Maturity also exerts control over bitumen and petroleum composition. The influence of the lithologies of source and reservoir rocks on these compositional changes is poorly understood. while others are only trace contributors. The large sizes of asphaltene units render
. have been studied in petroleums. Such correlations can be particularly useful in establishing genetic relationships among samples. Few of these heterocompounds have been studied carefully. A second fraction consists of aromatic hydrocarbons and some light sulfur-containing compounds. are more commonly studied. many unanswered questions remain about the processes that transform bitumen into petroleum. Bitumen and petroleum compositions can also be used as tools in correlating samples with each other. highly aromatic asphaltene molecules that are often rich in heteroatoms. particularly those derived from diterpanes. however.24
Bitumen. Asphaltenes tend to aggregate into stacks because of their planarity. contains a wide variety of small and medium-sized molecules with one or more heteroatoms. variously called polars. In order to understand bitumen and petroleum compositions and to use them for exploration. Most of the NSO compounds appear in the remaining two fractions. and how much is due to physical separation of chemical compounds having very different properties. Heavier aromatic and naphthenoaromatic hydrocarbons. bitumen is almost universally accepted as the direct precursor for petroleum. This chapter will compare and contrast bitumen and petroleum compositions and examine the factors responsible for the observed differences. branched hydrocarbons (including isoprenoids). Each of the fractions contains certain types of chemical compounds. The lighter of these fractions. and Natural Gas -
5 . and cyclics. and form complexes with molecular weights of perhaps 50. like benzene and toluene. triterpanes. but these compounds are lost from bitumens during evaporation of the solvent used in extracting the bitumen from the rock. Reservoir transformations in some cases greatly affect oil composition and properties. but we are not certain whether they occur mainly within the source rock or during migration through the reservoir rock. NSOs.Bitumen. 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.
COMPOUNDS PRESENT IN BITUMEN AND PETROLEUM GENERAL CLASSES OF COMPOUNDS
Both bitumen and petroleum contain a very large number of different chemical compounds. However. One fraction consists mainly of saturated hydrocarbons. Major compositional changes occur in going from bitumen to petroleum. Petroleum.000. Both bitumens and petroleums exhibit a wide range of compositions. n-alkanes. but they also exhibit many important differences. and steranes. Petroleum. Much of this variety is related to source-rock facies and the composition of the kerogens that generated the bitumens. Some of these are present in relatively large quantities. we first separate a crude oil or a bitumen into several fractions having distinct properties. and resins. and Natural Gas
Petroleum obtained from reservoir rocks and bitumen extracted from fine-grained rocks have many similarities. indeed. Light aromatic hydrocarbons. Saturated hydrocarbons are the most thoroughly studied of the components of petroleum and bitumen because they are the easiest to work with analytically. The final fraction contains very large. In order to investigate the individual compounds present. We also do not know how much of the change involves chemical reactions.
the CPI is greater than 1. especially 23. where input of terrestrial n-alkanes is minimal and diagenetic conditions are highly reducing.0. In most cases. or members of the n-alkane series. CPI values can therefore
Biomarkers. however. These compounds. They are. or CPI. and by their catagenetic formation from long-chain compounds such as fatty acids and alcohols. In a few cases specific precursor organisms or molecules can be identified. 29. marine algae produce n-alkanes that have a maximum in their distribution at C-17 or C22. and 31 atoms. an abbreviation for biological markers. In contrast. the lower-carbon homologs are given more weight in the calculation. which are derived from biogenic precursor molecules. Petroleum. Many sediments. The most useful biomarkers serve as indicators of the organisms from which the bitumen or petroleum was derived. Many of the compounds and classes of compounds that we find in crude oils and bitumens are called biomarkers. depending upon the species present. although we know for certain that the biomarker molecule is biogenic. 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. If the number of odd. Other compounds. However. was developed as a measure of the strength of the odd-carbon predominance in n-alkanes over the even alkanes (in the series from 23 upwards). For the most part n-alkanes present in terrestrial plants have odd numbers of carbon atoms. These n-alkanes are believed to be formed by hydrogenation (reduction) of longchain fatty acids and alcohols having even numbers of carbon atoms. Another important indication of the origin of n-alkanes is the distribution of individual homologs. however. even-carbon homologs predominate as strongly as do the oddcarbon homologs among the n-alkanes. are essentially molecular fossils. we are unable to use it as an "index fossil" for specific organisms. and Natural Gas . If odd-carbon homologs predominate.Bitumen.or even-carbon homologs is evident. Their n-alkane distributions reflect this mix. and no preference for either odd. 27. such as pentane or propane. the CPI is 1. The average of two ranges is taken to minimize bias produced by the generally decreasing n-alkane concentrations with increasing number of carbon atoms.and even-carbon members is equal. Their high concentration in bitumens and oils is best explained by their existence in plant and algal lipids. receive contributions of n-alkanes from both terrestrial and marine sources. of biological origin.) Even-carbon preferences occur principally in evaporitic and carbonate sediments.25
them insoluble in light solvents. of course. because the concentration of n-alkanes often decreases with increasing carbon number.
FACTORS AFFECTING COMPOSITION OF BITUMEN AND PETROLEUM SOURCE AND DIAGENESIS
Biomarkers n-Alkanes were among the first biomarkers to be studied extensively. 25. asphaltene molecules have not been studied in detail. Because of their molecular complexity and heterogeneity. (Among the acids and alcohols present in living organisms. Asphaltenes can thus be removed from oils or bitumens in the laboratory or refinery by adding a light hydrocarbon. The distributions are quite sharp.0. Sediments are also known that exhibit a strong preference for n-alkanes having an even number of carbon atoms. or of the diagenetic conditions under which the organic matter was buried. whereas in other instances we may be able to limit the possible precursors to only a few species. but their sources are simply no longer recognizable due to diagenetic and catagenetic transformations. Carbon Preference Index.
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.
it involves expulsion of hydrocarbons from their fine-grained. During intense hydrocarbon generation. Traps are the means by which migration is stopped and accumulation occurs. whereas accumulation of hydrocarbons requires concentration. oil-phase expulsion. and pressure release can be repeated. it is probably most effective in immature rocks. lowpermeability source rock into a carrier bed having much greater permeability. microfracturing occurs. The hydrocarbons within the pores then become isolated again because of the impermeability of the waterwet source rocks to hydrocarbons. Each of these steps is quite distinct from the others. where pre-existing light hydrocarbons bleed out of the rocks prior to the onset of significant generation and expulsion. the microfractures heal. Diffusion has been shown to be active on at least a minor scale and over short distances in carefully studied cores. Momper's value has been widely accepted as a reasonable average. Today there are only three mechanisms of primary migration that are given serious consideration by most petroleum geochemists: diffusion. microfracturing. Laminated source rocks may therefore expel hydrocarbons with greater efficiency than massive rocks. any contribution by diffusion will be overwhelmed by that from other expulsion mechanisms. particularly along lines of weakness such as bedding planes. There appear to be three distinct ways in which oilphase expulsion can occur. An important implication of the microfracturing model is that expulsion cannot take place until the strength of the source rock has been exceeded. Once the internal pressure has returned to normal. but those that have been discounted will not be discussed here. and overpressuring commences anew. Secondary migration is the movement of oil and gas within this carrier bed. In order to understand the complex sequence of events that we call migration. where they can be preserved over long periods of time. Many cycles of pressure buildup. The main problem with diffusion as an important mechanism of migration is that diffusion is by definition a dispersive force.Migration . Based on empirical evidence. Primary migration is the first phase of the migration process. we must look at each of these steps separately. One occurs most commonly as a result of microfracturing induced by overpressuring during hydrocarbon generation. Accumulation is the concentration of migrated hydrocarbons in a relatively immobile configuration. Although the exact threshold value must vary considerably as a function of rock lithology and other factors. Diffusion would therefore have to be coupled with a powerful concentrating force to yield accumulations of appreciable size.Migration
Migration is the movement of oil and gas within the subsurface. and solution in gas.29
6 . expulsion. Momper (1978) suggested that in most cases no microfracturing or expulsion could occur until a threshold amount of bitumen had been generated in the source rock.
. This chapter wi11 not go into the physics and chemistry of migration in detail. Furthermore. When the internal pressures exceed the strength of the rock. By far the most popular mechanism invoked today to explain primary migration is expulsion of hydrocarbons in a hydrophobic (oily) phase. Its importance is probably limited to the edges of thick units or to thin source beds. but will describe the most widely held views on the dominant mechanisms of primary and secondary migration and accumulation.
PRIMARY MIGRATION MECHANISMS
Many theories about primary migration (expulsion) have been popular at various times.
Because the driving force for microfracture-induced primary migration is pressure release. A second way in which oil-phase expulsion can occur is from very organic-rich rocks prior to the onset of strong hydrocarbon generation. but also an "exit tax.30
Once the threshold has been exceeded." We can only estimate the fraction of the bitumen left in the source rock during microfractureinduced expulsion. but the mechanism by which overpressuring is achieved is not understood. In most cases hydrocarbons are generated within short distances of viable secondary-migration conduits. it would be expected only in the late stages of catagenesis or in source rocks capable of generating mainly gas. depending upon the carrier-bed characteristics of the surrounding rocks. Finally. Such a phase could only exist where the amount of gas far exceeds the amount of liquid hydrocarbons. hydrocarbons will be expelled in any direction that offers a lower pressure than that in the source rock. expulsion of oil dissolved in gas. Primary migration is difficult and slow. unfractured source-rock units are relatively rare. Because the source rock is overpressured.
. expulsion can be lateral. we conclude that solution in gas is a minor mechanism for oil expulsion. Thus primary migration ends whenever a permeable conduit for secondary migration is reached. This type of expulsion is probably only operative in very rich source rocks during the main phase of oil generation. but a large proportion of NSO compounds and heavier hydrocarbons are left behind. Of course. Sand stringers within shale units can provide secondary migration conduits for hydrocarbons sourced in the shales. 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. By comparing the average hydrocarbon compositions of bitumen and crude oil. where they do exist. The third mechanism. also make excellent secondary-migration pathways. Thus inefficiency of expulsion is responsible for much of the difference in composition of bitumen and petroleum that we noted earlier. Massive. therefore. upward. primary migration may be of poor efficiency. In most cases the distances of primary migration are probably between 10 centimetres and 100 m.
DISTANCE AND DIRECTION
The distances traversed by hydrocarbons during primary migration are short. Therefore the threshold must represent not only a hurdle to be cleared by the bitumen before it can leave the source rock. Thus a source rock lying between two sands will expel hydrocarbons into both carrier beds. the migrating fluids will take them. or downward. Fracture and joint systems. As soon as easier paths become available. this early expulsion mechanism seems to be limited to rocks having very high original contents of lipids. and assuming that expulsion of hydrocarbons is ten times as efficient as expulsion of NSO compounds. we can estimate that once the expulsion threshold is reached the expulsion efficiency for bitumen is about 50%. Primary migration is unquestionably the most difficult part of the entire migration process. but it does give some idea of the efficiency of expulsion.Migration . requires that there be a separate gas phase. This expulsion process probably releases internal pressures in the rock. Therefore. most of the hydrocarbons are expelled. Expulsion of hydrocarbons is facilitated because water-mineral and water-water interactions no longer need be overcome. because petroleum is being forced through rocks having low matrix permeabilities. this approach is rather approximate. particularly in brittle carbonate and opal-chert source rocks. oil-phase expulsion can take place when bitumen forms a continuous network that replaces water as the wetting agent in the source rock.
Opposing the buoyancy is capillary-entry pressure. the pore throat is very tiny or if the buoyant force is small. These modifications to the overall scheme are probably minor. secondary migration will occur both laterally and vertically. whereas capillary-entry pressure retards or stops it. Buoyancy promotes migration. we say that accumulation has occurred. and becomes stuck until either the buoyant force or the capillary entry pressure changes. the globule will squeeze into the pore throat and continue moving upward. and therefore are more buoyant. secondary migration will cease until either the capillary-entry pressure is reduced or the buoyant force is increased. 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. hydrodynamic flow. Where faulting or facies changes create impassable barriers (capillary-entry pressure exceeds buoyant force). Hydrocarbons are thus capable of displacing water downward and moving upward themselves. but it is not essential and does not change our basic model. however. which is resistance to entry of the hydrocarbon globule or stringer into pore throats. This fact has important implications for tracing migration pathways through a thick conduit. 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.
Retardatin of buoyant movement as an oil globule (X) is deformed to fit in to a narrow pore throat (Y). Structural contours on the top of the carrier bed will
. the more deformation is required. subsequent movement of the hydrocarbons will be driven by buoyancy.Migration . If water is flowing in the subsurface in the same direction as hydrocarbons are moving by buoyancy. That is. the globule must deform to squeeze into the pore. If the capillary-entry pressure exceeds the buoyant force. can modify hydrocarbon movement. The upward buoyant force is partly or completely opposed by the capillary-entry pressure. then the rate of hydrocarbon transport will be retarded. requiring only the existence of two forces. migration may have to proceed at an oblique angle to structural contours.
DISTANCE AND DIRECTION
Secondary migration occurs preferentially in the direction that offers the greatest buoyant advantage. Within massive sandstone. If the upward force of buoyancy is large enough. the force required to deform the oil globule enough to enter the pore throat. This model is very simple. if bulk water movement opposes the direction of buoyant movement. A third force-namely. The smaller the pore throat. Hydrocarbons are almost all less dense than formation waters. then the rate of hydrocarbon movement should be enhanced somewhat. When hydrocarbons cease moving. In contrast. If. Whenever a pore throat narrower than the globule is encountered.31
SECONDARY MIGRATION MECHANISM
Once hydrocarbons are expelled from the source rock in a separate hydrocarbon phase into a secondary-migration conduit. 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.
by definition. Indeed. There is no a priori reason why secondary migration cannot be a very-long-distance phenomenon. can offer possible pathways (although sometimes rather tortuous ones) for vertical migration.
In the old days. but also because an active fault or the brecciated zone adjacent to a fault may itself have high permeability. large drainage areas and chances for very large accumulations. This model greatly simplifies the problem of accumulation.32
in general be more useful than contours on its base. Nevertheless. and has provided as carrier beds continuous blankets of sand juxtaposed with these source rocks. 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). Vertical migration can also occur across formations. Today we believe that hydrocarbons migrate as a separate phase. the largest hydrocarbon deposits known. Migration updip within a single stratum can accomplish a large amount of "vertical" migration rather painlessly. Lack of long-distance migration opportunities implies that supergiant and giant accumulations are far less likely and that exploration targets will be smaller. Hydrocarbons had to remain in solution until they reached the trap. Faults may play an important role in vertical migration. they are rare for very good geological reasons: they occur in extremely stable tectonic settings where major but gentle downwarping has deposited and matured huge volumes of source rocks. Most basins. Various mechanisms for exsolution were proposed to explain how all this was supposed to happen. Cap rocks having low
. Much more common. at which time they suddenly became immiscible with the water and formed a separate hydrocarbon phase. for example. because now accumulation can occur where the buoyancy-driven movement of the hydrocarbon phase is stopped or even strongly impeded. all must have migrated long distances. as a result of both tectonic disruption and facies changes related to tectonic events. however. However. and the Saudi Arabian crude oils. Stacked sands in a paleodelta.Migration . when migration was thought to occur mainly in water solution. distances of several thousand feet are not unheard of. Drainage area is one of the most important factors influencing the size of hydrocarbon accumulations. are broken up tectonically and have poor lateral continuity of carrier beds. Long-distance migration implies. Lateral migration is therefore often stymied. not only because they often juxtapose carrier beds from different stratigraphic horizons. 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 across stratigraphic boundaries is more difficult. the heavy oils in the Orinoco Belt of Venezuela. Unconformities also can juxtapose migration conduits. The problem in discussing long-distance migration is that such cases are rare. although it should be remembered that there are two fundamentally different types of vertical migration. leading to smaller fault-bounded accumulations and vertical migration. including the Athabasca Tar Sands of western Canada. thus providing a potentially very effective system for combined vertical and lateral migration. the process of hydrocarbon accumulation was somewhat mystical. however. The absence of both tectonic and stratigraphic barriers permits long-distance migration. Vertical migration distances can also be considerable. It is possible to have lateral migrations of as much as a few hundred kilometers in exceptional circumstances. The question of long-distance migration has been much discussed and disputed.
No traditional seal exists.
Kinetic traps represent a fundamentally new concept in trapping mechanisms for hydrocarbons.
Cross section across the Rhine Graben of West Germany showing the discontinuity of strata as a result of extensional tectonism endemic to rift basins. This model requires. while the structure or lithologic change prevents lateral updip migration. The Elmworth Field in the Alberta Deep Basin of Canada is the prototype for kinetic gas accumulations. a fractured shale that is both source and reservoir.
Most hydrocarbon traps are either structural or stratigraphic. Accumulations are small because drainage areas are small. Because the high permeability sand updip allows gas to migrate rapidly through. The much smaller Antelope Field produces from the Mississippian Bakken Formation. Because gas generation is very rapid. Fracturing associated with high races of oil generation in the Green River Shale has created a supergiant accumulation at Altamont.33
permeabilities to hydrocarbons provide barriers to migration: that is. that strong hydrocarbon generation and migration is going on today. Seals in the traditional sense of the word may not exist. it remains water wet. and vertical migration becomes important. Gas production is actually from the low-permeability sand rather than from the high-permeability sand updip and downdip. Lateral migration is of necessity short distance.
CLASSICAL TRAPS. rocks whose capillary-entry pressures are high enough to overcome hydrocarbon buoyancy.Migration . and will be covered separately. Much of the hydrocarbon storage at Antelope is apparently in silts and sands juxtaposed with the producible Bakken reservoir. of course. The simple principle behind a kinetic trap is that hydrocarbons are supplied to the trap faster than they can leak away.
. The seal prevents vertical migration from the reservoir rock into overlying strata. 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. Thus the Elmworth Field exhibits a water-over-gas contact. Classical traps are well understood. The low permeability sand thus creates a bottleneck to gas migration. the low-permeability sands become filled with gas. 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.
however. there may be a chromatographic effect during secondary migration. but it may also include some heavier hydrocarbons dissolved in the gas. Because hydrate zones are often hundreds of meters thick. Phase changes occur as a result of decreases in pressure and temperature during migration. and thus get left behind as the oil globule or stringer moves upward. The polar molecules once again interact most strongly with interstitial water and mineral surfaces. especially methane. In cases where no other structural or stratigraphic trapping mechanism exists. Because intense oil generation is going on now. These gas hydrates consist of a rigid lattice of water molecules that form a cage within which a single molecule of gas is trapped. Once expulsion has occurred. the quantities of gas in such accumulations are huge. of course. unconsolidated sediments that would have no other means of retaining the methane.Migration . Cap-rocks in those fields are often poor.
Tar mats produced by biodegradation can create excellent seals. Methane is by far the most commonly trapped gas molecule. The polar (NSO) compounds interact most strongly with both mineral surfaces and water molecules. A second characteristic is that gas hydrates form effective seals against vertical hydrocarbon migration. The technology necessary for producing these hydrocarbons has not yet been developed. contain mainly light components. these changes in temperature and pressure can cause separation of the original phase into a liquid phase and a gas phase. and in zones of permafrost. Despite the rarity of tar-mat seals. and thus are not expelled as efficiently with the oil phase. Formation of hydrates thus provides an important trapping mechanism. the lighter (gas) phase will be far more buoyant than the liquid phase. tar mats may provide the only possible means for retaining any hydrocarbons. It will therefore migrate much faster and
. but in the future gas-hydrate accumulations may be of great economic significance. large accumulations have formed despite high rates of leakage. 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.34
Many of the accumulations in Pliocene reservoirs in southern California are also kinetic accumulations in a slightly different sense. Gas hydrates form and are stable under pressuretemperature regimes that occur at depths of a few hundred meters below the sea floor in deep water. and the poor producibilitv of the hydrocarbons they trap.
Formation of crystalline hydrates of natural gas provides an extremely efficient trapping mechanism for natural gas. At the present time the vast potential of gas-hydrate accumulations is just beginning to be recognized. because the same conditions that created the tar mat persist in the subsurface. As soon as two immiscible phases are formed.
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. Accumulations beneath tar-mat seals are generally biodegraded themselves. The base of the gas hydrate zone forms a pronounced seismic reflector that often simulates bottom contours and cuts across bedding planes. One important feature of methane hydrates is that they are much more efficient at storing methane than is liquid pore water. When the original hydrocarbon phase contains large amounts of light components. and would be incapable of sealing accumulations for long geologic periods. The gas phase will. because much of the methane trapped is biogenic and was formed in young. but hydrates large enough to accommodate butane molecules are known.
and how far they moved. Tectonically stable basins have the best potential for long-distance migration and supergiant accumulations. We need to know when hydrocarbons moved. and the timing of expulsion. We have already stated that oil is expelled primarily as a liquid phase. Vertical-migration distances can be considerable. leading to an enrichment of hydrocarbons in the expelled liquid. Lateralmigration distances are strongly influenced by tectonic and depositional histories of basins.35
will also assume the structurally high position in any reservoirs containing both phases. as we have seen. and the possibilities of combined vertical and lateral migration. by faulting. vertical faulting. We already know two important facts about timing from our previous discussion: expulsion based on microfracturing cannot occur before generation. in what direction they moved. Barriers can be created by folding. In summary. as explorationists we have very pragmatic interests in migration. Thus if we can determine the timing of generation. Efficiency of expulsion of liquids has already been estimated to be in the neighbourhood of 50% after the expulsion threshold has been reached. Polar compounds interact more strongly with water and rock minerals and thus move more slowly than hydrocarbons. Pathways. or by the presence of tars. are determined by structural contours on the top of the carrier beds. In using our understanding of secondary migration for exploration. When separation of a single hydrocarbon phase into two phases occurs.
. and expulsion occurs concurrently with generation to relieve generation-induced overpressuring.
SIGNIFICANCE FOR EXPLORATION
Explorationists who are reading about migration will surely ask.Migration . we will also have determined the timing of expulsion. "What does this mean for exploration?" From their perspective the important aspects of primary migration are the nature of the hydrocarbons expelled (oil or gas). gas is presumably expelled as a gas phase. by decreases in permeability as a result of facies changes. both new phases will have compositions that differ drastically from the original phase. depending upon stacking of reservoirs. the barriers that modify die direction of migration and eventually stop it. the efficiency of expulsion. Many light oils (often called condensates) probably have such an origin
Proposed separation of petroleum components during secondary migration as a result of chromatographic effects. Unstable basins seldom have depositional or tectonic continuities necessary for longdistance lateral migration to occur. we want to determine the main pathways and conduite through which migration occurs. and the vertical and horizontal distances involved. Timing of expulsion must be dealt with in a different way. Proximity to effective source rocks and their permeabilities to hydrocarbons determine conduits. Efficiency of expulsion for hydrocarbons is apparently much higher than for NSO compounds.
7 . we need a few definitions. A structure contour map resembles an ordinary topographic contour map. but there must also be some sort of blockage to prevent further migration. To give a true representation. and furthermore we can map out the extent and shape of the trap with a good deal of precision-thanks mostly to modern seismic techniques. This may be caused either by the reservoir itself dying out or by an interruption of its upwards continuity to the surface. To complement the structure contour map.Petroleum Traps . they can be mapped by means of contours drawn on the top of the reservoir formation. (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. exploration used to consist largely of finding a trap. The location of a trap in the subsurface is often the first objective of an exploration program. if more continues to migrate up into the trap than can be
. (a) A simple hypothetical anticline. it will escape to surface as a seepage. one or more cross-sections may be drawn. The highest point of the reservoir. The top of a reservoir formation. The lowest point. These are illustrated using a simple anticline as an example. The contours are in feet below mean sea-level. Nowadays we can do better. drilling a well into it. First. where it is lost. is known as the crest of the trap. is the spill-point: this is where oil. Such a configuration of the reservoir is known as a trap. and hoping for the best. is mapped by contours showing depth below sealevel.(2-18)
Before we go further. which may refer either to its depth or to the spot under the ground where it lies. before we reached our modern understanding of the geology of petroleum. Any oil getting there will be unable to migrate further and so it starts to accumulate.
THE REPRESENTATION OF TRAPS
Traps are commonly depicted in two ways. If then we are to find any of it still preserved.Petroleum Traps
We have seen petroleum generated in and expelled from the source rock formation into an overlying or underlying reservoir. up towards the ground surface. the ticks are on the downthrown sides of the faults. they should properly be drawn with the same scale for both the vertical and the horizontal. as the beds on one side are dropped down relative to the other. If it can. Faults will be marked by jumps of the contours. by displacing the water already there in the porosity. except that the contours are in depth below sealevel. so that the highest points on the map have the lowest values. Note that we commonly highlight petroleum accumulations by shading or colouring the reservoir formations where they contain oil or gas. which may give a misleading impression of `lakes' of
petroleum under the ground!
Structure contour maps. Indeed. 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). but it is often convenient to exaggerate the vertical to show the individual beds more clearly.
Stratigraphic. Let us remember.(or gas-) column. being lighter still.
The best known type of trap is the anticline: on reaching the crest. 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. The vertical height between the spill-point and the crest is referred to as the closure. Where there is more than one such pool in the same or overlapping areas.e. separates out on top within the pore-spaces of the reservoir. Similarly gas. If there is no oil. 3. will occur as a gas cap above a gas-oil contact. there are various types of
Some terms used to define a trap. however. Just a couple more terms. formed partly by structural and partly by stratigraphic effects. so that we can recognize a generally horizontal oil-water contact.37
accommodated. the only structural effect being a tilt to allow the oil to migrate through the reservoir.
Now we can start to consider the types of trap whose discovery may await us. petroleum migrating up along a reservoir can go no further and it accumulates there as a pool. using a cross-section of a simple anticline as example (2-19). or in their layering. Oil being lighter than water. that most reservoir formations include some tight intervals. 4. 2. and the same term is used loosely to refer to the area of the trap above the level of the spill-point. Structural. will spill out (under) and migrate on. which are rare and are mentioned mainly for completeness. Hydrodynamic traps. which have porosities and permeabilities too low for them to contribute oil to production. However. Combination traps. The vertical height of the oil (or gas) between the crest of the trap and the water contact is the oil. They are normally classified under four headings (2-21):
1.Petroleum Traps . i. in which the trap is formed by changes in the nature of the rocks themselves. they are embraced by the familiar terms oilfield or gasfield. the informal term pay is often used. The trap is due to water flowing through the reservoir and holding the oil in places where it would not otherwise be trapped. When referring to a single well. A single accumulation of oil or gas is called a pool. either by folding or faulting. but not entirely due to either. where the trap has been produced by deformation of the beds after they were deposited. perhaps if more than one reservoir is present. then we may see a gas-water contact.
Other types of anticline can be formed without any lateral compression at all: an important one is the drape or drape-compaction structure. the anticline is asymmetrical. in cross-section. and the blanket bulges upwards with an anticlinal shape. There is a definite limit to the depths to which we should drill.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. therefore in order to drill into a reservoir near its highest point (where we would expect the oil to be). The similar anticline.(2-22)
In the concentric fold the tops and bottoms of all the layers remain strictly parallel to each other. (b) The anticline is asymmetrical and the crest shifts with increasing depth. a well would have to be located off-crest at surface. Traps can also be formed against faults if a chopped-off reservoir is thrown against a shale or other impervious rock. In practice. depending on the nature and strength of the rock layers being folded. we can thus expect to find only smaller and smaller accumulations of petroleum down to the centre of curvature. In this case.Petroleum Traps . but an understanding of the shape and size of a prospect is clearly critical to programming an exploration well. Seismic may help. with one flank steeper than the other. and we may no longer be able to see where the bottle is. (a) The dips are the same on both flanks and the crest is beneath the same locality at all depths. on the other hand. These compressive structures pose one problem right from the start. and we may be able to continue exploration down to depths where we have to stop for other reasons. We will describe in a little detail the most important types of anticline. Below this point we have just too much rock to fit into the anticline. but we commonly have to undertake some form of geometrical construction to interpret what is happening at depth. maintains its shape constant down to depth. 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. beyond which there may be no trap left to explore as the consequence of decoupling of layers. These conditions mean that the anticline becomes smaller and tighter at deeper levels until we reach a common `centre of curvature'. The general principles of this are straightforward. In this type of structure. we have to know its depth to know where best to locate the well.
. This leads us into the next problem. 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. Let us see what the implications are for exploration. Cover it with a few more blankets and a duvet or two.
Cross-sections of trap-forming anticlines. noting the differences in shape and prospectivity that we have to try to interpret. This can only happen if there is an apparent thickening of some beds over the crest of the fold. then the position of the crest will shift with increasing depth. many structures have forms in-between the two extremes. we can find the trap present at all levels down to the basement. If. Compressive structures have a range of shapes between the purely concentric or parallel anticline and the similar fold. This is a very different kettle of fish from the concentric anticline. Anticlines. To test the crest at depth.
Ghawar in Saudi Arabia. then they will blanket the hill as an anticline. and hence the combined name. Nature. can be a perfect seal to any underlying accumulations. or over an upfaulted block or horst. the Gulf Coast of the USA. where the beds are draped over the eroded stumps of an old Jurassic volcano. This creates a rollover anticline.39
A drape-compaction anticline. which contains more than four times as much oil as the whole of the North Sea put together. The last type of anticline that we should be aware of is the roll-over anticline. A second effect comes into play here: because there is a greater thickness of beds off the structure than over the top. Another is the Forties field in the North Sea. being plastic. showing the variety of traps that may be associated with them. the beds being draped over an upfaulted block (horst) of basement rocks. a salt pillow or a salt dome. All of these possible traps may contain hydrocarbons. higher beds will gradually mute and suppress the structure until it is no longer present at shallow levels. In effect the downthrown side is being pulled away from the upthrown side which would tend to create an open fissure along the fault. The effect of salt diapirism will be initially to bulge up the overlying sediments as an anticline. Extensive salt deposits and plugs with associated traps occur in many parts of the world: the southern North Sea and northern Germany. does not like empty holes. note that the largest oilfield in the world. much of the west coast and continental shelf of Africa. but also
. the Canadian Arctic Islands. and then to burst through them in the form of a salt plug or salt wall. and the beds on the downthrown side above the curving fault collapse to fill the gap. 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 is not always easy to separate out the two effects. is in one such trap. and finally a residual bulge may be left between two nearby plugs: a turtle or turtle-back structure. Note a characteristic of these anticlines: not only do they `grow' with depth. Not only may an anticline be pushed up over the plug. the Middle East. This occurs alongside a normal fault that is curved.(2-25)
Similarly. it may extend up to the surface of the ground or only part way if the supply of salt is limited.Petroleum Traps . This compaction enhances the anticline formed by the drape. bending downwards into the hole. Note also that salt. however. In case anyone should think that this is unimportant. and several others.(2-26)
A wide variety of traps can be associated with salt plugs. Note that the anticline dies out upwards towards the surface. if the first sediments in a basin were deposited over a hilly surface.
Diagrammatic section through two salt plugs. it is also liable to fracture the overlying and surrounding beds creating fault traps. it may bend up and seal off the strata it cuts through. so that it is steep near the surface and flattens with depth.
trapped against faults to the south. a fault can provide a seal. It adds further uncertainties to our predictions of the subsurface occurrence of oil and gas. and it will depend on the amount of displacement on the fault. Much of the oil under the Niger and Mississippi Deltas is in such roll-over anticlines.
Roll-over anticlines: (A) a simple roll-over into a normal fault. the position of the crest is displaced with depth and that accumulations in successive reservoirs will not underlie the same surface position. Note that.
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. Again. therefore. down towards the deep ocean.
Tr. The oil is in two reservoirs. It also depends on whether the fault itself is sealing or non-sealing. in both ways. and in understanding them.Petroleum Traps . T. whether the fault is normal or reverse. we still do not fully understand what the difference is due to. as at Wytch Farm. at deeper levels the crest will shift away from the position of the fault at surface. or slumping as a sort of land-slide. and naturally we have some ideas on the subject. southern England. Fault traps We indicated above that a trap may be formed where a dipping reservoir is cut off up-dip by a fault. We know that sometimes. The proviso is that we also have lateral closure: this may be provided by further faulting. or by opposing dips. setting it against something impermeable. thus causing sand against sand to permit migration and sand against shale to be sealing. we have to know whereabouts in the succession our prospective reservoir lies. these predated the deposition of the Upper Cretaceous. All very puzzling! Although attempts have been made to investigate the problem in Nigeria and elsewhere. L. will depend on the dip of the reservoir as compared with that of the fault.40
they are asymmetrical. The reader may care to think through the various situations sketched as bits of cross-sections in the following figure in which the faults themselves are non-sealing. Lower Cretaceous. The sealing capacity of faults is a major difficulty confronting us. (B) a roll-over complicated by subsidiary faulting near the crest. and how big it is. Upper Cretaceous. (2-28)
We do not propose to discuss fault traps in detail.. Upper Jurassic. or have acted in the past. W. Triassic. Occasionally indeed. and its depth. to locate an exploration well in the right place. The large Wytch Farm oilfield of southern England offers a splendid example.
Cross-section through the Wytch Farm oilfield. but we also know that sometimes faults are pathways for migrating petroleum and non-sealing at all. whether or not the reservoir is completely or only partially offset. Whether or not there is a trap. Kim+P. it seems that one and the same fault may act. in both cases.
. UK. although there are many problems in trying to locate them in the subsurface. BS+MJ+O. Middle Jurassic. Tertiary. Lower Jurassic.
Non-unconformity traps are even more diverse. however. A lot of oil has been found in recent years in this sort of trap in the North Sea. is the biggest in the USA outside Alaska. but nevertheless known. to a large extent reflecting the restricted environments in which the reservoir rocks were deposited. to provide a trap when later covered with. cut across by erosion and later covered above the unconformity by impermeable sediments. but are generally classified as stratigraphic traps. we have an isolated trapping situation. if terminated updip as not infrequently happens.Petroleum Traps . and leave the reader to speculate on other possibilities. the porosity could be preserved beneath the unconformity. the beach sands will spread progressively over the land surface. gneisses) under an unconformity serve as reservoirs in China and North Africa. thus preventing further migration. A dipping reservoir. A sand deposited in a river channel will be confined by the banks and. More esoterically. may serve as an isolated stratigraphic trap. say. no structural control is needed. provides the classic case: the East Texas field. In fact. and on the amount of displacement of the reservoir. so we will mention a few to convey the general idea. strongly weathered basement rock (granites. its edges will provide an example of a reservoir dying out laterally. fan sands provide one of the prime present-day exploration
. depending on whether the fault is normal or reverse. We would be left with a sandstone reservoir dying out above the unconformity. It would be pointless to list all of the possible types of stratigraphic trap that can exist. It is presumed that petroleum cannot escape up the fault plane. on the direction of dip of the beds relative to the fault plane. A coral reef overwhelmed by muds. In this manner. The variety in size and shape of such traps is enormous. Unconformity traps can also be found above the break. until perhaps the supply of sand runs out. First. if drowned by shales. are formed by unconformities. will spread out as a fan over the ocean floor. for example. possibly through a submarine canyon. A flood of sand washed off the shallow continental shelf into the deeper ocean.41
Six trapping and two non-trapping configurations against a fault.(2-29)
Petroleum may be trapped where the reservoir itself is cut off up-dip. some of them very important. they differ somewhat in principle from the others. Consider the sea gradually encroaching over the land as sea level rises. We mention just three examples. claystone. a hill on the old land surface may be formed of permeable rock. let us note that a number of traps. becoming younger as time goes on.
tilted westwards. which were eroded and unconformably overlain by Cretaceous shales. We may note here one most important consideration. although such prospects are not easy to locate and may require a lot of sophisticated seismic.
An investigation into the sealing qualities of faults affecting roll-over anticlines in the Niger Delta. where there is enough of it in the section. The oil is held in the reservoirs by younger shales overlying the erosion surface (Fig. The reservoir beds were folded into an anticline. possibly even before it
A number of fields. as the fault moved. which was tilted west and eroded before deposition of the overlying beds now dipping east. and where an oil-water contact is continuous across a fault. The Prudhoe Bay field in northern Alaska. or the oil would have been lost. As the more easily found structural traps are running out in much of the world.Petroleum Traps . there always seems to be something new as a challenge. Where a reservoir is full to spillpoint against a fault. Again the range of possibilities is almost infinite. occur in traps formed by a combination of structural and stratigraphic circumstances. A couple of examples may give the idea.42
targets. it is presumed that the fault is non-sealing. elsewhere it appears to form a trap. Both the faulting and the unconformity control the traps.
A block representation of the trap at the Prudhoe Bay field in northern Alaska.(2-31)
The oil in the Argyll and many other fields in the North Sea is trapped in tilted and faulted Permian to Jurassic reservoirs. The oil in these fields can only have migrated there after the traps were sealed by the higher sequences.). This vital factor. The difference is believed to be due to clay being smeared into the fault plane. This combination trap is partly structural (the anticline) and partly stratigraphic (beneath the unconformity). neither completely controls the trap. has most of its oil and gas trapped in a Carboniferous to Jurassic sequence which includes more than one reservoir. these beds were folded into a faulted east-west anticline. that the trap must be shown to have been there before the oil migrated. and truncated by erosion. some of them large. where the reservoirs overlie overpressured shales. the biggest field in the USA.
therefore. The number of structural field of this size may partly reflect the fact that structural traps are easier to find than the others. Furthermore. up in the hills and percolating downwards towards a spring. but the oil reserves they contain show clearly that generally they are also bigger. are the more obscure and generally smaller prospects. and the oil will be free to move again. from our present-day point of view. The oil-water contact in such a hydrodynamic trap is normally tilted in the direction of water flow. only for as long as the water keeps coming: dry up the supply of water. indicating the former presence of an oil accumulation now lost. Such tilted contacts. We would recognize this from residual traces of oil in a water-bearing reservoir. essentially anticlinal. Note that the oil-water contact is tilted down in the direction of water flow. of course. It is totally dependent on the flow of water and is effective. Oil. is held against an unevenness of its upper surface by water flowing in the opposite direction. as we do not want to waste the money drilling wells that would miss the oil altogether. is that in most parts of the world the larger anticlines have now been drilled.
Imagine surface water. we would have to be careful where we locate and drill our oil production wells. Oil has found its way into the reservoir and is battling to migrate upwards to the surface against the flow of water. are not all that rare. perhaps from rain. The trouble.Petroleum Traps . a regime of water flow cannot normally be expected to remain constant for long. This is what has been described as a hydrodynamic trap. is yet another aspect of the petroleum geology that we have to assess in proposing exploration drilling. What our efforts are increasingly directed towards. attempting to escape to surface up a reservoir. entering a reservoir formation. it may find itself caught against an unevenness of the reservoir surface where there is no conventional trap at all.(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. There is no structural or stratigraphic closure. they are known in a number of parts of the world. in say ordinary anticlinal traps. Depending on the balance of forces acting on the oil. It is therefore always important to get a handle on the hydrodynamic regime in a reservoir for both exploration and oilfield development purposes. This may be one of the reasons why oil accumulations trapped hydrodynamically are rare. or aquifer. cases are known where flowing water has apparently been able totally to flush oil out of an anticlinal trap.
. traps in both number and size.43
was generated. geologically speaking.
A hydrodynamic trap. In this sort of situation. The timing of trap formation versus oil migration has not always worked out favorably.
The logs show SP (Self Potential or Spontaneous Potential) on the left and R (Resistivity) on the right.
.Petroleum Traps .Make the interpretations from easy (A) to more difficult. Interpret the geological relationships shown in each by drawing a
structural cross-section through the logs.45
EXERCISES EXERCISE 1: The following well logs have been hung on a structural datum. multi-interpretable (D).
The Onondaga forms a thick biohermal reef over part of the field.Petroleum Traps .. showing the interval from top of Onondaga to bottom of Oriskany. Use this information to construct a northeastsouthwest structural cross section from the Richards well to the Dibble well. Elevations and marked logs are provided for 6 wells in the Wyckoff Field. located in Steuben County. Wyckoff Reef Gas Field WellElevation
CORNELL DIBBLE GUILD CHASE BANKS RICHARDS 2257' 2098' 2037' 2206' 2182' 2066'
.Y. Only the porous core facies is productive in the reef section (see map on next page). N. A deep-seated downto-the-southwest fault extends upward along the southwest flank of the reef.46
EXERCISE PetroleumTraps 2 The Wyckoff Gas Field. produces from Onondaga Limestone and/or Oriskany Sandstone. Oriskany production is from a small anticline on the upthrown side of the fault.
Petroleum Traps .47
Petroleum Traps .48
The term "effective source rock" obviously encompasses a wide range of generative histories from earliest maturity to overmaturity. a possible source rock in a nearby unstudied region. Analysis normally requires about one gram of rock. It follows from these definitions that a particular stratum could be an effective source rock in one place. For example. that usage is a bit too broad and loose.49
8 . where G and Go are identical. we actually measure its remaining (or untapped) source capacity at the present day. but which may have generated and expelled hydrocarbons. which we can call G.
MATURITY OF ORGANIC MATERIAL
Knowing a rock's remaining source capacity G solves only one part of the puzzle. the following distinctions can be made: Effective source rock: any sedimentary rock that has already generated and expelled hydrocarbons. and inexpensive analysis serves as the first and most important screening technique in source-rock analysis. For better communication. The quantity actually measured in the laboratory is always G. the remaining source capacity and not the original capacity (Go).
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. When we analyze a rock sample in the laboratory. in which case virtually all the initial
. but if the rocks contain abundant organic matter. quick. The difference between Go and G represents the hydrocarbons already generated in the effective source rock. or is it because the rock is "burned out" (i. However.Source Rock Evaluation . we cannot measure G directly for a sample that has already begun to generate hydrocarbons. Although the term source rock is frequently used generically to describe fine-grained sedimentary rocks. Go. overmature. if G is very low. a potential source rock in a less-mature area. For example. much smaller amounts can be analyzed. the Phosphoria Formation of Wyoming and Idaho belongs to each of these classifications in different areas. instead it must be estimated by measuring G for a similar sample that is still immature. 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.e. This simple. Go can only be measured directly for immature source rocks. is most meaningful if we can compare it to the rock's original source capacity. is it because the rock never had a high initial source capacity. it is also necessary to know what level of thermal maturity is represented by that particular G value. Possible source rock: any sedimentary rock whose source potential has not yet been evaluated. This quantity. Potential source rock: any immature sedimentary rock known to be capable of generating and expelling hydrocarbons if its level of thermal maturity were higher.Source-Rock Evaluation
DEFINITION OF SOURCE ROCK
Much of modern petroleum geochemistry depends upon accurate assessment of the hydrocarbonsource capabilities of sedimentary rocks..
TAI measurements are carried out on bisaccate pollen grains whenever possible. the plot is a straight line. in some cases it is essential. vitrinite reflectance. At the end of the analysis a histogram of the collected data is printed. leading to frequent difficulties in establishing which vitrinite population is indigenous. and none can be applied in all cases. along with a statistical analysis of the data. The most commonly used maturity parameters today are spore color (Thermal Alteration Index. TAI values are estimated. If enough vitrinite particles can be found. Such histograms are quite often difficult or impossible to interpret. All the methods have strengths and weaknesses. unless surrounding samples help us determine the indigenous vitrinite population. Because what is present is often reworked. All the techniques discussed are useful and probably reasonably accurate if the analytical work is carefully done. and then embedding the kerogen particles in an epoxy plug. Vitrinite-reflectance techniques were developed for measuring the rank of coals. in which the vitrinite maceral is usually very common. the reflectance value of vitrinite increases. in fact. In all cases it is worthwhile to supplement vitrinite with other measures of maturity. In many areas it is easy to use and valuable. In many rocks vitrinite is rare or absent. whenever possible. Results are reported as Ro values. 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. from amorphous kerogen. its maturity is not related to that of the rock in which it is found. however. and pyrolysis temperature. between 50 and 100 measurements will be taken.50
hydrocarbon-source capacity has already been used up)? The exploration implications of these two scenarios are. Reflectance values are normally plotted versus depth in a well. After the plug is polished. In order to minimize differences in color caused by changes in the type or thickness of the kerogen particles. Vitrinite reflectance (Ro). of course.
. Less commonly used are fluorescence and conodont color (CAI). far more common in shales than in coals. Because each maceral type increases in reflectance in a slightly different way as thermal stress increases. If a log scale is used for the reflectance.Source Rock Evaluation . The darkening of kerogen particles with increasing thermal maturity can be used as an indicator of maturity. Thermal Alteration Index (TAI). Vitrinite-reflectance measurements begin by isolating the kerogen with HCl and HF. Reworked vitrinite is. very different. The method is based on the fact that with increasing thermal stress. the microscopist shines light on an individual vitrinite particle. A substantial number of techniques for measuring or estimating kerogen maturity have been developed over the years. even for experienced workers. Despite its weaknesses. misidentification of macerals can cause problems. There are many problems with vitrinite reflectance as applied to kerogens. A few of these parameters will briefly be discussed. Other macerals or solidified bitumens can often be misidentified as vitrinite. or TAI). The fraction of the incident beam that is reflected coherently is measured and recorded and stored automatically on a computer. If no pollen can be found. TAI measurements are made on the same slides prepared for microscopic kerogen-type analysis. In other rocks. in obtaining more than one maturity parameter. The key to using maturity parameters effectively lies in evaluating the measured data carefully (and sometimes with skepticism) and. paucity of first-cycle vitrinite renders vitrinite-reflectance measurements essentially worthless. The feeling of most workers today is that there is no single maturity indicator that tells the whole story unerringly all the rime. The ideal histogram of reflectance values is therefore rather rare. vitrinite reflectance is the most popular technique today for estimating kerogen maturity. where the o indicates that the measurements were made with the plug immersed in oil. with lower confidence.
Colors of the specimens thus obtained are determined under a binocular microscope and compared with standards. The technique is simple and quick and can be done even by inexperienced workers. they offer a means of measuring maturity in rocks that do not contain pollen grains or vitrinite. Finally. Conodonts are isolated. by removing the mineral matrix with acetic or formic acid. Conodonts do not occur in rocks younger than the Triassic. TAI values estimated from amorphous material are always suspect and should be corroborated by other analyses. 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. the absence of spores and pollen in the samples. A careful worker can reproduce earlier work with excellent precision. CAI is inexpensive and easy to measure and. Finally. and thus helps expand the range over which maturities can be measured.
Conodont Alteration Index (CAI). One advantage of CAI over other maturity parameters is that because conodonts existed as early as the Cambrian. TAI values must be estimated from amorphous debris. changes in conodont color are apparently due to carbonization of inclusions of small amounts of organic matter during catagenesis and metagenesis. thus defusing to a large degree the criticism that TAI is too subjective to be valid. lack of proper standardization. Although TAI determinations are subjective.Source Rock Evaluation . The chief problems arise with inexperienced workers. because the organic metamorphism displayed by conodonts is not related to hydrocarbon generation or destruction. and thus are of no value in many areas. Conodonts are not very sensitive indicators of maturity within the oil generation window.51
Each laboratory has reference slides so that microscopists can continually compare the color determinations they are now making with those they and their colleagues made in the past. When palynomorphs are absent. which can vary greatly in its chemical and physical properties. Carbon Preference Index (CPI). Although conodonts are composed of carbonate apatite. The first maturity indicator applied to sediments was the Carbon Preference Index. TAI measurements are therefore often quite accurate and correlate very well with results from other techniques. most commonly from fossiliferous carbonates. where pollen and vitrinite are often absent. conodonts are plentiful in carbonate rocks. leading to an inaccurate assessment of kerogen maturity. the CAI scale is most sensitive at levels of maturity much higher than can be measured by TAI. where most of the interest is. with the help of color charts can be carried out by inexperienced personnel. Thirdly. use of careful standards and the same type of palynomorph in each analysis greatly aid reproducibility. Early investigations showed that immature rocks often had high CPI
. Furthermore. or most commonly. CAI is only an indirect indicator of hydrocarbon maturity.
and therefore should be easy to avoid. atomic H/C ratios measure the present day status of the kerogen rather than its original chemical composition. Fortunately. Well Samples . have low CPI values even when immature. Hydrocarbon contamination is rare except in the immediate vicinity of production or where vehicles are used. because of their friability.
ESTIMATION OF ORIGINAL SOURCE CAPACITY
Of the three major methods of determining kerogen type. Problems with living organic matter are easily avoided by physically removing tiny plant roots and other recognizable debris. Without additional information. Drilling-fluid additives have been a severe headache for petroleum geochemists for a long time. Pyrolysis yields are. It is capable of impregnating sidewall and conventional cores as well as cuttings. but it can be devastating in cuttings samples.52
values (> 1. only microscopic analysis is relatively unaffected by maturity. Like pyrolysis. and lignite from lignosulfonates. whereas those of oils were almost always below 1. Careful picking of lithologies and comparison with up-hole samples can often recognize caved materials. in the last decade kerogen analyses have replaced bitumen analyses as the routine procedure in source-rock evaluation. Furthermore. however. In particular. Walnut hulls and other organic debris are also easy to detect microscopically. 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. vitrinite reflectance measurements offer the best means of recognizing caving. walnut hulls and other solid debris. In contrast to solid additives.5%. Mold or other surface growth may also be present.
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. It breaks down at high maturity levels. TOC values will be raised and vitrinite-reflectance values lowered by the presence of adsorbed diesel. Contaminants of particular notoriety are diesel fuel. This method works fairly well if the kerogen is still within the oil-generation window. palynological analysis can usually detect the presence of lignosulfonates because of the unique pollen assemblages present in the lignite. because all kerogens have low pyrolysis yields. rocks deposited in pelagic environments. in which the input of terrestrial lipids was very limited. diesel fuel affects both kerogen and bitumen.The main causes of contamination among samples obtained from wells are caving and adulteration by drilling-fluid additives. it is impossible to determine which maturation path brought it to that point.2. In many cases. In such cases TOC values will be raised and reflectance histograms will show a large population near 0. As long as kerogen particles are not completely black. which affect only the kerogen portion of the sample.Source Rock Evaluation . it can lead to an overly optimistic assessment of the organic richness of the section. and can be removed prior to beginning the analytical sequence. This discovery led to the use of CPI as an indicator of maturity. of course. however. Caving is not a problem for conventional or sidewall cores. Atomic H/C ratios must therefore be corrected for the effects of
. As a result. they can usually be identified with reasonable confidence. strongly affected by maturity. Caving is a particular problem for coals. of course. 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. therefore. The exception to this rule is with amorphous material. fewer CPI determinations are made now.5). where the fluorescence that enables us to distinguish between oil-prone and non-oil-prone disappears toward the end of the oil-generation window.
These immature H/C ratios can then be used to calculate Go. Pyrolysis results are normally reported in two ways. and S3) are expressed in milligrams of hydrocarbon or carbon dioxide per gram of rock sample. S2. because the type of kerogen preserved in rich rocks is often more oil-prone than in lean rocks.Source Rock Evaluation . The oil-generative macerals are those of Type I and Type II kerogens: alginite. Interpretation of TOC values therefore does not simply focus on the quantity of organic matter present. Smyth (1983). because the kerogens they contain are woody or highly oxidized. These raw data are then normalized for the organic-carbon content of the sample.0% TOC are marginal.0%). however. cutinite. and thus of limited source potential. We must still determine whether the kerogen present is in fact of good hydrocarbon-source quality. Raw data (S1. on the basis of deductive reasoning. Furthermore.
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. As such these quantities are a measure of the total capacity of a rock to release or generate hydrocarbons or carbon dioxide. Rocks containing more than 1% TOC often have substantial source potential.0%).5% and 1. where preservation of lipid-rich organic matter with source potential for oil can occur. but they may expel small quantities of hydrocarbons and thus should not be discounted completely. fluorescing amorphous kerogen.53
maturation by using a van Krevelen diagram. gas-generative. etc. Because the density of organic matter is about one-half that of clays and carbonates. and which are definitely worthy of further consideration (TOC > 1. Rocks containing between 0. has dissented from this pessimistic view. In some rocks TOC values between 1% and 2% are associated with depositional environments intermediate between oxidizing and reducing. Many rocks with high TOC values. They will not function as highly effective source rocks. Inertinite is considered by most workers to have no hydrocarbon-source capacity. Nevertheless. yielding
. Kerogens in rocks containing less than 1% TOC are generally oxidized. however. which ones might be of slight interest (TOC between 0.5% TOC. have little oil-source potential. We therefore use TOC values as screens to indicate which rocks are of no interest to us (TOC < 0. resinite.5% and 1. and inert. the kerogen in such lean rocks is almost always highly oxidized and thus of low source potential. the actual volume percent occupied by the organic material is about twice the TOC percentage. The amount of hydrocarbons generated in such rocks is so small that expulsion simply cannot occur. claiming. Thus high TOC values are a necessary but not sufficient criterion for good source rocks. In interpreting these observations we normally divide these macerals into oil-generative.5% TOC are considered to have negligible hydrocarbon-source potential.
TYPE OF ORGANIC MATTER
Microscopic kerogen-type analysis describes the proportions of the various macerals present in a sample. TOC values above 2% often indicate highly reducing environments with excellent source potential. Gas-generative kerogen is mainly vitrinite. exinite.5%). A rock containing 3% TOC is likely to have much more than six times as much source capacity as a rock containing 0. Those rocks containing less than 0. that at least some Australian inertinites can generate significant amounts of oil. the direct evidence for such a statement is rather meager.
the hydrogen index serves as an indicator of kerogen type. with CAI of 8 reached in a marble. and the end of liquid-hydrocarbon generation is thought to be at about 1. exinite) or from marine algal material.54
values in milligrams per gram of TOC. respectively. either from terrestrial macerals (cutinite. The ultimate limit of oil stability is not known for certain. Because vitrinite reflectance is the most popular method of determining maturity. because they vary with kerogen type as well as maturity. Because some Cenozoic land plants are richer in resins and waxes than Paleozoic plants. They have excellent potential to generate liquid hydrocarbons. CAI can actually measure high-grade metamorphism.5% Ro. a unified scale for comparing them with Ro values has not been adopted. Thus. this generalization has two fallacies: most of the coalfields originally studied were of Paleozoic age. Kerogens with hydrogen indices above 600 usually consist of nearly pure Type I or Type II kerogens. Although Tmax values are determined objectively. most other maturation parameters are related to Ro values. Conodont Alteration Index (CAI) values ranging from 1 to 5 were tied loosely to vitrinite reflectance and fixed carbon content of coals. Because variations in TOC have been removed in the normalizing calculation. Hydrogen indices above 150 reflect increasing amounts of lipid-rich material. and the coals were of bituminous to anthracite rank.35% Ro. but in most cases is probably not much above 1. make sure that you have a copy of their equivalency between TAI and Ro. Those between 150 and 300 contain more Type III kerogen than Type II and therefore have marginal to fair potential for liquids. because during the Paleozoic the biota was quite different than during the Cenozoic.
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.
Kerogen Parameters. Some laboratories put the onset of maturity at 435° C. The correlations among maturity parameters have been fairly well established. A second. and thus are considered to have good source potential for liquid hydrocarbons. if you are using TAI determinations determined by an analytical laboratory.
. others use 440°. The limits of the oil generation window vary considerably depending upon the type of organic matter being transformed. but there are still some minor variations from one laboratory to another. However. resinite.9% Ro.6% Ro. The normalized S2 and S3 values are called the hydrogen index and the oxygen index.Source Rock Evaluation . Age of coals is important. Measured hydrogen indices must be corrected for maturity effects by using a modified van Krevelen diagram as outlined above. It is particularly difficult to generalize about TAI values because the numerical values of TAI scales have not been standardized among laboratories. Hydrogen indices below about 150 mg HC/g TOC indicate the absence of significant amounts of oil generative lipid materials and confirm the kerogen as mainly Type III or Type IV. less common application is to decide whether oil will be stable in a given reservoir. some Cenozoic coals should have better potential for generating liquid hydrocarbons. Determination of the oil-generation window in a particular section is the objective of most maturity analyses performed on possible source rocks. Nevertheless. Interpretation of hydrogen indices for immature kerogens is straightforward. for most kerogens the onset of oil-generation is taken to be near 0. Kerogens with hydrogen indices above about 300 contain substantial amounts of Type II macerals. Peak generation is reached near 0.
To do this intelligently we must have the ability to develop regional models of organic facies and thermal maturity. type.0 4. rather. We should always attempt to extrapolate our measured data over as large an area as possible.00 Thermal Alteration Index (TAI) 2.2 3.60 0. we should attempt to corroborate the measured data by other analyses.35 1.40 0.8 4.50 2.8 3.3 2.80 1. unconformities and erosional events.50 0.0 Pyrolysis Tmax (°C) 420 430 440 450 460 465 470 480 500 500 + 500 + Conodont Alteration Index (CAI) 1 1 1 1.55
Any source-rock evaluation should attempt to answer three questions: What are the quantity.5 2 2 2 3 4 4 5
Correlation of various kerogen-maturity parameters with vitrinite-reflectance (Ro) values
. therefore.6 2.00 1. Interpretation of source-rock data on a basic level is quite simple.0 3. In some areas one technique may fail completely or may be only partially successful.5 3.20 1.Source Rock Evaluation . With increasing experience one can also learn to derive important information on thermal histories.0 2.
Vitrinite Reflectance (%Ro) 0.00 4. and organic facies. and maturity of the organic matter present in the rocks? Satisfactory methods are available in most cases to answer all these questions. we should not rely on a single analytical technique.4 3. Whenever possible.00 3.
7 1.5 2." Two independent quality measurements have been made.15 0.1 2.2 1.6 0.7 3.0 0.65 0.3 1.7 1.72 0. The calculated immature H/C ratios are listed in the table on next page.05 0.77 0.98 0.5 2-2.
A) Calculation of the immature kerogen H/C ratio(at A) from the present-day H/C ratio and vitrinite reflectance data(at P) . present-day H/C ratios to the ones that the kerogens had when they were thermally immature. B) H/C versus TAI for Mauve Well samples.7 2. To use the H /C data. and both should be utilized and examined for possible discrepancies.86 0.8 % Alginite + Exinite 75 80 80 75 80 90 85 75 70 50 45 60 45 40 ? ?
Data are available on quantity (%Corg). presenting the kerogen quality factor as a
.2 3.27 1.5 2-2.22 1.7 2.5 2.1 3.41 0.5 1.5 1.33 1.5 0.5 0.6 2.2 Atomic H/C 1.2 2.81 1.38 TAI 2.
Both the immature H / C ratios and the maceral analysis data need to be scaled to calculate "Total Oil." To do this.56
Worked out example: Perform a source-rock analysis on the Mauve Well. so "Total Oil" can be plotted against "Oil Already Generated. This can be done easily by plotting H/C versus TAI.07 1.0 3. refer to the graph on next page. 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 0.8 0.3 0.6 2. and then tracing the H/C ratio back to its immature value.9 3.5 2.66 0. as shown in Figure B (derived from Figure A).6 2. one must first convert the measured. however.Source Rock Evaluation .0 2-2. quality (H /C and %Alginite + Exinite).75 0. and maturity (TAI).
90 0.6 1.77 0. The most important point being made here is that these discrepanties must be taken seriously by the interpreter. 2000. The samples at 1000.50 1.27 1.30 1.65 0.05 0.17 0.85 1.00 0.90 0.72 0.
Scaled Quality Data tor Mauve Well Samples
Depth (m) macerals) 1000 1200 1500 1750 2000 2300 2700 3000 3500 3600 3800 4000 4500 4600 4800 5000 Measured H/C 1. and not
. 1500. such as pyrolysis.20 1.43 1.4 1.65 0.22 1. Without more knowledge. If these attempts produced no resolution of the problem.77 0. The prudent interpreter might now ask that some of the H/C ratios be rerun.60 0.07 1. In likewise manner (not illustrated here) the quality factor can be determined from maceral analysis data.33 1. it is impossible to pinpoint the error.5 1.05 0. the H/C ratio gives the lower quality factor.41 0.Source Rock Evaluation .05 1.15 0.6 1.81 1.98 0.86 0. 1750.05 0.38 Immature H/C 1.90 ? ? Quality Factor Quality Factor (from H/ C) (from 1.0 0.70 1. 4000.35 0.2 0.8 ? ?
* Indicates discrepancy between quality factors calculated from H /C and from maceral analysis.22 1.90 0.60 0.81 1. to check for analytical error. the interpreter might then decide to try a third technique. so some systematic error is likely. 2300.57
function of H/C ratio of the immature kerogen in order to determine the quality factor from H/C.05 1. In each case.8 1.9 1.5 1. The scaled quality factors are given for each parameter in the table on next page.35 0.35 1.6 1.66 0. and would certainly request that the slides made for maceral analysis be reviewed. and 4500 meters all show differences in the quality factors calculated from the two types of data.5 1.07 1.60 ? ? * * * * * 1.
It is apparent that there are serious discrepanties between the H/C and maceral analysis results for several of the samples. however.
Kerogen quality factor as a function of H/C ratio of the immature kerogen.75 0.90 0.9 0.7 1.
Future exploratory activity could include an attempt to find such a section. One can say little.
"Total Oil" and "Oil Already Generated" profiles tor the Mauve Well. about the oil-source history of the section below 4600 meters. More samples between 3000 and 3500 meters should be obtained to define better the zone of high "Total Oil" values. although the section between 2000 and 3500 meters shows fairly good potential. The relative organic richness of the blackened samples below 4600 meters makes them interesting for further investigation. These two kerogens are highly mature and quite black. It may be necessary occasionally to offer two alternative interpretations without choosing between them. 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. The only sample where the discrepancy is significant is that from 2000 meters. "Total Oil" values are generally unexciting. The rest of the section shows a good correspondente between the two parameters. Let us take this last approach to this problem. In fact.
. Most of the discrepanties among the different quality factors turn out to be unimportant.Source Rock Evaluation . because sourcerock potential is not good for most of the section.58
be overlooked or swept under the rug. 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.
"Total Oil" and "Oil Already Generated" profiles are plotted in above figure. and the H/C ratios are not helpful because the maceral types cannot be ascertained from such low H/C values. Finally. no maceral analysis was possible here. except for the two deepest samples.
7 0.2 2.0 2.65 0.88 0.3 Bit/TOC 0.07 1.91 0. Source-rock data tor the Turquoise Well
Depth (ft) 3000 3500 4000 4500 5000 5500 6000 6500 7000 7500 8000 8500 9000 9500 10.21 0.8 0.5 2.3 2.5 3-3.4 0.06 0.03 0.0 2.52 0.18 0.06 0.60 0.5 3.00 1.27 0.07 0.10 0.41? 1.86 1.08 0.91 1.09 0.65 0.27 1.02 0.91 1.49 0.42 0.08 0.51 0.0 2.0 2. 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 2.21 1.12
*TAI and Ro are interconverted according to the correlation table at the end of chapter 7.71 0.5-3 2.5
TOC = Total Organic Carbon Bit/TOC = Bitumen/Total organic carbon ? indicates a poor histogram
TAI = Thermal Alteration Index Ro = Vitrinite reflectance
EXERCISE Source Rock 2 Perform a source-rock evaluation of the section penetrated in the Turquoise Well.3 2.5 2. Explain how you resolved any apparent discrepancies.2 0.06 0.90 0.61 0.0-2.5 0.0-2.51 0.25 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.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10
2-2.05 0.6 2.03 0.5 2.5 2.000 Type of Sample Cuttings Cuttings TOC 1.0 2.5 2.8 1.5 2.51 0.5-3 2.66 0.05 0.02 0.60 0.66 0.5 2.17 0.5-3 2.99 1.25 0.3 1.5 3.5 2.5-3 2.55 0.6 0.33? 1.49 0.0 2.22 0.5 2.60 0.44 0.08 0.01 0.46 0.6 4.59 0.9 1.7 0.08 0.09 0.1 0.59 0.5 2.03 0.5-3 3.0 0.Source Rock Evaluation .26? 1.63 0.3 2.1 2.85 0.67 0.48 Ro 0.5-3 2.0-2.0 3-3.21 1.5 2.11 0.5-3.07 0.02 Atomic H/C 0.17 0.
a time stratigraphy can sometimes be constructed using seismic data. Time-stratigraphic data are usually available as formation tops and ages obtained by routine biostratigraphic analysis of well cuttings. If our measurements indicate that a rock has already passed through the oil-generation window. Even in maturely explored basins the samples available for analysis often do not give a representative picture of maturity in the basin.
CONSTRUCTION OF THE GEOLOGICAL MODEL
One of the advantages of Lopatin's method is that the required input data are very simple and easy to obtain. In most cases. Furthermore. If no subsurface data are available. In some areas there are no well samples available. If no well data are available. 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. for it is in keeping with the predictions of chemical-kinetic theory. methods have been developed for calculating maturity levels where measurements are not available. 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. Nevertheless. estimates can be made. we still have no clue as to when oil generation occurred. measured maturity data are of limited value in exploration. 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. These considerations are important when we want to compare timing of generation. maturity measurements can only tell us about present-day maturity levels. however. 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. however. This assumption is a logical and defensible one. perhaps from thicknesses of exposed sections nearby. early efforts to take both time and temperature into account in studying the process of hydrocarbon generation were only partially successful because of the mathematical difficulties inherent in allowing both time and temperature to vary independently. It has even been suggested that maturity models are more accurate than measured data for determining the extent of petroleum generation.Predicting Thermal Maturity . In 1971. expulsion.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. especially if the seismic reflectors can be tied to well data.60
9 . 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. and migration with timing of structure development or trap formation. in frontier basins there may not be a single well within tens or hundreds of kilometers. We need data that will enable us to construct a time stratigraphy for the location of interest and to specify its temperature history. He developed a "Time-Temperature Index" of maturity (TTI) to quantify his method. 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. indeed. In order to circumvent these difficulties.
and that a corrected bottom-hole temperature of 133° C was obtained at 3800 m. Nevertheless. a burial-history curve may represent only a rather uncertain guess. Connecting the six dots completes the burial-history curve. The burial-history curve was constructed in the following way: two points. we can construct the complete figure. are marked on the age-depth plot. which was constructed from the time stratigraphy for the Tiger well.
. In cases where biostratigraphic data are available and deposition has been reasonably continuous. The next step is to locate the first control point from the time-stratigraphic data on the input table. we can construct the temperature grid with equally spaced isotherms parallel to the earth's surface. for example. sediment has accumulated continuously but at varying rates since deposition of the oldest rock 100 million years ago (Ma).(9-2)
All of the shallower and younger horizons will have burial-history curves whose segments are parallel to those of the oldest horizon. Using these present-day data and extrapolating them into the past. that the Tiger well was logged. Suppose. it is easy to construct burial-history curves with a high level of confidence.Predicting Thermal Maturity . The simplest way to do this is to compute the present-day geothermal gradient and assume that both the gradient and surface temperature have remained constant throughout the rock's history. Today the rock is at a depth of 3700 m. Neglecting compaction effects. representing the initial deposition of the sediment (point A) and its position today (point B). In cases where biostratigraphic data are lacking or where the sediments have had complex tectonic histories. The subsurface temperature must be specified for every depth throughout the relevant geologic past. Using the other control points from the input table. Burial-history curves are based on the best information available to the geologist. by 80 Ma the sediment had been buried to a depth of 900 m (point C).
The next step is to provide a temperature history to accompany our burial-history curve. This geometry is a direct consequence of ignoring compaction effects.61
Implementation of Lopatin's method begins with the construction of a burial-history curve for the oldest rock layer of interest. if constructed as carefully as the data permit. An example is shown in the following figure. Suppose further that local weather records indicate a yearly average surface temperature of 19° C. In the Tiger well. burial-history curves represent our best understanding of the geological history of an area.
There are numerous other variations that can be employed in creating temperature grids. The individual segments of each of the burial-history curves in a family will remain parallel. In many poorly explored areas. 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. the movement of hot rocks from the bottom of the overthrusted slab over cool rocks at the top of the underthrusted slab will affect
. but the geothermal gradient varies in response to heating or cooling events. If. If thrusting is rapid compared to the rate of thermal equilibration between thrust sheets. burial-history curves for both hanging wall and footwall can be represented on a single diagram. some part of the section is repeated as a result of thrusting. Causes for such events could include global warming and cooling or local climatic variations resulting from continental drift or elevation changes.Predicting Thermal Maturity . More complicated temperature histories account for changes in thermal conductivities caused by variations in lithology.
In other cases the surface temperature remains constant. we can change surface temperatures through time without altering the geothermal gradient. we are limited only by our own creativity. however.62
Where measured bottom-hole temperatures are not available. For example (9-7). Given adequate data or an appropriate model on which to base complex temperature reconstructions. the data necessary for highly sophisticated temperature reconstructions are simply not available. Whenever erosional removal occurs. however. The effects of thrusting on thermal maturity are not well understood. Erosion is indicated in a burial-history curve by an upward movement of the curve. maps of regional geothermal gradients can be useful in estimating the gradient at a particular location. Faulting can be dealt with by considering the hanging wall and footwall as separate units having distinct burial histories. If deposition resumes later. the resultant thinning of the section must be represented in the entire family of burial-history curves. In most cases. If part of the section is missing as a result of faulting.
SPECIAL CONSIDERATIONS ABOUT BURIAL-HISTORY CURVES
The most common complicating factor in constructing burial-history curves is erosional removal. two separate diagrams should be used for the sake of clarity. There is no theoretical limit to the complexity that can be introduced into our temperature histories. temperature profiles will be based largely on guesswork. the burial-history curve again begins to trend downward.
decreases by 1000 m. respectively. The temperature factor.(9-12)
CALCULATION OF MATURITY
Once the burial-history curves and temperature grids have been constructed. These dots define the time and temperature intervals that we shall use in our calculations. in contrast. This intervalTTI value represents the maturity acquired by the rock in that temperature interval during the time
. Multiplying the time factor for any temperature interval by the appropriate temperature-factor for that interval gives a product called the Time-Temperature Index of maturity (TTI). Testing of his model and the successful application of Lopatin's method in numerous published examples have confirmed the general validity of this assumption. we need to define both a time factor and a temperature factor for each temperature interval. spent by the rock in each temperature interval. increases exponentially with increasing temperature.Predicting Thermal Maturity . for any temperature interval the temperature factor (?) was given by: ? = 2n The temperature-factor thus reflects the exponential dependence of maturity on temperature. Lopatin defined each time factor simply as the length of time. but the distance between the two lines which bracket the erosion. Individual burial-history curves remain parallel. A Time interval is the length of time that the rock has spent in a particular temperature interval. 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.
Loss of 1000 m of section by erosion during an uplift event lasting from 70 Ma to 60 Ma. Index values increase or decrease regularly at higher or lower temperatures intervals. Studies in the Overthrust Belt of Wyoming indicate that a slow-equilibration model is superior to a simple model invoking rapid thermal equilibration. Lopatin (1971) assumed that the rate of maturation followed this doubling rule. more work is required before we will understand fully how thrusting influences hydrocarbon generation and destruction. Because the rate of maturation was assumed to increase by a factor of two for every 10° C rise in temperature. Now we can carry out the maturity calculations.63
organic maturation by causing important perturbations in subsurface temperatures. However. 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. expressed in millions of years. we must paste them together. Total maturity is calculated by summing the incremental maturity added in each succeeding temperature interval.400 cal/mol will approximately double with every 10° C increase in reaction temperature. In order to carry out maturity calculations conveniently. Intersections of the burial-history curve with each isotherm are marked with dots.
Predicting Thermal Maturity . by 10 Ma of uplift and erosion. even if a rock cools down.(9-20)
It is also possible to determine the total-TTI value at any time in the past simply by stopping the calculation at that time. the specific burial history of a rock can strongly affect its maturity. Figure C shows rapid burial during the first 20 Ma.
. The first step in calculating TTI is illustrated in the following figure. maturity continues to increase (albeit at a slower rate) because y is always greater than zero. In B burial was very slow during the first 70 Ma of the rock's existence. On the other hand. To obtain total maturity. no matter how much or how rapidly we cool it down. if we forget about the cake when the oven is hot and let it burn. the cake will bake slowly at first but will bake faster and faster as the temperature rises. If we put a cake in a cold oven and turn the oven on. where the time factors and yfactors for each temperature interval are shown on the burial-history curve. although at increasingly slower rates. but quite rapid in the last 10 my. A good analogy can be drawn between oil generation and baking. we simply sum all the interval-TTI values for the rock. as the oven cools down. baking will continue. we cannot "unburn" it. In D 40 Ma of rapid burial to a depth of 4000 m was followed by a hiatus lasting 30 Ma and. In A the rock was buried at a constant rate for its entire 80-my history. followed by a nonerosional depositional hiatus for the last 50 Ma. If we turn off the oven but leave the cake inside. In the adjoining table interval-TTI values and total-TTI values up to the present day are calculated. it can never go backward because interval-TTI values are never negative. 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). Maturity always increases. finally.64
given. TTI values differ appreciably among these four scenarios. Furthermore.
FACTORS AFFECTING THERMAL MATURITY
Because maturity is affected by both baking time and baking temperature.
the dependence of maturity on time is linear.(9-29)
Family of burial-history curves for a well in the Big Horn Basin. showing the evolution of the oilgeneration window through time. Secondly. our uncertainties about the true values of subsurface temperatures are much greater than about time. and can be even better in Cenozoic rocks. Most logged temperatures are too low and require correction. Km = Lance-Meeteetse formations. Tfu = Fort Union Formation. In actuality. but there is no guarantee of their accuracy in any particular case.Predicting Thermal Maturity . Wyoming. Temperature.
. Only in cases where micropaleontological dating was not or could not be carried out.65
A) Initial proposed burialhistory model for Well #1. 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. The sensitivity of maturity to temperature is clearly indicated by the exponential
dependence of maturity on temperature predicted by the Arrhenius equation. Kc = Cody-Frontier formations. we usually have excellent control on rock ages through micropaleontology. in contrast. B) Revised burial-history model for Well #1 based on the poor correlation with measured maturity data. First. is the single most important cause of uncertainty and error in maturity calculations. might we anticipate possible problems with time. Present-day subsurface temperatures are difficult to measure accurately. Age calls are often made within a million years. Various methods have been developed for this purpose. 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. time data are seldom a problem.
however.52 0.4 0.22 0. 3500 ft of Pliocene.66 0.25 1.000 ft of Upper Miocene before being abandoned at 16.41? 1.66
Even if we could measure present-day subsurface temperatures with perfect accuracy.1 2.5-3 2.03 0.
EXERCISE Thermal Maturity 1 Perform a source-rock evaluation of the section penetrated in the Turquoise Well. A question of some concern comes from the previously mentioned fact that most of the maturity models treat all types of kerogen identically.000 Type of Sample Cuttings Cuttings TOC 1. an accurate interpretation of the ancient geothermal history may be critical.0 0.08 0. where presentday temperatures are maximum paleotemperatures.5-3.02 Atomic H/C 0. Construct a family of burial-history curves for the well and calculate the present-day TTI at total depth.Predicting Thermal Maturity .1 0.5 2.91 0.5-3 2.90 0.5 0. In such cases we should be very careful about using predicted maturities unless we have some independent confirmation of the validity of our model from a comparison with measured maturity data.60 0.5 3.48 Ro 0.00 1.6 4.65 0.0 3-3.18 0.21 1.03 0.5 2.8 1.21 1.65 0. and 11.3 2. Base Pleistocene 2 Ma Base Pliocene 5 Base Upper Miocene 11 Base Middle Miocene 50 Ma
. however.91 1.85 0.99 1. The corrected bottom-hole temperature was 270° F. particularly where Paleozoic rocks are involved.86 1.150 ft in the Middle Miocene. do not utilize different kinetic parameters for the various kerogen types.5-3 3.02 0. we still would have to extrapolate the present somehow into the past.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.51 TAI % Alginite + Exinite 40 30 35 40 50 80 75 75 25 40 70 80 20 15 10
2-2.05 0.91 1.26? 1.06 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 3.27 1.7 0. In other cases.3 1. In many cases.71 0.3 Bit/TOC 0.01 0.33? 1.08 0.67 0.7 0.5 2.9 1.8 0.2 0.88 0. It penetrated 1000 ft of Pleistocene sediments. Despite experimental evidence indicating that different kerogens decompose to yield hydrocarbons at different levels of maturity models.5-3 2.5-3 2.27 0.5 2.5-3 2.07 1.5 3-3.59 0. even an inaccurate extrapolation into the past may not cause significant problems.51 0. A plausible average surface temperature is 20° C.06 0.51 0.49 0.08 0.17 0.
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. micropaleontology indicates the rocks to be of Maestrichtian age.5 base Turonian base Cenomanian base Cretaceous top Kimmeridgian base Kimmeridgian 91 Ma 97 144 150 156 Ma
EXERCISE Thermal Maturity 3 Calculate present-day TTI at 3000 m in the Red Well. Total depth is reached at 6120 ft in Middle Jurassic rocks. Determine when each of the strata began to generate oil. Age data
top Paleocene base Paleocene base Maastrichtian base Campanian base Santonian base Coniacian 55 Ma 65 73 83 87.Predicting Thermal Maturity . At a depth of 1500 ft. Find when the rock at 3000 m began to generate oil (TTI = 10). Evidence from related sections indicates that the Paleocene was originally about 3000 ft thick and that no other Cenozoic sediments were ever deposited. It is also believed that 500 ft of Lower Cretaceous sediments were deposited before uplift and erosion began. draw a burial-history curve for the section penetrated and calculate maturity for the Kimmeridgian shale.end Cretaceous: 15° C 141° C 25° C
EXERCISE Thermal Maturity 4 The Ultraviolet Well is spudded in Paleocene sediments. Corrected BHT (4200 m): Estimated surface temp. Assuming a surface temperature of 10° C and a geothermal gradient of 2° F/100 ft. assuming a constant geothermal gradient through time.5 88. 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. Total original thickness of the Kimmeridgian is thought to be 1500 ft.
evaluate the prospect. upper management has decided that gas and condensate are not economical. From 40 Ma to the present about 500m of additional burial occurred.000 25. Nearby well control indicates that a geothermal gradient of 3.500 21.0° F/100 ft.
. Carboniferous '' '' '' '' E.500 27.000 8. No other source rocks were noted.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.
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.Predicting Thermal Maturity . At that time nearby orogenic activity caused the first traps to be formed during a gradual 1200m uplift lasting until 40 Ma.000 23.65°C/100 m and a surface intercept of 15°C are reasonable for the area. The geothermal gradient was found to be 1.000 11. Because of the high operations cost. Your responsibility is to make a recommendation regarding the nature of hydrocarbons that might be present in die prospect. oil-prone source rock at about 4300m depth near the prospect. Time-stratigraphic data are given in the following table. The source rock is thought to be about 300 Ma old.000 18. No other reservoirs are anticipated.
"A regional study of the area suggests the probable presence of a thin. No unconformities are recognized within the Paleozoic. Carboniferous '' Ordovician '' Depth (ft) 7. The basin filled at a generally uniform rate from about 300 Ma to 100 Ma. and the surface temperature today is about 15° C. 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. Erosional removal since the Permian probably totals about 2000 ft. Highly fractured carbonates overlie the source rock. rich."
Utilizing the principles of hydrocarbon generation and preservation.68
EXERCISE Thermal Maturity 5 Analyze the timing of oil generation in the Pink Well.000 13. The following geological summary is available to you. The reservoir is sealed by a thick salt layer. they are in turn overlain at 2750m by a sandstone of excellent reservoir quality.
once a discovery is made. we are involved with a greater or less degree of uncertainty about quantities.
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. however. until actually all of the oil has been produced. How do we handle these problems? Before we get into this. even within oil companies. What they think is beyond that in the accumulation. methods. just what these changes amount to. Recoverable reserves: The volume of oil that can actually be produced to surface from an accumulation. they might designate as `probable'. of a well. companies tend to use `proven' for those reserves that are believed to be present with an 85 or maybe 90 per cent degree of
. It usually refers to what was there originally. and oil may be produced directly into it. but the same considerations. is liable to change between our information points. located at surface near the well-head. However. measured in barrels or other units that is present in an accumulation under the ground. First. let alone how much. We will refer to oil. and tertiary reserves using more exotic techniques. secondary reserves. And yet oil companies need to know what to expect. Now we must see how we can apply our knowledge of the geology to assessing the amounts of petroleum that we have found. 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. Similarly. let us again emphasize that we are dealing all the time with uncertainties. which can be produced using assisted or enhanced recovery techniques. half a mile or whatever. of the following terms:
OIL IN PLACE
This is the total volume of oil. Note. We may distinguish between primary reserves that can be produced without any artificial assistance other than pumping. Because anyway there is uncertainty about this amount. before we started to take any of it out. or predict. Some might use the term to refer to the amount of recoverable oil that is believed to lie within a given radius. This may be done via a standard deviation or by a statistical probability (see below).Quantitative Assessment . and terms can be used equally for gas. we have to clear a good deal of misunderstanding and misuse. it is desirable to be able to express our degree of confidence in it. we have to remember that we are dealing with a resource and that we are very concerned with the quantities involved. unless we can be more specific about how we are going to produce them. We have to try to understand. 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. in the case of small fields.69
10 . So. which controls the amounts of oil in the reservoir. A bald figure for `recoverable reserves' is somewhat meaningless. or hope to find. Proven reserves: Here we start to enter a minefield! Different companies have different definitions of what is proven. This section is included to give an idea of what is involved. The stock tank is.Quantitative Assessment
So far we have been talking in rather generalized terms. You may see the engineers using the term STOOIP: stock tank oil originally in place. our wells. Increasingly these days. We cannot regard these quantities as `reserves'. there is no way that we can know precisely how much we have found: the geology. since we are never able to recover all of the oil that is down there in the reservoir. and therefore without any dissolved gas of significance. 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.
to cover the reserves that have only a 15 or 10 per cent chance of being present. We have to discount those parts of it that are useless and just consider the net reservoir thickness. and what is still there for the taking at a given date. then we can go straight to the bulk reservoir volume containing the oil. it shrinks because gas bubbles out of it as its pressure is eased during production. that are meant. It may well be that it is best to avoid the terms `proven'. but what happens between and beyond our well control? – Sw is the water saturation. and regional and local geological interpretation.Sw)] * RF * Constant FVF where: – BV is the volume of the reservoir formation within the closure of the trap above the spill-point.
Once a discovery of oil has been made. This will be controlled by variations in the nature of the sediments that comprise the reservoir. 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. then this factor may be little more than a guess. the volume of the gas cap and the water-bearing rock below the oil-water contact being discounted. If we do not know where the gas-oil and oil-water contacts are. They refer respectively to what was there and recoverable before we started producing. 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. What this means and how we arrive at the figure.Quantitative Assessment . – ? is the porosity. We then eliminate progressively everything from this volume that is not oil. including the adequacy of the source rock to provide enough oil to the trap. – FVF is the formation volume factor. the higher will be the water saturation. 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.70
confidence or statistical probability. if we hear simply about `reserves'. The shape of the trap. `probable'. BV will be determined from seismic and well data. Recoverable reserves = [BV * Fill * N/G * ? * (1 . Probable reserves: Equally dodgy! One definition was given above: the term may be used. It is affected by many factors. meaning that we have to try to interpret in detail the environments that the sediments were deposited in. – Fill is the `fill factor'. What anyway should we regard as net reservoir? A rather arbitrary porosity cut-off value is often used. Again we need an average value for the field. Not all of a reservoir formation is going to be sufficiently porous and permeable to contribute oil to production. and the thickness of the reservoir govern it. in this case 50 per cent. the percentage of the porosity that is occupied by the immovable water. like `proven'. and the quality and strength of the cap rock.
. – N/G is the net to gross ratio. to refer to a degree of confidence or probability. We do our best from measurements on core samples and from wireline log interpretation. So we multiply the bulk volume of the reservoir in the trap by those factors that represent the non-oil. which is the percentage of the bulk volume that actually contains the oil. faulting. This can be pretty subjective. if we do. we shall see shortly. Usually. or rather the average porosity of the net reservoir across the entire accumulation. the normal way of estimating how much has been found is to start with the volume of the reservoir within the closure of the trap. even when we have information from a lot of wells. it is the remaining reserves. Sometimes `possible' is also seen. We may actually be able to measure the FVF if we have a sample of oil collected under subsurface pressures from the bottom of our well.
and arrive at perhaps wildly different answers. Alternatively one may plot the frequencies as percentages of the total number of answers: the statistical probabilities.
Diagrammatic plots of the outputs from two Monte Carlo simulations. then we don't have to worry. somewhere within which the `true' figure must be. The number of answers in successive reserve ranges is plotted against the size ranges themselves. If we plot out the answers on our list falling within successive size ranges (in barrels of oil).. even though they may be well aware that any such figures will eventually turn out to be wrong. and we also specify the total range. but it may be a good deal less from carbonates.). and again. in producing figures for all of these factors. however. Then we get a computer to pick a value for each factor at random from the range we have given. Instead of estimating single figures for the factors that go into the reserves formula. we shall find that the bulk of them tend to cluster round the middle (Fig. Different geologists will certainly come up with different values for at least some of the input factors. So we have a whole list of answers. A constant is needed to adjust the units. It is a figure that we cannot know exactly until we have finished producing. for each of the factors we work out our best estimate. the proportion of the oil in the reservoir that we can actually recover and produce. we have to multiply the figure we calculate by 7758. known as a Monte Carlo simulation. The computer does the sum using these values. So we usually have to base our estimate on prior experience elsewhere. If we are working entirely in the metric system. Note that the preferred answer that is usually used is the mean value. The one that has the most answers in (= the modal class of the distribution) we can regard as the most probable value -in other words.This is because. having regard to all of the geology.. doubtful estimates by doubtful estimates. this is commonly about 50-60 per cent. Then we ask it to do the same thing again. The Americans measure reservoir volume in acre-feet: area in acres multiplied by reservoir thickness in feet. is to multiply uncertainties by uncertainties. In a sandstone reservoir. there must be considerable uncertainty to say the least. we give as our preferred figure the average of all the answers (the mean). for this average value. we can work out the standard deviation (the ±) which will give an idea of our confidence in our answer. our best estimate. companies. What we are doing. maybe 500 or 1000 times. Most commonly these days. and governments must have numbers that they can use for planning purposes. until we begin to wonder whether our answer has any reality or meaning at all. the problem is tackled through a statistical technique.
It will be clear to anyone that. The list is put into order from the smallest to the largest.Quantitative Assessment . and then analysed statistically. then. More commonly. but biassing its pick towards our best estimate. any one of which could be the real value. from minimum possible to maximum possible. since it is about this that the standard deviation can be calculated. Who is right? Whose answer should we use? Can we indeed believe any of them? Unfortunately we cannot escape from the problem. and to try to be as honest and objective as possible. and again.71
RF is the recovery factor. To get an answer to our sum in barrels of oil.
We have to give not only our best estimate of how much petroleum there might be. The risk factor. the same values are discounted by a 50 per cent risk factor. and then merely combine the probabilities to give an overall probability .at least until we start also considering the costs and economics.
This is all very well. different geologists will arrive at different figures for the probability of success. but it assumes that we have already discovered oil. Indeed it does not! When we are looking at exploration of the unknown. 50.72
The output from a Monte Carlo simulation with the percentages plotted cumulatively. now gives a more complete picture of the viability of an undrilled prospect .
Most usefully. we have to go a stage further. if any one of them fails or is lacking. 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. Of course we try to be as scientific. it doesn't take any account of the fact that our exploration well may. of our confidence that there will be at least some oil. It cannot be worked out completely objectively. It will give a graph which shows the probability that the reserves will be of a certain size or more. We try to assess the probability that each factor will be satisfied.Quantitative Assessment . objective. but also the chance of there in fact being any oil at all. Incidently. It is this sort of thing that helps to make the oil exploration business so competitive. the 90. if the engineers say that a field of so many million barrels is going to be needed to justify development and production costs. By plotting the answers from the 100 per cent probability downwards. turn out to be totally dry-lacking in hydrocarbons. the curve represents the chance (probability) that the reserves are a certain size or greater. probable. combined with the estimate of how much. there really is no such thing as the risk factor. that is exactly what it is.
. This is what is used to determine those reserves that may be called proven. for geological reasons. then no oil. So this type of graph has now become one of the standard key tools in exploration/development decision. perhaps. and possible at. say. to give the chance of discovering certain reserves or more including the 50 per cent chance that we may find nothing at all. we can read off from the graph the chances of our field containing that much oil or more. you may say. and ensures that all possibilities are considered. in numbers. And if all this sounds like a gambling game. When it comes down to risk. In the lower plot.). 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. For example. It is also used to assist management in making their exploration/development decisions. as opposed to assessing what we already know to be there. but rather it is the number an individual geologist might produce to reflect his/her personal interpretation of the geology. This chance (probability) is known as the risk factor: it is an expression. we can plot out the percentages of answers in successive size ranges cumulatively as we work down the list (Fig. management can then decide whether or not to take the gamble on developing the field at those odds. and 10 per cent levels of probability respectively. and honest as can be in assessing exploration risk.the risk factor.
We could make comparisons between known and unknown basins. the expected reserve estimates from our Monte Carlo simulation multiplied (discounted) by the risk factor (Fig. and use the figures for the known also for the unknown ones. qualify it by a statistical probability. and the area under that bit will represent what. This starts with the volume of mature source rock in the basin and then. unless we really have a lot of information (we never have enough!). on average. it is a pretty wild sort of plot. This combines in a single estimate. The obvious thing to do is to add together the risked reserves estimates of all the remaining prospects. 6. if we draw a smooth line through it to even out the peaks and the troughs. In a similar vein the amount of oil found world-wide each year from the beginning of the century can be plotted. however. 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. or underlying each square mile of surface area.). This figure is extremely imprecise and may be not much more than a guess. If all else fails. and made available for entrapment (the `charge') can be calculated. let us note a number known as the risked reserves. but some will be dry. Should we. 3. But we have to admit that. There are lots of uncertainties in this but the calculation would be amenable to a Monte Carlo type of simulation. 5. we can. this technique may bring us into the right ball-park. 2. the two elements of size and chance of success. otherwise we may be doing little more than guessing. 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. remains to be found. knowing how rich it is. expelled. then use these figures for the unexplored parts of the basin. Let us look at the more important ones. is a hypothetical figure. Use past statistics (number of barrels of oil found on average for each 100m of exploration drilling?) and extrapolate to future drilling. If we have a reasonable amount of information and control.Quantitative Assessment . We could adopt what is known as a `geochemical material balance' approach. 4. get a number of experts to make their forecasts by whatever technique they prefer and. Delphi was the place in ancient Greece where one went to consult the oracle about one's future. and a number of techniques have been employed. This kind of plot can be used also for individual basins or for the whole world. all of them are very dodgy
. to believe that we can do this would be the height of conceit. then the area under it represents the total volume of oil found to date.
So far we have been talking about a single oil accumulation or a single prospect.73
Lastly. Adding this to the original reserves will give us what is sometimes called the `ultimate reserves'-a grand total for the basin. we are said to be consulting the oracles! All of the above techniques have been used. Extrapolate this smoothing line out into the future. however. This is known as the Delphi technique. and some may be more appropriate in given circumstances than the others. and as such can be very useful in planning an exploration program. However. sometimes in combination. However. the built-in risk factor takes care of this. go for a large but very risky prospect. for our `best estimate'. 1. Undiscovered are thus what we hope to find in a prospect area or sedimentary basin in the future. for example. We might look at explored and known parts of the basin. we have to assume that today we can identify and assess all of the prospects that ever will be found in the basin. and calculate average quantities of oil per cubic mile of sediment. merely use the average of the figures they produce. 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. on this tack. Some of these will be successful. or would our money be better spent on drilling a smaller but safer one? The risked reserves. the amount of oil generated.