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Geochemistry: The field of geochemistry involves study of the chemical composition of the Earth and other planets, chemical processes and reactions that govern the composition of rocks, water, and soils, and the cycles of matter and energy that transport the Earth's chemical components in time and space, and their interaction with the hydrosphere and the atmosphere. Geochemistry and Hydrocarbon Assets: Hydrocarbon assets proceed through stages that include basin evaluation, prospect evaluation, discovery drilling, developmental drilling, production, enhanced recovery, abandonment and reclamation. During the progress through this life cycle there are constant changes in the types of information needed to make decisions about developing and managing the asset. Application of geochemical techniques to oil and gas exploration Application of geochemical techniques to oil and gas exploration provide increased understanding of hydrocarbon generation, migration, and accumulation processes within a basin prior to drilling. As more samples become available, geochemical techniques can outline complex basin filling histories, explain unusual oil and gas distributions, and identify the sources of oil and gas. When considered against random drilling, geophysics (trap size) alone provides a forecasting efficiency of 28%, while geophysics in conjunction with geochemistry provides a forecasting efficiency of 63% for locating hydrocarbons during exploration (Sluijk and Parker, 1986). Petroleum geochemistry has proven to be an effective and inexpensive tool for reducing exploration risk. In applying petroleum geochemistry to exploration problems, a major focus is the analysis and interpretation of the compositions of the complex hydrocarbon fluids. The composition of oil and gas is dependant on many factors, including the original source material, the source maturity, the migration distance, the attributes of the carrier bed, and post accumulation processes such as biodegradation, leakage, thermal stress and water-washing. Each of these processes establishes or alters the fluid composition in predictable ways. Fluid composition can be used to detect and characterize these processes. Learn more at Geochemical Laboratory Analysis for Oil and Gas Identifying Mixed-Sourced Petroleum: An example of applying geochemistry to determine oil source can be seen in a study of an offshore Tertiary rift basin in eastern Asia (Bissada, Elrod et al., 1993). The basin contains three large deltaic systems along a northeastward trend. Examination of the oil compositions from each of the three systems indicated that the northernmost oil accumulation was sourced from a hypersaline lake facies, while the southernmost was from a freshwater lake facies. The center accumulation has compositional and isotopic characteristics of both types of sources and was determined to be a mixture of the two oil types. When the geochemical findings were placed in the geologic setting, it was clear that the two oil types were generated from two separate generative troughs and the mixed oil was accumulated on a ridge situated such that it could receive oil from both troughs. The findings had significant implications with regard to further exploration in the area. Understanding the Distribution of Oil Quality in a Basin: Geochemistry can also be important in assessing the distribution of hydrocarbons in a basin with regard to oil versus gas, high-sulfur versus lower-sulfur oil, heavy versus light oil, and other parameters. This is illustrated by a study done on the Barinas Basin in Venezuela (Anka, Callejon et al., 1998). An integrated geochemical-geologic approach, which included computer simulations, was able to determine that the source of the oil was the more distant La Luna formation, not the nearby La Morita formation, and that the basin had a complex filling history.

The Barinas Basin study revealed that there was an initial pulse of oil that filled the reservoirs, however, the reservoirs were shallow and the oil was subsequently degraded. Next, thrusting rapidly buried reservoirs and source sequences in the northernmost part of the basin. This resulted in cracking of the reservoired oils in the deeply buried sections to condensates and additional gas condensate generation from the local source rocks. Finally, the source in the center to southern parts of the basin is currently mature and expelling oil to the reservoirs above. This filling history explains the distribution of oil in the basin, with gas condensates in the north, lighter oils (initially degraded, then lighter oil added) in the center to southern parts of the basin, and heavy degraded oils in the south. Enhancing Hydrocarbon Asset Life: As we have seen, the processes that result in generation and accumulation of hydrocarbons determine the composition of the fluids and can be characterized based on the fluid compositions. Production and enhanced recovery processes also alter the composition of the hydrocarbon fluids, therefore composition of the fluids can also be used to monitor and characterize production and enhanced recovery processes. In recent years, geochemistry has been increasingly applied to development, production, and enhanced recovery processes. Petroleum geochemistry is proving to be an effective and inexpensive tool these processes. Identifying Missed Payzones: Geochemistry can be utilized to identify new or missed opportunities during exploration and development. For example, in some situations, a reservoir can be uplifted or breached resulting in a sudden change in the pressure-temperature relationship in the reservoir. When the conditions are right, this can cause the oil to separate into two phases, with the lighter phase migrating to a shallower reservoir. The resulting condensate and residue have distinctive geochemical compositions that indicate the phase separation history of the hydrocarbons. When the residue portion of the hydrocarbons is encountered during drilling, it indicates that a lighter phase has migrated up dip and may have accumulated there. Conversely, if the condensate portion were encountered first, that would indicate that a residue hydrocarbon accumulation is likely somewhere down dip. Delineating Reservoir Compartmentalization: During production of oil or gas, it is important to understand the geometry of the reservoir, that is, the locations of any faults or permeability barriers that could affect production. Since the reservoirs are filled with fluids and the composition and characteristics of the fluids are sensitive to reservoir processes, we can expect fluids within separated compartments of the reservoir system to have different compositions. In recent years, high-precision analyses of the compositions of oil and gas have been successfully employed to delineate reservoir compartments and communication. In a recent study (Ramos, Callejon et al., 1999), geochemistry was used to determine reservoir compartmentalization within a gas field in Mexico. Seventeen gas samples from the field were analyzed for component and isotopic compositions. As expected, the gases produced from different fault blocks had different compositions. However, the results revealed significant differences among some gases produced from the same fault blocks. Since the rate of diffusion of gas is relatively rapid, any significant difference was interpreted to be due to a barrier to fluid communication. Thus, the data were used to identify previously unknown barriers to migration

within the fault blocks and provided a more in-depth understanding of fluid movement within the field. Subsequent comparison indicated that the geochemical conclusions were consistent with recently acquired 3D seismic data. Geochemistry has provided key information that distinguished between two geologic interpretations of a field. In the study (Kaufman, Ahmed et al. 1989), the geologic information was ambiguous leading to two interpretations of the location of significant faults in the field. To distinguish between the two models, oils from the producing wells were analyzed and the result presented in a star diagram, a plot of the data on a radial axis that enables easy recognition of differences. The results revealed three groups of similar oils that were consistent with one of the geologic interpretations. This clearly indicated that one geologic interpretation was more correct and improved understanding of the field for further development. Maximizing Waterflood Efficiency: Geochemistry can also be useful for planning and monitoring enhanced recovery processes. In a study of the Centro Lago Field, Venezuela (Elrod, Vierma et al. 1997), hydrocarbons from different sand units were analyzed for the purpose of identifying fluid flow units within the reservoirs and optimizing a waterflood project. The data identified barriers to fluid flow that were previously undetected and reservoir connectivity among some of the units that was previously unknown. The results were critical in planning and optimizing a waterflood program in the field. Monitoring Produced Fluids: The fact that hydrocarbon fluid compositions are affected by geologic and reservoir processes is what makes fluid composition useful for studying hydrocarbon generation, migration, and entrapment history. Production and enhanced recovery processes also affect hydrocarbon fluid compositions in predictable ways. Slow or sudden changes in the composition of produced fluids can indicate changes in reservoir characteristics, subsurface fluid conditions, or problems with the production equipment. Periodic monitoring of produced hydrocarbon fluids can identify such changes at low cost. Periodic geochemical analysis of produced fluids has been successfully applied as a useful tool to a number of production issues. Allocating Commingled Production: In many wells, oils from different stratigraphic zones are commingled and produced from a single production string. In many cases, legal or ownership requirements will necessitate the monitoring of production from individual commingled zones. Even without those requirements, it is necessary to monitor the production from individual zones to optimized production of from the reservoirs. When there is sufficient (even a small) difference in the composition of the oils from the different zones, periodic geochemical monitoring can be used to determine the production from each zone. The technique requires only that a small sample of the produced hydrocarbons be taken periodically for analysis. Changes in the composition can identify and quantify depletion of individual zones relative to one another and recognize changes in production related to reservoir or other production problems. The techniques can be applied to a larger number of commingled zones, provided there are sufficient differences amount the oils in the various zones to distinguish each. Initially, oils from each zone are fully analyzed and the differences identified. After the initial analyses, a smaller number of diagnostic analyses can be used for monitoring the composition of the commingled fluid during production. There are techniques available for monitoring even when samples from the individual zones are not available. Periodic hydrocarbon monitoring data can also be useful when zones are not commingled. In cases where different zones are produced in separate

tubing, periodic monitoring of the hydrocarbon fluid composition can detect failures in the production apparatus. Learn more at Allocation Engineering Services Recognizing Production Tubing Failure: In one case, a deeper, higher-pressure zone and shallower, lower-pressure zone were being produced through separate tubing. Ownership interests were different for the two zones, so the integrity of the separate production was important beyond the production ramifications. Gas chromatograph (GC) analysis of the oils from the two zones showed that they were clearly different and easy to distinguish. Years later, another GC analysis of the two production oils revealed that they were the same and matched the oil from the high-pressure zone. Further investigation revealed that corrosion had breached the containment of the high-pressure oil and was allowing it to flow into the lower pressure zone. This meant that the production from both strings had been from the higher-pressure zone since the breach and the owner of the higherpressure oil had been giving away oil to the owner of the lower pressure zone. Learn more at Corrosion Services Detecting Cementing Failure: In another case from California, a well was producing solely from the Monterey formation, but the shallower Sisquoc zone had been cemented. During production, fluid was discovered behind the well casing. Analysis indicated that the fluid did not match the oil from the Monterey. Because samples had been taken and analyzed from the Sisquoc prior to cementing, the geochemists were able to compare the fluids and determine that the behind-casing fluid matched the Sisquoc. This indicated that the cement job had failed and the work was redone. Predicting Flow-assurance Problems: Another problem encountered during production is that of solid deposition and plugging. Asphaltenes, paraffins, and gas hydrates can, under the right conditions, precipitate and cause plugging problems during production. Geochemical analysis of reservoir fluids can quantify and characterize asphaltenes and paraffins and permit prediction of precipitation problems during field appraisal. Recent work also suggests that the evaluation of gas, water, asphaltene, resin, and other surfactant content can enable the prediction of hydrate formation. Prediction of precipitation problems early in the exploration process allows planning and inclusion of costs of specialized production techniques or avoiding problems by selecting production areas that do not exhibit tendencies to precipitate solids. Learn more at Flow Assurance Services Identifying the Source of Environmental Contamination: Geochemistry is an important element in addressing environmental issues related to petroleum exploration, production and transportation. Keith Kvenvolden (Kvenvolden, 1993) of the USGS performed a study of residual tar in Prince William Sound, following the Exxon Valdez spill in 1989. He gathered tar from beaches and other areas around the sound and used carbon isotopic composition to determine the source. In 1990, most of the tar samples matched Alaska oil that was spilled from the Exxon Valdez. However, a 1992 sampling yielded mostly tar from California oil. After some investigation, Kvenvolden concluded that most of the tar contamination remaining in Prince William Sound is the result of the destruction of an asphalt storage facility in Valdez by the earthquake of 1964 and subsequent tsunamis. This event spilled large amounts of asphalt into the sound. Since asphalt is more resistant to evaporation and degradation than lighter Alaska oil it has remained, while most of Geochemistry in Tax Litigation: Geochemistry can be useful in other areas of the petroleum business. For example, a few years ago, Four Star Oil entered litigation with the Internal Revenue Service (IRS) to recover overpayment of

taxes. The issue involved whether oil produced from certain wells in California in the early 1980s was tar sand by the IRS definition. A major issue in the definition is whether the oil is produced in its natural state. An important point in showing that the oil was not produced in its natural state was to show that it was necessarily chemically altered during production. A geochemical approach was able to show that the oil was chemically altered during steam flooding. The finding was based on laboratory tests on a number of asphaltenes and on the kinetics of conversion of California Monterey kerogen (which is similar to the asphaltenes found in the oil) to oil. The study demonstrated that a substantial proportion of asphaltenes are converted to lighter, oil-like substances when exposed to the temperatures of the steamflooding for a few hours to a few weeks. This was an important part of the overall case by Four Star that led to a favorable settlement prior to going to court. Geochemistry is a proven tool for managing and monitoring hydrocarbon assets in every stage of asset life. From exploration to enhanced recovery and beyond, geochemistry provides vital information about almost every aspect of hydrocarbon asset management. Geochemistry is inexpensive, compared to the value of the hydrocarbon assets, investments in drilling and production hardware and compared to other sources of information used. We recommend that geochemistry be utilized at every stage of petroleum asset life as part of an integrated toolbox that includes geophysics, geology, engineering data, and other sources. Intertek Westport has the analytical capability, expertise and experience to address geochemical problems in any phase of petroleum asset life. How to make Geochemistry an effective tool: Collect samples: During exploration and development, drilling sediment and all encountered hydrocarbon fluids should be sampled and stored. Sediment should be sampled with cuttings. Organic rich sediments and reservoir intervals should be cored, especially during the exploration phase. Drilling fluids, especially oil-based and those with organic additives, should be periodically sampled as well. All encountered hydrocarbon fluids should be sampled. When possible, reservoircondition samples are best. Although this will add some cost to drilling, the samples can have enormous value in later stages of asset life. Analyze hydrocarbon samples when initially taken: Simple compositional and isotopic analyses are not expensive, but can be valuable. For example, an unexpected composition for a sample during development drilling could indicate an undetected barrier to reservoir communication, and indicate that the drilling program may need modification. Alternatively, it might indicate a phase segregation event that could lead to new discoveries in the field. In addition, the analyses provide a baseline for comparison with later production samples and can be useful for monitoring production effectiveness. types of organic matter Organic matter (or organic material, Natural Organic Matter, or NOM) is matter that has come from a once-living organism; is capable of decay, or the product of decay; or is composed of organic compounds. The definition of organic matter varies upon the subject for which it is being used. Organic matter is broken down organic matter that comes from plants and animals in the environment.[1] Organic matter is a collective term, assigned to the realm of all of this broken down organic matter. Basic structures are created from cellulose, tannin, cutin, and lignin, along with other various proteins, lipids, and sugars. It is very important in the movement of nutrients in

the environment and plays a role in water retention on the surface of the planet. These two processes help to ensure the continuance of life on Earth. Kerogen Kerogen is a mixture of organic chemical compounds that make up a portion of the organic matter in sedimentary rocks. It is insoluble in normal organic solvents because of the huge molecular weight (upwards of 1,000 daltons) of its component compounds. The soluble portion is known as bitumen. When heated to the right temperatures in the Earth's crust, (oil window ca. 60 160 C, gas window ca. 150200 C, both depending on how quickly the source rock is heated) some types of kerogen release crude oil or natural gas, collectively known as hydrocarbons (fossil fuels). When such kerogens are present in high concentration in rocks such as shale they form possible source rocks. Shales rich in kerogens that have not been heated to warm temperature to release their hydrocarbons may form oil shale deposits. Formation of kerogen t the demise of living matter, such as diatoms, planktons, spores and pollens, the organic matter begins to undergo decomposition or degradation. In this break-down process, (which is basically the reverse of photosynthesis [4]), large biopolymers from proteins and carbohydrates begin to partially or completely dismantle. These dismantled components can come together to form new polymersreferred to as geopolymers. Geopolymers are the precursors of kerogen. Compositions kerogen is a mixture of organic material, rather than a specific chemical, it cannot be given a chemical formula. Indeed its chemical composition can vary distinctively from sample to sample. Kerogen from the Green River Formation oil shale deposit of western North America contains elements in the proportions carbon 215 : hydrogen 330 : oxygen 12 : nitrogen 5 : sulfur Types kerogen breaks down to form heavy hydrocarbons (i.e. oils), refractory kerogen breaks down to form light hydrocarbons (i.e. gases), A Van Krevelen diagram is one example of classifying kerogens, where they tend to form groups when the ratios of hydrogen to carbon and oxygen to carbon are compared Type I: Sapropelic containing alginite, amorphous organic matter, cyanobacteria, freshwater algae, and land plant resins Hydrogen:carbon ratio > 1.25 Oxygen:carbon ratio < 0.15 Shows great tendency to readily produce liquid hydrocarbons. It derives principally from lacustrine algae and forms only in anoxic lakes and several other unusual marine environments Has few cyclic or aromatic structures Formed mainly from proteins and lipids Type II: Planktonic Plankton (marine) Hydrogen:carbon ratio < 1.25 Oxygen:carbon ratio 0.03 to 0.18 Tend to produce a mix of gas and oil. Several types: Sporinite: formed from the casings of pollen and spores

Cutinite: formed from terrestrial plant cuticle Resinite: formed from terrestrial plant resins and animal decomposition resins Liptinite: formed from terrestrial plant lipids (hydrophobic molecules that are soluble in organic solvents) and marine algae They all have great tendencies to produce petroleum and are all formed from lipids deposited under reducing conditions. Type IIsulfur Similar to Type II but high in sulfur. Type III: Humic Land plants (coastal) Hydrogen:carbon ratio < 1 Oxygen:carbon ratio 0.03 to 0.3 Material is thick, resembling wood or coal. Tends to produce coal and gas (Recent research has shown that type III kerogens can actually produce oil under extreme conditions) Has very low hydrogen because of the extensive ring and aromatic systems Kerogen Type III is formed from terrestrial plant matter that is lacking in lipids or waxy matter. It forms from cellulose, the carbohydrate polymer that forms the rigid structure of terrestrial plants, lignin, a non-carbohydrate polymer formed from phenyl-propane units that binds the strings of cellulose together, and terpenes and phenolic compounds in the plant. Type IV (residue) Hydrogen:carbon ratio < 0.5 Type IV kerogen contains mostly decomposed organic matter in the form of polycyclic aromatic hydrocarbons. They have no potential to produce hydrocarbons.

Origin of material Terrestrial material The type of material is difficult to determine but several apparent patterns have been noticed. Ocean or lake material often meet kerogen type III or IV classifications. Ocean or lake material deposited under anoxic conditions often form kerogens of type I or II. Most higher land plants produce kerogens of type III or IV. Some coal contains type II kerogen. Extraterrestrial material [7] Carbonaceous chondrite meteorites contain kerogen-like components. Such material is believed to have formed the terrestrial planets. Kerogen materials have been detected in interstellar clouds and dust around stars. Type I kerogen is freshwater lacustrine with anoxic bottom conditionsTertiary Green River shale, Wyoming). Of the four kerogen types, Type I is richest in alkyl chains; it is lowest in polycyclic and nonhydrocarbon compounds. From laboratory heating experiments (pyrolysis) Tissot and Welte (1984) determined that Type I kerogen is an excellent source of bitumen and can yield up to 80% by combined weight of volatile and extractable materials. For geochemical interpretive purposes, Type I kerogen is classified as oil-generative during catagenesis. Because of the relatively restricted life forms and depositional environments requisite for Type I kerogen, however, this type is not abundant in the geologic column and, therefore, not the major source of crude oil.

Type II kerogen, compared to Type I, is less rich in hydrogen relative to carbon. It is commonly considered to be a degraded mixture of phytoplankton, zooplankton, and bacteria ( Figure 3 , exinites) ; its most common originating environment is marine with reducing bottom conditions (e.g. , Lower Toarcian shales of the Paris basin). Compared to Type I, Type II kerogen contains shorter alkyl chains plus more naphthenic, polyaromatic, and nonhydrocarbon components. Type II kerogen is a good source of bitumen and can yield up to 60% volatile-extractable materials by weight with pyrolysis. Type II kerogen is oil-and-gas generative during catagenesis; its far greater natural abundance in the geologic column, compared to Type I, makes it the major petroleum-producing kerogen type. Type III kerogen, when initially formed, has a relatively low hydrogen-carbon ratio and what is considered a high oxygen-carbon ratio. The principal source of Type III kerogen is woody vegetal material ( Figure 3 , vitrinites). Diagenetic alteration of soluble woody material in a terrestrial setting commonly is through the humic process; rapid burial in marine waters near continental margins (e.g., Tertiary deltas) can lead to incorporation of nearly nondegraded Type III precursor plant detritus into sediments. Type III kerogen is rich in heteroatoms, aromatic and polycyclic molecules, and long-chain alkanes related to plant waxes, plus shorter chains and methyl groups. Low amounts of bitumen are generated from Type III kerogen by pyrolysis. Type III kerogen is principally gas generative during catagenesis; paraffinic liquid bitumen can be derived from the alkane chains. Type IV kerogen was introduced previously as recycled or oxidized organic material. Relative to generative kerogen types, Type IV kerogen has a very low hydrogen-carbon ratio; it can have a high oxygen-carbon ratio reflective of its oxidized past. Type IV kerogen generally is considered to have no petroleum-generative capacity. However, some controversy exists on this interpretation (Smyth 1983, Cooper basin oil source) as it does with many generalizations when applied rigorously to exploration geochemistry. For example, if Type IV kerogen is inferred from visual presence of opaque macerals, hydrocarbon source potential can be understated. Hydrogen-rich organic matter (e.g., resinite, exinite) can be present but obscured by opaqueness, thereby leading to poor estimation of generative capacity (Powell, Creaney, and Snowdon 1982). The common method used in geochemical studies to establish kerogen type and related generative potential based on hydrogen, carbon, and oxygen content is depicted in Figure 4 , (Kerogen classification based on chemical parameters: Van Krevelen diagram based on hydrogen-carbon and oxygen-carbon ratios from elemental analysis). Composition andstructure: Properties of Petroleum Petroleum is commonly categorized according to two sets of characteristics:

as an organic substance commonly subdivide it into related chemical compound types (e.g., hydrocarbon versus nonhydrocarbon compounds; paraffin content; presence of sulfur-bearing compounds). Others that deal with oil and gas primarily as a market product, are more apt to categorize petroleum on physical bases (e.g., gas versus liquid; distillation ranges; API gravity). Exploration geochemistry as a discipline deals with both perspectives. Those who use geochemical programs and data have to integrate both chemical and physical properties and must recognize how the two can but need not be directly related. Petroleum is composed of two principal fractions

ydrocarbon compounds

Figure 1 The first of these consists of molecules that are combinations of hydrogen and carbon atoms only, hence their name. The molecules of the other fraction also contain high percentages of hydrogen and carbon atoms nonhydrocarbons, however, also have additional atoms bound into the molecules, The most common of the additional atoms, or heteroatoms as they are designated, are nitrogen, sulfur, and oxygen. Because these three elements are the most common heteroatoms, the names NSO compounds, or just NSOs,"non-hydrocarbons" for that fraction of petroleum containing heterocompounds. The nonhydrocarbon fraction can have molecules which contain heteroatoms besides nitrogen, sulfur, and oxygen. Typically these heteroatoms consist of metals such as nickel, vanadium, magnesium, and copper. In some heteromolecules the metals represent trace elements originally taken in by biotic processes. In others, metals have been incorporated in organic compounds as a result of postdepositional alteration and migration processes. Volumetrically, hydrocarbons generally make up more than 70% of liquid petroleum, that is crude oil, as it is withdrawn from subsurface reservoirs (Tissot and Welte, 1984); nonhydrocarbon compounds make up the remainder, Hydrocarbon and nonhydrocarbon fractions can be subdivided into four chemically distinct groups based on molecule types present General classification system used for petroleum); the four major subdivisions are (1) saturated hydrocarbon molecules called alkanes,

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Saturated Hydrocarbons (Alkanes) Hydrocarbons are molecules consisting entirely of hydrogen and carbon atoms. In classifying petroleum, saturated hydrocarbons - alkanes - have been separated from unsaturated hydrocarbons - aromatics - on the basis of whether more hydrogen can be added to the molecule without disrupting the structure of the molecule. If we wish to subdivide the alkane group further, the one major variable left is the manner in which the carbon atoms are linked together. This carbon-skeleton linkage can be straight chain, branched chain, or closed (looped) chain (show in fig 3) Normal AlkanesIf carbon atoms bond together in a straight chain using single bonds, then the hydrocarbon molecule is referred to as a normal alkane ( Figure 3 ,

(Methane gas, which contains only one carbon atom, is considered the simplest of normal alkanes, although one carbon atom alone cannot form a carbon-chain structure.) In order to balance the valence charge, a continuous carbon chain bonds hydrogen atoms at the remaining free electrons available for bonding along the sides of the chain, plus the two unused bonds at the end of the chain. This gives all normal alkanes the basic formula CnH2n+2 . For normal alkanes with carbon numbers less than five, the names used are the historical ones-methane (C1), ethane (C2), propane (C3), and butane (C4). These unsystematic names of gaseous straight-chain hydrocarbons must be memorized. Low molecular weight compounds like propane (C3), however, seldom carry the n prefix because branched-chain and cyclic alkanes found in petroleum do not occur below C4 and C5, respectively. A common method of diagramming the skeletal arrangement of normal alkanes, and that approximated in many geochemical reports and articles, is shown in Figure 5(Methodology for depicting organic compounds: normal alkane representation).

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Figure 5

(2) unsaturated hydrocarbon molecules called arenes Unsaturated Hydrocarbons Aromatic hydrocarbons (also called arenes in some geochemical reports) are the unsaturated hydrocarbons found in petroleum. Their diagnostic characteristic is the presence of at least one unsaturated, six-carbon benzene ring (Benzene ring structure in aromatic compounds). Other unsaturated-series hydrocarbons commonly present in organic matter and refinery products, but not in petroleum, are alkanes (one carbon-carbon double bond), dienes (two carbon-carbon double bonds), polyenes (more than two carbon-carbon double bonds), and alkynes (containing a triple carbon- carbon bond) ( Figure a, General classification system for nonaromatic unsaturated hydrocarbon molecules

Fig,A . Aromatic Hydrocarbons The requisite character of aromatic compounds is the presence of at least one six-carbon benzene ring. This places aromatics in the cyclic hydrocarbon category like the cycloalkanes, in contrast to the acyclic normal and branched alkanes. Unlike nearly all other unsaturated hydrocarbon molecules found in organic compounds and refinery products referred to previously ( Figure 2 ), the unsaturated benzene ring is thermally stable for temperatures found at typical oil-reservoir depths. Therefore, aromatic compounds can make up a major portion of crude oils. The formula of the simple benzene ring is C6H6. This means that benzene has six carbon atoms (C6) with alternating or shared double bonds and six hydrogen atoms (H6). Therefore, the hydrogencarbon ratio of this simple, pure aromatic is 1:1. Because the smallest aromatic molecule is

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benzene, aromatics do not occur in the C5-or-lighter (gaseous) range of petroleum. In the light liquid, gasoline range (C4-C7) analysis, only two aromatic compounds existbenzene with six carbon atoms and toluene with seven. The latter represents a benzene ring with one methyl group attached to it. Under a carbon skeletal classification, this molecule could be called a methylbenzene.

(3) small nonhydrocarbon molecules called resins, and (4) large nonhydrocarbon molecules called asphaltenes. Because arenes (ar for aromatics - fragrant - and enes for unsaturated) in petroleum consist entirely of aromatic-series compounds, the series term aromatics is generally substituted for the group term arenes in geochemical data dealing with petroleum. This discussion follows that convention and for the four petroleum groups uses the terms ics

Alkanes (al (k) for aliphatic-fatty-and ane for saturated), as defined in our Fundamentals of Petroleum Series, are those hydrocarbons that are fully saturated with hydrogen

Figure 3

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Figure 4

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Figure 6

Figure 7 Cycloalkanes The definitive characteristic of cycloalkanes, also called naphthenes, is that the saturated carbon chain closes or cycles on itself to form a ring ,

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Figure 4 Isomers Cycloalkane molecules can have side branches and chains resulting in molecules with the same chemical formula but different arrangements of carbon and hydrogen atoms. Any further addition of hydrogen, consequently, must occupy a preexisting carbon-carbon bond position. Such a bond exchange either breaks a hydrocarbon molecule into smaller saturated molecules or breaks a saturated ring (cyclic) structure into a saturated open (acyclic) structure . Aromatic hydrocarbon compounds consist of molecules that contain an unsaturated benzene ring

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Figure 8 Resins are smaller heterocompounds present in the gross non-hydrocarbon fraction ( Figure 1 ) that remain in liquid form (can be extracted) in the presence of hydrocarbon solvents such as methane and pentane. Asphaltenes are larger heterocompounds which, because of their relatively large molecular sizes, generally will precipitate in the presence of hydrocarbon solvents such as methane and pentane. (Note: Asphaltene precipitates can trap molecules of other groups within their large condensed structures. However, it is standard convention to apply the term asphaltenes to all precipitated materials because they responds like asphaltenes to chemical treatment and analysis.) API Gravity The specific gravity or density of an oil is often used to categorize it. API gravity is a common oilindustry method of expressing this physical property. API oil gravity ( API)(American Petroleum Institute) values are calculated by this formula:

PI means of showing this relationship is the formula In general, the higher the API gravity (e.g., 350 versus 550) the lower the density or lighter the liquid (e.g., medium weight oil versus condensate).

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Techniques used for source rock study and estimation of source potential: The geochemistry laboratories provide detailed oil reservoir source rock evaluation services that includes TOC determination, source rock potential determination through Rock Eval Pyrolysis and source rock proclivity and maturity determination utilizing Vitrinite Reflectance and Visual Kerogen Typing techniques. Vitrinite Reflectance provides measurement of maximum palaeotemperatures in hydrocarbonbearing basins. Visual Kerogen Typing offers identification of Kerogen. Kerogen is solid, waxy, insoluble organic matter found in oil shale rock, consisting of a variety of hydrocarbons. Oil and gas source rock analysis: Sample Washing, Picking, Lithological Description Solvent Extraction of Oil Based Mud Contamination TOC Content Analysis Combustion Rock Evaluation, Pyrolysis Analysis, He Pyrolysis Vitrinite Reflectance Analysis (Whole Rock) Reflectance Vitrinite Reflectance Analysis (Coals, point count to 1000 counts) Reflectance Kerogen Maceral Analysis (qualitative) Optical Kerogen Maceral Analysis (quantitative Point Count) Optical

Evaluation of sorce rock Hydrocarbon source rock evaluation Sediments that have been able to generate petroleum or which may have the potential to do so are called source rocks. Organic rich shales, mudstones and certain very ne-grained carbonates deposited under suitable conditions and oxygen decient waters are considered excellent source sediments. Both autochthonous and allochthonous organic debris contribute to the total organic matter (TOM) of a litho-unit. Type of organic matter and its facies are considered very important while evaluating source rock potential. These types of organic matter must be identied and distinguished, for dierent types of organic matter have dierent hydrocarbon potentials and products. The dispersed organic matter is classied in to various categories depending on the degree of alteration The dierent types of organic matter identied in the investigated sedimentary sequence of the Marhighat area are broadly classied into: humic and sapropelic. The humic organic matter is land or terrestrially derived and is easily recognizable, however, sapropelic organic matter is derived both from marine and terrestrial sources. These broad organic matter types are further subdivided and classied in to subfacies (based on Swamy et al 1994) to evaluate hydrocarbon source rock potential of these sediments. The dierent types of organic matter and their frequency variation patterns as revealed in the Marhighat section of the Subathu Formation is depicted in gure 2 and the hydrocarbon source rock potential based on the type of each of the recovered organic matter subfacies and TAI is discussed as below Structured terrestrial (wood/cuticle): This organic matter comprises unaltered cellular remains of leaf, root and stem tissues and is represented in low frequency, i.e., 01% (avg. 0.3%) in the study area. It mainly contributes for gaseous hydrocarbons. Biodegraded organic matter: This is the plant derived organic matter that has undergone a considerable amount of biodegradation, but still shows visual traces of its cellular structure. The

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frequency of biodegraded organic matter in the investigated area is 036% (avg. 4.9%). This organic matter is considered to possess enhanced hydrocarbon source potential than structured terrestrial organic matter. Amorphous organic matter: This organic matter is completely structureless and is the end product of structured and biodegraded plant parts. Amorphous organic matter in the present section is of yellowish to grey in colour which indicates the presence of reducing environmental conditions during deposition (Masron and Pocock 1981). The frequency of this organic matter is quite high (avg. 75%) in the studied sediments and the range varies from 199%. Amorphous organic matter is considered to be an excellent source for liquid hydrocarbons Black debris/charcoal: This is the product of oxidation of structured materials. Occurrence of black debris in the above sediments ranges between 1 and 65% (avg. 16.6%). Black debris suggests oxidizing environment during deposition. It has no/negligible hydrocarbon source rock potential except for dry gas. Spores/pollen: Spores and pollen are known to be rich in lipids, which contribute mostly to liquid hydrocarbons. The frequency of spores and pollen is quite low (<1%) in the studied sediments. Fungal remains: The frequency of fungal remains in the sediments ranges from 039% (avg. 3.3%). Fungal remains are the major agents of biodegradation of organic matter eventually converting it to an amorphous mass. They are rich in proteins and lipids and could be a moderately good source of hydrocarbon Structured marine (phytoplankton): Structured marine organic matter in the sediments is mainly contributed by dinoagellates and itsm frequency ranges from 01% (avg. 0.1%). The overall dominance/trend of dierent types of organic matter in the Marhighat section is: Amorphous organic matter> black debris> biodegraded terrestrial organic matter> fungal remains> spores/pollen> structured terrestrial organic matter> structured marine (phytoplankton). The dominance of amorphous organic matter and biodegraded terrestrial organic matter in the Subathu Formation of the area indicates goodmsource-rock potential for hydrocarbons. The distribution of dispersed organic matter (gure 2) clearly reveals that the lower and middle parts of the Marhighat section are dominated by,amorphous organic matter whereas, the upper part of the section is dominant in black debris (charcoal) facies. The lower and middle parts of the succession, therefore, can be categorized as sapropelic organic matter facies with adequate maturity (TAI 3.0) to generate liquid hydrocarbons, while the upper part of the succession has sapropelic humiccharcoal facies with TAI 3.0, which is considered to be moderate to good for gaseous hydrocarbongeneration. Quantity of Organic Materia: TheamountoforganicmaterialpresentinthesedimentaryrocksisalmostalwaysmeasuredasTotalOrganicCarbon(TOC)content,whichis thefirstandmostimportantscreeningtechniqueusedtoindicatewhichrocksareofnointeresttous(TOC<0.5%),whichonesmightbeof slightinterest(TOCbetween0.5%and1%),andwhicharedefinitelyworthyfurtherconsideration(TOC>1%),(Waples,1985,1980).According toPeters,1986thesourcerocksareclassifiedasfollows(Table1 (b) Source Potential (i) Hydrocarbon Potential Samples having total organic carbon values below 0.5% are generally regarded as containing insufficient organic material to be of commercial value (2). Thus this value is used as a cut-off point in this report and sediments with organic carbon values less than 0.5% are regarded as having no significant source potential. Source potential ratings based on conventional geochemical data are given below. Poor Potential Less than 0.5% Moderate Potential 0.5% to 1.5%

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Good Potential Greater than 1.5% Quality of organic matter: The quantity of organic matter usually expressed as total organic carbon (%TOC) The quality of organic matter: The most important factor controlling the generation of oil and gas is the hydrogen content of the organic matter (OM). The quantity of petroleum generated and expelled increases as the atomic hydrogen-to-carbon(H/C) ratio of the OM increases. TOCs generally increase in shales as the colour goes from red to variegated, to green, grey and finally black (TOC-0.1% to 17.5% ) Most sandstones and red beds have very low TOCs because the organic matter has been destroyed by oxidation. Source Rock Studies Three diagnostic characteristics are normally used to evaluate the overall potential of a sedimentary rock to generate or to have generated petroleum: Richness - or quantity - of organic matter present in the rock. Was adequate carbonaceous matter deposited in the sediment and preserved following burial for it to be a satisfactory source of bitumen? Proneness - or quality - of organic matter dispersed in the rock. Is the kerogen mixture present in the rock apt to yield bitumen which can be a source of oil, gas, or oil and gas; or is the kerogen most apt to be nongenerative? Maturity - or thermal alteration state - of organic matter in the rock. Has carbonaceous matter entrapped in the rock undergone catagenesis to yield bitumen and be a possible source of petroleum, or is it too thermally altered so that bitumen (and related crude oil) has been destroyed? The first two diagnostic characteristics, richness and proneness, are a measure of a rock's inherent source potential (also referred to as genetic potential), or the "maximum" generative potential the sediment had at the time of deposition and preservation. The third characteristic, maturity, on the other hand, is a measure of the degree to which the inherent potential of the rock has been realized. Maturity, therefore is an indication of realized source potential. To evaluate inherent potential, kerogen is the principal source of data. To evaluate realized source potential, both kerogen and bitumen are primary sources of data. Realized Source Potential Kerogen Evaluation: When kerogen is used to evaluate sample maturity, we continue to follow the visual and chemical approaches used to evaluate kerogen proneness; however, we look at other data provided by such methods. In visual characterization we focus on darkening due to thermal alteration, called the thermal alteration index (TAI), and the conodont alteration index (CAI). To monitor maturation trends we also incorporate vitrinite reflectance (%R0) and fluorescence data from microscopy techniques. Chemically, to H:C, O:C, HI, and OI we add pyrolysis productivity index (PI) and temperature of greatest rate of pyrolysate production (Tmax) . Thermal Alteration Index Thermal alteration index (TAI) is based on kerogen color; as thermal alteration of kerogen increases, kerogen color darkens progressively from yellow-green through orange-brown to black. A TAI value, therefore, is an estimation of kerogen color, particularly spore and pollen grains, often converted to a numerical rating. The numerical TAI rating scale used generally depends upon the palynological service performing the work. In each scale, however, immature, mature, and postmature numerical ranges have been established.

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When a number of TAI observations are available, they generally are plotted in well-profile or mapview format so that trends and discontinuities can be recognized and comparisons made with other maturation parameters. TAI is limited to some degree by the fact that full darkening and opaqueness occurs during metagenesis; therefore, higher levels of postmature thermal alteration cannot be differentiated. In addition, spore and pollen grains are from higher plant forms, so these materials are not found in sediments older than Middle Paleozoic. Vitrinite Reflectance Vitrinite reflectance (%R0) measures the amount of incident light reflected from vitrinite macerals. In general, the procedure is for a photometer to record the amount of incident light being reflected by polished vitrinite macerals (embedded in a binder, such as a plug)) immersed in oil. The measurement is less subjective than TAI estimations and preferred by some evaluators for this reason. Reflectance measurements are recorded in values generally extending from 0 to 4.0 %R0. Typically, reflectance readings from the same polished surface, usually 40 to 60 maceral readings, are recorded in histogram format. Ranges or averages are then determined and can be plotted in formats similar to TAI, CAI, or other numerical data.Figure 1,

Figure 1 Vitrinite reflectance values for kerogen in the oil window typically range from about 0.5 to 1.4 %R0, with light liquid and gas generation continuing on to about 2.0 %R0. Reflectance above 2.0 %R0 indicates metagenesis. These ranges and limits can vary with geographic area. Increase in vitrinite reflectance continues throughout metagenesis, and therefore higher levels of thermal alteration can be differentiated by this method. However, vitrinite is derived from lignin, which, as you will recall, comes almost entirely from land plants and was not common before

21

Middle Paleozoic time. Therefore, use of vitrinite reflectance, like TAI, is limited by related organic source and geologic age factors. Some alternate macerals (e.g., exinite) may be used, but the reflectance gradations are less reliable and not necessarily directly correlative to vitrinite reflectance values. Kerogen Reflectance To measure kerogen (vitrinite) reflectance (%R0) using incident light: 1. Wash isolated thoroughly. 2. Dry (vacuum, freeze) separation. 3. Mount separation in 1-in. bioplastic plug ( Figure 1).

Figure 1

Note: Whole-rock samples can also be prepared for reflectance and compositional study by mounting rock fragments in a bioplastic plug and proceeding from Step 4. 4. Polish plug and embedded sample to very smooth surface. 5. Place polished plug under microscope and immerse surface with oil. 6. Expose plug to incident white light and/or ultraviolet (UV) light to excite fluorescence in order to identify vitrinite (or other usable) macerals. 7. Measure reflectance on approximately forty particles (or more) of each maceral type with standardized photomultiplier. 8. Plot individual reflectance values (histogram) and determine reflectivity average of representative first-cycle population. Elemental Determination To measure elemental contents in kerogen (Durand and Monin, 1980). 1. Prepare a primary kerogen separation in the same manner as that used in TAI-SCI and %R0 separations. 2. Make an ultrasonic extraction to remove soluble organic material. 3. Concentrate kerogen further with heavy liquid separation. 4. Combust concentrate in oxygen-charged analyzer and trap carbon dioxide (CO2), water (H2O), and nitrogen oxides (NOX). 5. Combust pyrite-free concentrate in oxygen-charged analyzer and trap sulfur dioxide (SO2).

22

6. Combust concentrate in inert-atmosphere analyzer and trap CO2 formed from oxygenbearing kerogen. Note: When individual determinations of sulfur and oxygen concentrations are not required, Steps 5 and 6 are omitted, and O + S is calculated as the difference between total saniple weight and C, H, N, plus ash content. 7. Measure individual gas volumes; convert to molecular C, H, N, S, and O, plus ash. 8. Tabulate data in relative concentrations and selected ratios plot H/C and O/C ratios on van Krevelentype diagram ( Figure 1).

Figure 1

Pyrolysis . Pyrolytic methods are widely used for estimating thengenerating capabilities of potential source rocks (3).nPyrolysis techniques have superseded the more traditional method of assessing hydrocarbon potential using total organic carbon measurements, because they provide more meaningful data, Pyrolysis does not take into account any reworked material and/or inertinite present in source rocks/ which adds to the organic carbon value/ but has very limited or no hydrocarbon potential. Pyrolysis is a programmed heating technique used to thermally generate and extract bitumen from a rock sample in an oxygen-free system. In most cases in exploration geochemistry this means Rock-Eval analysis ( Figure 1, Characteristics of pyrolysis: Pyrogram).

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The first peak (PI) is often considered as representative of the quantity of free hydrocarbons that were present in the sediment at the time of sampling. The second peak (P2) is considered to be representative of the quantity of hydrocarbonsmpresent in the sediment and yet to be generated. The P2 peakmis produced by conversion of the Kerogen in the rock samplemby thermal cracking in the instrument. This is generallymconsidered to be a reasonable estimate of the amount of hydrocarbons, which could theoretically be generated by complete conversion of the Kerogen in sediments undernatural conditions throughout their geological lifetime. Both the PI and P2 yields are expressed in Kg./tonne.Comparison of pyrolysis data with conventional geochemical data to provide a source potential rating gives the P2 hydrocarbon potential in practical exploration terms Poor Moderate Good 0.1 to 1.5 Kg./tonne 1.5 to 5.0 Kg./tonne Greater than 5.0 Kg./tonne

Figure 1 Pyrolysis is a programmed heating technique used to thermally generate and extract bitumen from a rock sample in an oxygen-free system. In most cases in exploration geochemistry this means Rock-Eval analysis An initial low-temperature heating of a pulverized rock sample drives off contained bitumen. This

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pyrolysate is designated S1 and is considered an indicator of realized source potential. In other words, the bitumen driven off is probably indigenous to the sample and the result of natural bitumen-generative Processes. With progressively higher temperatures, kerogen is thermally decomposed; this results in a second surge of pyrolysate. This pyrolysate, designated S 2, is considered an indicator of unrealized source potential. The higher temperatures, in effect, create instant maturation in the sample. A combination of S1 and S2 provides an approximation of the total bitumen-generative characteristics of the sample. (If this characteristic were combined with the sample's TOC, an approximation of the rock's true inherent source potential could be made; this approach is used by some groups.) During pyrolysis, carbon dioxide also is liberated by thermal cracking of kerogen. This pyrolysate, trapped and analyzed separately, is designated S3. It is considered to be an indicator of the oxygen content of the pyrolyzed kerogen. By relating S3 to the TOC of a sample, the oxidation level, or oxygen index (OI), of the kerogen is obtained. Similarly, by relating S2 to TOC the hydrogen that remains available for hydrocarbon generation, or hydrogen index (HI), is approximated. We can see both indices plotted in the modified van Krevelen format for visual estimation of kerogen maturation level ( Figure 2

Figure 3 gas chromatography: Chromatography is the principal method currently used to iso-late major groups of organic compounds from bitumen and petroleum samples and quantify the presence of common compound types within those groups. Chromatography simply separates different organic

25

compounds based on each compound's natural retention characteristics as any mixture of organic molecules is carried along through a permeable medium. Gas chromatography, however, is effective in separating compounds within any group. A third type of chromatography, thin-layer chromatography (TLC), is becoming more common in laboratories, though its use is specialized as for rapid separation of very small quantities needed for downstream analysis (e.g., porphyrin analysis). TLC is based on solvent movement by capillary action up a treated glass plate Gas chromatography uses a single inert gas as a carrier or solvent for the mobile phase and a glass or metallic column for the stationary or retention phase. The column can be thick enough to be packed with a porous medium or thin enough for the inner surface to be coated with a nonvolatile liquid to act as a capillary ( Figure 3 , Capillary column gas chromatograph). In gas chromatography, the column is heated so that the sample is maintained in vapor phase as it moves along in the carrier gas. Separation occurs as compounds move back and forth between vapor (movement) and liquid (stationary) phases. Order of separation, therefore, is dependent on (1) molecular size small molecules move more rapidly than large because they remain more readily in a vapor state; and (2) compound polarity compounds of similar size but different polarity move at dissimilar rates. Gas chromatographic analysis generally deals with specific types and limited ranges of hydrocarbons. As we saw in GL701, common types and ranges are gaseous saturates (C1-C4 to C1C7), light liquid saturates and aromatics (C4 -C7 to C4-C10), and heavier liquid saturate, aromatic, and resin separations (C10+ or C15+). The need to analyze specific hydrocarbon types and narrow molecular ranges is the result of two overriding considerations: (1) To keep analytical runs relatively quick, the number of compounds must be limited to a workable number or range. (2) For effective chromatographic separation of very similar compounds, analytical columns and programs must be tailored to a limited molecular range. Typically, compound separation is presented graphically on a gas chromatogram. The concentration of individual or selected (e.g., normal alkanes) compounds is tabulated. Generally, selected ratios (e.g., paraffin:naphthene; pristane:phytane) and calculations (carbon preference index; CPI) are also included. Two additional causes of irregularities in analytical data are common to samples analyzed by gas chromatography: (1) the incorrect identification of compounds (peaks) and (2) the use of different analytical columns and heating programs among laboratories. Misidentification can occur when a chromatogram is being planimetered by hand or when an integrator is not in full synchronization with emergent times. The error may show up in a C15+ analytical data table, for example, by a marked shift in CPI as from odd-even predominance to even-odd predominance. Where diverse gas chromatographic columns and procedures are used, data for the same compound type and range can vary simply because of slightly different responses by organic compounds. When comparing data from two or more analytical facilities, watch for variations that "correlate" to laboratories; similarly, always request that copies of gas chromatograms, particularly in the C10+ or C15+ ranges, accompany the data sheets. A word of caution about chromatograms is in order for the explorationist: visual differences can be very misleading. Vertical (peak height) scales on chromatograms are often changed between and during analytical runs to keep all peaks within recorder limits. This means that when working with chromatograms, relative similarities or differences in peak heights and patterns are the critical factors to evaluate. Some laboratories now provide "normalized" chromatograms that show peak

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patterns adjusted to a standardized presentation (e.g., tallest peak height set at 90% of plotter limit; Figure 4 ). Gas Chromatography To separate compounds by gas chromatography: 1. Inject separated or narrow-range sample into heated port and carrier gas flow as recorder and integrator are started (zero time). 2. Allow chromatographic separation to occur as carrier gas moves compounds through heated column. 3. Detect (FID) arrival (emergent times) of separated compounds at end of chromatographic column. 4. Convert (electronically) magnitude of detector response to peak area plotted on strip chart (gas chromatogram) 5. Identify compounds (emergent times) represented by peaks, and measure (planimeter) areas under peaks to determine quantities. Note: When an integrator is used in place of a planimeter to measure quantities, as is the case in most modern recorders, Steps 4 and 5 occur simultaneously. 6. Prepare data table of compound types and quantities while gas chromatograph is backflushed in preparation of next analysis.

Maturation of organic matter: As organic matter enters the depositional cycle, it does so with some predisposition to be a potential good or poor source of oil and/or gas. This predisposition depends largely on the varying percentages of lipids, proteins, carbohydrates, and lignins that make up the organic remains being deposited. We may trace the postburial chemical evolution of natural combinations of preserved carbonaceous debris as they are converted to kerogen. Bitumen generation pattern with maturation) through progressive thermal stages of: diagenesis low-temperature/bacterial alteration catagenesis intermediate-temperature alteration metagenesis high-temperature/premetamorphic alteration

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Figure 2

We may also discuss hydrocarbon generative characteristics of organic detritus as it matures through these three thermal regimes ( Figure 3,

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Figure 3 the three correlative kerogen maturation intervals are: immature thermal generation of bitumen not yet initiated; biogenesis of gas active mature thermal generation of bitumen active; biogenesis of gas completed postmature thermal generation of bitumen completed; breakdown of bitumen active There are three paramount factors to keep in mind in such a discussion: ethane, can evolve under all three subsurface temperature conditions ( Figure 3 ). Therefore, such gases can be thought of as biogenic gas (diagenesis), associated gas (catagenesis), and thermal gas (metagenesis). -range bitumen, and thus crude oil, is generated by thermal processes during catagenesis ( Figure 3 and Figure 4 ); this intermediate temperature interval is often referred to as the oil window phase.

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Figure 4 Diagenesis, or the low-temperature alteration interval, extends from the sediment-surface interface to a depth at which biological activity ceases because of inhospitable conditions and chemical reactions begin in response to geothermal conditions. Diagenesis includes (1) the breakdown of organic matter through biochemical processes and reconstitution of insoluble components into kerogen, (2) generation of gases through biogenesis, and (3) initiation of expulsion of liquids through compaction. The upper-temperature limit of diagenesis can be over are rapid ( Figure 1, Thermal alteration as related to temperature, time, and depth of burial. During diagenesis, organic matter alters to kerogen along a number of pathways. For more watersoluble and readily biodegradable compound types, such as proteins and carbohydrates, the following general progression dominates: Products of Diagenesis As organic matter progresses through diagenesis and is converted to kerogen, systematic changes occur that set the stage for hydrocarbon generation which will follow at higher temperatures in the catagenesis phase Sequence of biochemical steps typically encountered during early diagenesis) across which metabolic processes shift from aerobic (CO2-producing) alteration to anaerobic sulfate-reducing (H2 S-producing) alteration, and then to anaerobic carbonate-reducing (CH4-producing) alteration. These latter two appear to be nearly mutually exclusive, and biomethane generation is very limited until nearly all sulfate is removed from interstitial water. It should be remembered, however, that these zones are continually migrating upward in the sedimentary column as new sediments accumulate; therefore, the carbonate-reducing zone may have added methane to each portion of the sedimentary column as it migrated upward. One near-surface condition occasionally develops in the sulfate-reducing interval that markedly imprints on bitumen generated during catagenesis. If the liberated H2S of the sulfate-reducing zone cannot be removed from the closed depositional/ chemical system by recombination, as with iron

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(e.g., pyrite FeS2) in the confining sediments, it may be altered to free sulfur and recombine with kerogen as it forms during late diagenesis. The resulting high sulfur content in the kerogen can be carried over to bitumen generated during catagenesis Catagenesis Catagenesis, the intermediate-temperature alteration interval, begins at the burial depth where thermal generation of hydrocarbons and nonhydrocarbons commences. Catagenesis ends in that depth/temperature range where bitumen generation from kerogen is replaced by thermal breakdown of organic compounds to methane and pyrobitumen. Catagenetic limits, therefore, bracket the oil window. The initiation of bitumen generation, varies with kerogen type and with the length of time a sediment has been buried at elevated temperature

The dependence of bitumen generation on both geologic time and geothermal temperature, however, causes catagenesis temperature limits to vary widely. While sediments are in the oil window, Types I and II kerogen generate both liquid bitumen and associated gas; heavy liquids will give way to light liquids and wet gases as catagenesis proceeds ( Figure 3). Gas will be the principal product of Type III kerogen Metagenesis

Figure 9 Metagenesis, or the high-temperature alteration interval, commences, as we have stated, in the subsurface where the principal form of hydrocarbon evolution is the breakdown of preexisting bitumen and petroleum toward the end products of thermal methane and pyrobitumen. At that point, hydrogen-carbon ratios in kerogen will be very low (<0.5:1) as will oxygen-carbon ratios

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(<0.05:1). The oil window will have been exited and the dry gas regime entered. Currently, no generally accepted temperature/depth limit has been established beyond which methane does not survive. Modification of Kerogen Chemically, kerogen in the dry gas zone shows continued condensation and stacking of aromatic layers. Consequently, it becomes more and more resistant to further thermal generation of bitumen. Measurable changes continue in the trend of increasing kerogen reflectance established during catagenesis. In addition, kerogen macerals develop anisotropy as internal structuring becomes better developed. Further thermal darkening of kerogen can be observed, although near opaqueness may be reached before full effects of metagenesis are experienced by kerogen. Evolution of Hydrocarbons As noted, the principal change that occurs during metagenesis is the thermal cracking of existing bitumen and petroleum to methane and residual pyrobitumen. Methane may also be generated from kerogen, particularly Type III, by the release of methyl and short alkyl groups as polyaromatic components condense further. In short, the decrease in petroleum liquids and gas wetness, combined with abrupt methane dominance, is the trademark of the postmature zone. maturation modeling - TTI concept. Burial history curves:( implementation of Lopatins method) Step 1; Two points representing the initial deposition of the sediment and its position today are marked on the age depth plot. Step 2; to locate the first control point from the time Stratigraphic data table, by 80my the sediment had been buried to a depth of m (difference of 1st and 2nd control depth points) Step 3: plot the remaining control points then connecting all the points complete the burialhistory curves shown in the figure. All of the shallower and younger horizons will have burialHistory curves whose segments are parallel to those of the oldest horizon (ignoring the compaction effects)burial-history.

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Step 4: is to provide a temperature history to accompany our burial-history. Subsurface temperature must be specified for every depth throughout the relevant geologic past. For the sake of simplicity the present day geothermal gradient and assume that both the gradient and surface temperature have remained constant throughout the rocks history. Calculate the bottom-hole temperature and yearly average surface temperature. Using the present day data and extrapolating them into past, we can construct the temperature grid as shown in the figure. Constant surface temperature and constant geothermal gradients or constant geothermal gradients and variable surface temperatures.

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More complicated temperature histories are possible. dog leg gradients can be used to reflect changes in thermal conductivities caused by variations in lithology. Erosion is indicated in a burial history curve by an upward movement of the curve. If the deposition resumes later, the burial-history curve again begins to trend downward. Faulting can be dealt with by considering the hanging wall and footwall as separate units having distinct burial histories. If part of the section is missing, the burial history curves for both hanging wall and footwall can be represented on a single diagram Van Hinte (1978) has used geohistory diagrams which are similar to burial-history curves . Geohistory diagrams take sea level as the datum, where as for burial history curves use the sea floor. Calculation of maturity Once the burial history curves and temperature grids have been constructed, we must put them together. The intersections of burial history curve with each isotherm are marked with dots. These dots define the time and temperature interval that we shall use in our calculation. Temperature intervals are defined by isotherms spaced 10 oC apart. A Time interval is the length of time that the rock spent in a particular temperature interval. Total maturity is calculated by summing the incremental maturity added in each succeeding temperature interval. Lopatin chose the 100-110o C interval as his base and assigned to it an index value n = 0. Index value increase or decreases regularly at higher or lower temperatures respectively. The rate of maturation was assumed to increase by a factor of two (r = 2 n)for every 10oC rise in temperature. The r-factor thus reflects the exponential dependence of maturity on temperature. The time factor, Lopatin used the length of time (in m.Y) that sediment spent in each temperature interval. The maturity added in any temperature interval i is given by

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maturity=(Ti)(rni) The total maturity (TTI) of a given sediment is given by the sum of the maturities acquired in each interval. n max TTI = (Tn)(rn) n min where n max and n min are the n-values of the highest and lowest temperature intervals encountered. It is also possible to determine the total TTI value at any time in the past simply by stopping the calculation at that time. Factors affecting thermal maturity Maturity is affected by both baking time and baking temperature; the specific burial history of a rock can strongly affect its maturity. -Burial was very slow followed by rapid; -rapid burial for some period followed by a non erosional depositional hiatus; -rapid burial followed by a hiatus then uplift and erosion ; varying burial and geothermal history; effect of igneous intrusions tec. Interpretation of TTI values: -TTI values must be compared with measured maturity values like % Vitrinite Reflectance ( Ro);H/C ratios; API gravity of oils etc. TTI % Ro Generation 1 3 10 15 20 50 75 180 900 0.40 0.50 0.60 0.65 0.70 0.90 1.00 1.35 2.00 condensate from resinite from S-rich kerogen early peak late wet gas Dry gas

iso-TTI lines on burial-history curves is to begin by selecting the TTI values of interest which include those for the onset and end of oil generation or liquid deadlines. One calculates intervalTTI values and sums them until the desired TTI value is reached. The points marked desired TTI are connected on burial history curve. If TTI values corresponding to the onset and end of oil generation are plotted, the resulting maturity band defines the oil-generation window through time. Iso maturity lines can be superimposed on cross sections possibilities for migration of hydrocarbons at various times can be examined and correlated with structural events that regulate migration pathways TTI values can also be contoured SUMMARY Models for predicting thermal maturity have been developed to aid in understanding the hydrocarbon generation and preservation histories of sedimentary basins. Knowledge of oil deadlines is important to know the economic accumulations are unlikely to occur below the deadline Applications include defining the hydrocarbon-generation window, timing of generation, defining deadlines for liquid hydrocarbons

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Reconstructing the history of an area. Lopatins methodology except with minor variations is the most widely used technique to day.

Study of biomarkers biomarkers are a suite of organic compounds composed of carbon, hydrogen and other elements which are found in oil, bitumen, rocks and sediments and show little or no change in structure from their parent organic molecules in living organisms. They are complex molecules derived from formerly living organisms.Thus, biomarkers can frequently be linked directly to the specific group of plants, animals,or bacteria from which they originated. Examples of the originating material that can leave remnants of biomarkers are spruce wood, oak leaves, Scots-pine needles, phytoplankton, diatoms, or lycopodium in plants and zooplankton, copepods, oysters, and higher invertebrates in animals. By definition biomarkers are not destroyed during diagenesis like proteins or carbohydrate structures. Even many biomarkers do not survive long past the oil-generating stage. They are most useful in following the geochemistry of an oil from generation to maturity. These compounds are typically analyzed using gas chromatography/ mass spectrometry (GC/MS). Sterane and hopane biomarkers provide the most geochemical information and are therefore the most widely used biomarkers for crude oil maturation evaluation and oil correlation studies. Other important biomarkers are the isoprenoids such as pristane, phytane, the carotanes, and the porphyrins. Geologists and Geochemists utilize biomarkers to identify source rocks and migration pathways ofmodern petroleum deposits. References 1.Wang, Z.; Stout, S.; Fingas, M. Environmental Forensics, 2006 7, 105-146. 2.Hunt, J.H. Petroleum Geochemistry and Geology, 1996, 64-65. Biomarkers are a group of compounds, primarily hydrocarbons, found in oils, rock extracts, Recent sediment extracts, and soil extracts. What distinguishes biomarkers from other compounds in oil is that biomarkers can reasonably be called "molecular fossils". Biomarkers are structurally similar to, and are diagenetic alteration products of, specific natural products (compounds produced by living organisms). Typically, biomarkers retain all or most of the original carbon skeleton of the original natural product, and this structural similarity is what leads to the term "molecular fossils". Biomarkers have a variety of applications in petroleum exploration. For example:

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(1) When samples of oil and candidate source rocks are available, biomarkers can be used to make oil-source rock correlations, or (2) When samples of candidate source rocks are NOT available, the biomarker distribution in an oil can be used to infer characteristics of the source rock that generated the oil WITHOUT examining the source rock itself. Specifically, biomarkers in an oil can reveal (1) the relative amount of oilprone vs. gas-prone organic matter in the source kerogen, (2) the age of the source rock, (3) the environment of deposition as marine, lacustrine, fluvio-deltaic or hypersaline, (4) the lithology of the source rock (carbonate vs. shale), and (5) the thermal maturity of the source rock during generation (e.g., Peters and Moldowan, 1993). Such data may be key inputs to effective basin modeling of a prospect or block. To characterize charge risk, these biomarker parameters can be used in a variety of innovative ways. For example, specific biomarker parameters can be calibrated against specific kerogen quality parameters in a given basin. Then, the biomarker ratios are measured in an oil sample from the basin, and the values are projected onto calibration curves to quantitatively predict characteristics of the source rock. This approach, allows explorationists to assess whether an oil was generated primarily from an oil-prone or gas-prone organic facies (Dahl et al., 1994; McCaffrey et al., 1994). The information gained from oil biomarkers (source type, age, maturity, kerogen quality) when

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integrated into a basin model has substantial economic impact because it provides early estimates of oil quantity and GOR for exploration targets in the area of interest. The relative abundances of certain biomarkers in petroleum change as a function of source rock maturity. As a result, a variety of biomarker parameters have been identified that are very useful for characterizing the source rock maturity simply from analysis of the migrated oil (e.g., Peters and Moldowan, 1993). Biomarker maturity parameters make use of several processes that occur during source rock maturation: Cracking--large molecules break into smaller molecules Isomerization--changes in the 3-dimentional arrangements of atoms in molecules. Aromatization--formation of aromatic rings (loss of hydrogen from naphthenes). Several considerations must be kept in mind when using petroleum biomarkers to assess source rock thermal maturity. For example: (1) The exact relationship between a biomarker parameter and the source maturity is a function of heating rate, source lithofacies, and source organic facies (kerogen type). As a result, the exact maturity (i.e., vitrinite reflectance equivalent) associated with a given value for a biomarker parameter can change from basin to basin. Furthermore, the relationship between a biomarker maturity indicator and source rock maturity is generally non-linear. (2) With increasing maturity, many biomarker maturity indicators reach terminal values; hence, a given biomarker parameter is applicable only over a specific maturity range. (3) The concentrations of biomarkers in petroleum decrease with thermal maturity. Despite these limitations, biomarker indicators of source maturity can be extremely useful. For example, biomarker maturity parameters can be used to determine what the API gravity of a biodegraded oil was prior to biodegradation. This is accomplished by collecting a suite of nondegraded oils from the same petroleum system as the degraded oils. Using the non-degraded oils, the geochemist develops a correlation or "transform" between a biomarker maturity parameter and API gravity. The same biomarker parameter is then measured on a degraded oil, and the original gravity is determined using the transform developed from the non-degraded oil suite. The most effective biomarker parameters are those based on compounds that are highly resistant to biodegradation, such as [Triaromatic/(Monaromatic +Triaromatic steroids)]. Source Rock descriptions and source rock maturity information derived from oil biomarkers are often key input data for basin modeling of a prospect or block. Biomarkers in Petroleum are analyzed by gas chromatography mass spectrometry (GC-MS) or gas chromatography - tandem mass spectrometry (GC-MS-MS). Analyses are typically performed on the saturated hydrocarbon fraction or the aromatic hydrocarbon fractions. The oil fractions are prepared by liquid chromatography. Biomarker Precursor n-alkanes (>C-22) terrestrial plant waxes n-alkanes (C-17, C-22) algal lipids isoprenoids (<C-20) various chlorophyllus isoprenoids (> C-20) lipids or chlorophyll of hypersaline algae porphyrins chlorophylls steranes steroids triterpanes bacterial triterpenoids diterpanes hydrocarbons in plant resins

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large naphtheno aromatics

steroids, triterpenoids

Oil-Source Rock Correlatio Oil-source rock correlations rely on geochemical parameters that do not differ significantly between an oil and its source rock. Obviously these parameters have to be measurable in both sample types, so the molecular and isotopic composition of the bitumen are used. In practice, correlations between oils and source rocks rely mainly on biomarker composition, as such compounds, by definition, are related strongly to their biological sources and thus should be similar in related samples. For biomarker parameters to be useful in oil-source rock correlations they should be relatively insensitive to differences in maturity, effects of biodegradation, etc. Examples of parameters that remain relatively constant between oils and their source rocks include sterane carbon number distribution and the stable carbon isotope composition of bulk oil (or extract) and fractions. Many other parameters are influenced by other processes, and these effects need to be considered in making oil-source rock correlations. Particular difficulties that are regularly encountered in oil-source correlations are discussed by Peters et al. (2005), and briefly summarized here: The available source rock samples may not be representative of the source rock section as a whole. It should be noted that an oil expelled from a source rock will be a composite fluid comprised of hydrocarbons generated from the various horizons within the source section. The bitumen composition of rock samples might contain migrated hydrocarbons or contamination. Differences in maturity level between oils and source rock samples can be large, as source rocks are often only available from basin edges rather than within the source kitchen itself. As such, they represent lateral equivalents of the actual source, and are often immature. Artificially maturing the samples in the laboratory using a pyrolysis technique is sometimes employed to help in the correlation. The processes of expulsion from the source rock and subsequent migration might modify the oil composition, for example through preferential adsorption of certain components. In fact such changes in composition can form the basis of molecular tools to assess migration distances. However, hydrocarbon biomarkers of similar overall structure are probably not modified extensively as a result of migration, although expulsion efficiencies may be slightly different (e.g. Leythaeuser et al., 1984). Oils may be derived from more than one source rock - i.e. mixed source oils may be rather more common than is generally suspected. Oils, even if derived from a single source rock, may be the result of different phases of charge, representing different source rock maturity levels (Wilhelms & Larter, 2004). Biomarkers are present in much lower concentrations in late stage, high maturity oils, complicating oil-source correlation. Oil-Oil Correlation Oil-oil correlation uses geochemical characteristics that allow the geochemist to distinguish between different sources whilst being resistant to secondary alteration processes such as maturation, migration fractionation, water washing and biodegradation. In some cases, simple bulk parameters (e.g. sulphur content, Ni/V, stable carbon isotope composition) may be sufficient to provide a confident positive or negative correlation. However, in most cases, molecular parameters

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from gas chromatography (GC) or GC-MS are utilised, and these provide more specific sourcerelated correlation information. Nevertheless, it should be remembered that most biomarker parameters are influenced by secondary alteration processes to some extent, so care must be taken to recognise and allow for such factors in making a correlation. Correlations (either oil-source or oil-oil) can be made either empirically (visual observation, simple cross plots, etc.), or by using multivariate statistical analysis. These different approaches are discussed in the following sections: 1.Empirical techniques 2.Multivariate statistical techniques Macro and micro seepages: Rock macro-structures On a large scale, structural geology is the study of the three dimensional relationships of stratigraphic units to one another withinterranes of rock or within geological regions. Rock microstructures Rock microstructure or texture of rocks is studied by structural geologists on a small scale to provide detailed information mainly aboutmetamorphic rocks and some features of sedimentary rocks, most often if they have been folded. In recent years, the geochemical method known as "hydrocarbon fingerprinting" has been become one of the most applied oversurface exploration tool for oil and natural gas. Hydrocarbon fingerprinting can be basically generalized as the detection and interpretation of hydrocarbon originated gaseous phase seepages, and beyond its high precision prospecting feature, it guarantees time and cost gain too. Including gaseous phase nearsurface sampling, chromatographic analyses and geological modelling of results, this method comprises a series of interdependent processes. It is based on the principle of "all hydrocarbons which are formed under ground seep to surface or near surface in macro or micro(ppb) scales". With respect to this, research teams can obtain information about undiscovered oil and gas reservoirs by examination the chemistry of hydrocarbons or their alteration products seepage on or near surface. This surface geochemical method includes these and other basic principles as listed below; Hydrocarbons seep to the surface in macro or micro scale from all oil reservoirs The seepage of the hydrocarbons can be active or passive The seepage of hydrocarbons generally migrates vertically from thousands of the meter depth The relationship between the surface seepage anomallies of hydrocarbons and the accumulated hydrocarbons underground may be simple or complex The surface hydrocarbon seepage is the end of the migration path. Therefore the geological structures as fault, fracture etc. along the migration path must be considered for the correct comments of the anomalies of hydrocarbons(Schumacher, 2000) Near surface geochemical methods for the studies of oil exploration evalutes the low concentration microcseepage. As a result of recent past inventions in chromatography equipments, constituents of soil vapor samples can be determined in "ppb(particle per billionen)" scale. This capability of todays analytical measurement instruments, further increased the importance of micro-scale leakage. In our term, "microseepage" is defined as the occurence of hydrocarbons in soil, sediment

41

or water at the measurement concentration value. "Many researchers believe that the gas found in the layer below the soil or not so many depths from the surface is formed due to seepage of the petroleum reservoir. However the other source as the soil with rich organic matter, the shale near the surface etc. can be considered "(Steven, 1995). Therefore, the geological structure of the survey area, choosing of the sample points, the evaluation of gas chromotographic analysis results of the samples must be done under the light of the parameters which may influence the study results. If all parameters are taken into consideration, the success of the geochemical studies are inevitable. The new methodology developed by JeoTim includes all the procedures from choosing the sample point coordinates to construction of 3D anomally maps step by step. Our methodology is developed as a result of many research and development studies. We are aware of the success of surface geochemical studies is dependent on firstly the usage of one trustable soil vapor sampling kit. Hence we use our own special sampling kits developed and produced by our staff. As superior than its competitors, our sampling kit guarantees elimination of external effects such as atmospheric pressure changes, bacterial activities etc. and includes many efficient properties like working at hard conditions, precise standardization, fast operations etc. Applications of hydrocarbon fingerprinting method are not only limited to oil and gas exploration studies, with this method man made deposition facilities, like artificial underground reservoirs can be planned and controlled. This is a very recent environmental technical approach and becoming widespread day to day and has been used firstly in Europe. Under control of this method, industrial waste gases can be pumped into suitable underground geological structures for getting rid of them. The controlling of seepage resulted from these depositions is necessary, because even in formations with adequate nominal capacity some of the injected CO2 is expected to leak as a result of the buoyancy of the separate phase carbon dioxide, the induced pressure gradients from the injection and the variable nature of strata acting as barriers to upward migration(Bruant and others,2002). Additionaly, extensive properties of hydrocarbon fingerprinting method to detect and interpretate the gaseous phase chemicals, provides the most suitable tool for determining the enviromental pollution caused by hydrocarbon seepage(Rosso and others,1997). Due to capabilities of our new methodology and soil vapor sampling kit, JeoTim has a wider perspective in the usage of surface geochemical methods, in addition to oil&natural gas exploration studies, also embracing environmental researchs and underground deposition facil Surface geochemical prospecting for hydrocarbons includes a myriad of techniques ranging from the direct detection of hydrocarbons escaping from subsurface accumulations and source beds to identifying secondary responses in the soils, rocks and biota in proximity to such accumulations or source beds. In the historical sense, the observation of visible seepage of hydrocarbons is the oldest method of prospecting for petroleum. Drake's historic well near Titusville, Pennsylvania, was drilled on the basis of a seep in the adjacent creek bed. The relationship of such "macroseeps" to reservoirs was well established by Link (1952), who stated: "A look at the exploration history of the important oil areas of the world proves conclusively that oil and gas seeps gave the first clues to most oil-producing regions. Many great oil fields are the direct result of seepage drilling". In this respect, few would argue that the presence of a macroseep indicates the presence of petroleum migration or surface source beds. Microseeps, or smaller scale macroseeps, also occur because of the physical continuity necessarily imposed by nature. These are invisible seeps, usually detectable only by sensitive instruments or by the visible result of their effect on the near-surface environment. These microseeps, although perhaps not as obvious or dramatic as macroseeps, are just as valid for the exploration of undiscovered reserves. This chapter presents the conceptual and

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practical application of microseepage detection and interpretation in the evaluation of areas for their subsurface hydrocarbon potential. Five factors are necessary to form a hydrocarbon reservoir. These are: (1) a source, (2) a reservoir in which the hydrocarbons can collect or concentrate, (3) a means of trapping these fluids in this reservoir (a seal), (4) a pathway to the reservoir (migration) and (5) the proper timing such that the source, reservoir, seal and migration pathway are present when required. Near-surface seepage of thermogenic hydrocarbons indicates the subsurface presence of a mature source and migration pathway. It also suggests that, if the hydrocarbons are reservoired, the seal is imperfect. This is true of both macroseepage or microseepage. Patton and Manwaring (1984) found that even in an area of extensive evaporites (Hugoton Field, Kansas), the seal was not perfect, and that microseepage could be detected in the vicinity of the Syracuse Fault. Basically, surface geochemical prospecting is a source rock tool applied at the surface. The magnitude of a microseep from a reservoir is related to the permeability of the migration pathway (and not to the economic worth of the reservoir). A surface geochemical survey is not currently, and perhaps never will be, a stand-alone prospect tool. However, with judicious use, this technology can provide information on the maturity of source beds in a basin and the composition of subsurface hydrocarbons. In addition, detection of surface microseepage allows mapping the surface expression of the migration patterns created by the expulsion of fluids as a basin compacts and matures. When used in conjunction with geophysical and geological information, geochemical data can refine subsurface models of hydrocarbon trapping and migration configurations. It is only through careful analysis and integration with other exploration tools that one can achieve the optimum benefits from this technology. Near-surface hydrocarbon detection techniques have been shown in both the former USSR and the United States to be capable of distinguishing basins (or large portions of basins) that are unproductive from those that are productive, and of distinguishing the type of production (oil, gas, or mixed oil and gas). This ability has been independently recognized by Jones and Drozd (1979), Mousseau and Williams (1979), Janezic (1979), Weismann (1980), Drozd et al. (1981), Jones and Drozd (1983), Richers (1984), McCrossan et al. (1971), Richers et al. (1982, 1986), Horvitz (1985) and Klusman and Voorhees (1983). Surface geochemical techniques can select which of several frontier basins has the greatest chance of containing reservoired hydrocarbons, and the expected composition (gas, oil, mixed), in addition to high-grading portions of these basins that have the highest potential. The premise that microseeps occur and that they provide useful information for exploration is no longer questionable. . free and adsorbed gas relationship in macro seepages PHYSICAL BASIS FOR MIGRATION OF HYDROCARBONS TO THE SURFACE Basic assumptions The fundamental assumption of near-surface hydrocarbon prospecting techniques is that thermogenic hydrocarbons generated and trapped at depth leak in varying quantities towards the surface of the Earth. That these hydrocarbons present in the near-surface environment represent the products of generation and migration from subsurface points of origin is a necessary conclusion that is universally accepted with respect to hydrocarbon macroseepage. Examples abound, such as the Santa Barbara Channel seeps, the La Brea Tar pits of Los Angeles, the Athabasca Tar Sands, etc. The same relationship has been equally well established, although less commonly accepted, for microseepage. A further assumption is that the pattern and intensity of this leakage also provides information on preferential pathways that the leakage follows, and as such can be combined with additional

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geologic information to predict broad subsurface hydrocarbon fairways. In fact, in some instances it has been claimed that such data can identify areas of reservoired hydrocarbons. This last claim is often the subject of heated debate, however, commonly depending in which camp (for or against geochemistry) the explorationist resides. The physical state of the hydrocarbons during transport is not well known. The reader is referred to Matthews (1996) for a more complete discussion. Nevertheless, most of the models proposed for the transport of these fluids from source to reservoir (aqueous transport, micellular, discrete oilphase transport, gaseous transport, etc.) are applicable to the continued transport of hydrocarbons from these source beds and/or reservoirs to the near-surface environment. An additional constraint on land is that the last stage of transport is generally above the water table. The physics of transport can be subdivided into two categories, effusion and diffusion. Physical transportation by effusion Effusion transport is believed to be the dominant mode of moving hydrocarbons to the reservoir and to the near-surface environment. The sharp localized nature of many anomalies associated with microseepage and macroseepage is more consistent with an effusion model rather than a diffusion model. The experience of the authors in monitoring leakage from gas storage reservoirs and controlled experiments where subsurface gas pressures were typical of true reservoirs suggests vertical transport rates of several meters (tens of feet) per day, clearly greater than the distances of migration dictated by the diffusion mechanism alone (Jones and Thune, 1982). The sharp and often linear nature of anomalies suggests that faults and fractures play an important part in the movement of these gases. Major linear features discernible on satellite images, as well as other remotely sensed media, from Patrick Draw, Wyoming, show such a relationship (Richers et al., 1982). The Lost River, West Virginia, Geosat study (Matthews et al., 1984) shows anomalously high soil gas values in relation to linear features on imagery. There are anomalously high gas values along faults in the San Joaquin Basin and in the Wyoming-Utah Overthrust Belt (Jones and Drozd, 1983). The Russians have shown that the magnitude of soil gas values on faults increases dramatically shortly after an earthquake in which fault movement is involved (Zorkin et al., 1977). An extensive study, involving 105 observation wells, 3 meters to 5 meters deep, was set up over the Mulchto oilfield in northeastern Salchalin. A total of 3,700 samples were collected and analyzed over a four month period with the most active wells sampled daily. The results from this study provide impressive evidence for the tectonic relationship of this leakage gas flux (Fig. 5-7). This study leaves no doubt that faults and fractures provide the main control on the effusion of gases from the subsurface. Physical transportation by diffusion Diffusion, on the other hand, is a slow and widely dispersive process. Antonov et al. (1971) measured hydrocarbon diffusion coefficients for a variety of rock types from several hydrocarbon provinces in the former USSR. They discovered that the coefficients of diffusion vary over a wide range (from 10-3 to 10-8 cm2/s) depending on the particular lithology and geologic conditions. The time required for diffusion to occur can sometimes be restrictive. Table 5-IV shows that the time required not only often exceeds the age of the hydrocarbon accumulation, but also quite often exceeds the age of the host rock. If this were the dominant process for migration, then the appearance of soil gas anomalies in the near subsurface would indicate only very shallow accumulations. If a non-steady state exists, where the hydrocarbon signal observed represents only 0.001 times the steady state signal, then these times could be reduced by a factor of 25 times that

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of the steady-state model. Table 5-IV shows some of the times that this scenario would require. However, diffusion can still be considered as a potential secondary process in microseepage. Sokolov et al. (1965) calculated diffusion to be sufficient to have resulted in the dissipation of oilfields formed in the Palaeozoic, although to what extent, if any, this has occurred is not known. Furthermore, if any such fields had leakage along faults and fractures or due to erosion of the seal, diffusion might not be able to bring about accumulation before much faster effusive loss caused depletion. Diffusion of benzene into brines adjacent to accumulations has been demonstrated and used as an exploration tool by Zarella et al. (1967). In productive basins the process of diffusion from both source rocks and reservoirs may be responsible for observed elevated background concentrations which have no apparent relationship to the known accumulations. Alternately the presence of free hydrocarbons effusing outward and upward in areas of microfractures and dispersed by groundwater flow could similarly account for this background. If diffusion were the responsible mechanism, then one might expect broad anomalous zones, with localized effusive "spikes" superimposed on the background. Starobinetz (1983) listed as typical examples of diffusion the studies of Driepro-Douetsk and Anuddria grabens. Aside from the potential of diffusion for producing a broad dispersive background, it would also be expected to alter the composition of the gases detected in surface methods. Starobinetz (1983) notes that not only can diffusion affect composition, but two additional processes have a similar effect. These are chromatographic separation and selective adsorption. An example of such chromatographic separation is shown in Fig. 5-8 (Sokolov, 1971 b) which shows the results of a mixture of methane and benzene injected into the bottom of a hand-bored 6-metre deep well. Samples of subsoil air were taken periodically from observation wells 1 meter to 2 meters deep, resulting in the obvious separation shown in Fig. 5-8. Indeed these processes have been cited by detractors of surface prospecting as evidence that the technique is not a valid means of searching for subsurface hydrocarbons deposits, arguing that pulses (non-steady state) of gases will have a different composition from their source because of the chromatographic separation. The example shown in Fig. 5-9, taken from an artificial underground coal gasification experiment near Rawlins, Wyoming (Jones and Thune, 1982), shows that such effects are only temporary. In this experiment, a pulse of gas travels from a retort at a depth of 180 meters (600 feet) and migrates vertically and laterally to a series of observation wells 5.5 meters (18 feet) deep. As shown in Fig. 5-9, although the first gas to be seen in high concentrations is methane, the compositional separation does not last more than a few days before equilibrium is achieved when all the migrating gases have ultimately reached the surface. As to the second point, if selective adsorption is occurring, the volumes of material escaping over geologic time should ultimately saturate (poison) the adsorber such that no additional material can be adsorbed, or at best, material is exchanged in a steady-state. The result will be a gradual return of the signal to the original composition. This is clearly shown in a study by Zorkin et al. (1977). There is, however, one important area where diffusion may be responsible for compositional changes; near the soil-air interface. Methane should, due to its lightness and zero net dipole moment, be preferentially lost (followed perhaps by ethane). This would possibly result in an oilier gas signal at the surface. This could be countered by the production of biogenic methane which might partially compensate for this loss. HYDROCARBON RESIDENCE SITES AT SURFACE The most important of the direct techniques shown in Fig. 5-6 involve the measurement of light hydrocarbons, methane through butane. Because of their volatility, these light hydrocarbons are generally found in the free pore space. The seepage of hydrocarbons into the near-surface

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environment above the water table must involves transport through both water-filled and air-filled pores. Sampling these pore gases is obviously one of the most fundamental concepts. However, gases can be bound in the sediment matrix. This latter possibility leads to the development of some disaggregation and desorption extraction techniques. Discussion of sampling techniques must involve both "free" and "bound" gases. To facilitate this discussion the collection, measurement and analysis of light (C1-C4) hydrocarbons will be broken into two main categories each with two subcategories: (1) free gas, which can be vapor or dissolved gas; and (2) bound gas, which can be adsorbed gas or chemi-adsorbed gas. Freegas: Gases in the free pore space can be found either in the vapor state or dissolved in water. Extensive research at Gulf Research and Development Company has demonstrated that the "free" and "dissolved" gas seeps yield comparable compositional results, both to one another and to their associated reservoirs when they are properly collected and 1979; Weisman Standard mud gas logging is one variant of dissolved gas analysis conducted on deeper drill holes. A gas trap is deployed in the return mud system for extracting the dissolved and free gases. Compositional information obtained from mud logging gas is useful for predicting the composition of a potential reservoir (Pixler, 1969). These same ratios have been found to be indicative of oil versus gas potential from surface seeps observed from 12-feet deep soil gas measurements or from analysis of gases dissolved in the shallow groundwater (Jones and Drozd, 1983). Bound gas Bound gas, which is adsorbed on both the organic and inorganic matter contained in the sediment by means of physiochemical binding, introduces new complexities into defining the appropriate sample for analysis. The difficulty with defining this bound gas is forced by the reality that rocks and/or sediments contain gases of multiple origins. By their very nature, sediments contain both migratory (epigenetic) and indigenous (syngenetic) gases. Migratory gases (biogenic and thermogenic) have migrated to the surface from a deeper, more concentrated source. Indigenous gas is related to biogenic, diagenetic and thermogenic generation within the rock sampled at the surface and to recycled materials which may contain some physically transported hydrocarbons tightly bound in inclusions or other interstitial sites within the sediment matrix. The nature of the bonding of the hydrocarbons to the grain surfaces leads to two categories, adsorbed and chemi-adsorbed. These form an important part of this discussion because of misnomers involved with the use of the word "adsorbed". True adsorbed gases are by definition bound to the surfaces of sediment or rock particles. As defined by Greenland (1981) adsorption is the process by which a chemical species passes from one bulk phase to the surface of another, where it accumulates without penetrating the structure of the second phase. Because the light hydrocarbons are so labile, they do not strongly adhere to surfaces and are easily desorbed if the source of these gases is removed. The gas must be replenished by continuous migration in order to maintain the presence of adsorbed gases on the available surfaces. Bound within the rock matrix, or within certain minerals (calcite, oxide coatings, etc.) gases are chemi-absorbed. They can be removed only by a chemical attack which completely dissolves the rock or sediment matrix. Sometimes these more tightly bound gases not only include indigenous gases, but also might integrate the signal over time, mixing the products of "dead" or "non-active" seepage with those gases actively migrating today. The non-active seeps are often coupled to the lithologies of transported, non-residual sediments (Richers et al., 1986). These last considerations provide two of the main reasons why "free" and "chemi-adsorbed" gases are often found to have

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no obvious spatial correlation. Methods of geochemical prospecting Geochemical methods of prospecting are classified as direct or indirect. The direct methods involve detecting the presence of dispersed oil and gas components in the form of hydrocarbon gases or bitumens in the soils, waters or rocks in the vicinity of oil and gas accumulations. The indirect methods involve detecting any chemical, physical, or microbiological changes in the soils, waters, rocks, or vegetation associated with the oil and gas deposit It appears therefore that the direct detection of hydrocarbon gases is not the only means of identifying areas of active microseepage, but that a myriad of other possible secondary techniques can be used either as adjuncts, or as solitary techniques in themselves, to infer the presence of hydrocarbons in the subsurface environment. Most of these utilize the detection and subsequent analysis of gaseous hydrocarbons, while other methods employ the detection and analysis of liquid hydrocarbons, non-hydrocarbon gases, the presence and relative concentration of bacteria, and even the presence (or absence) of inorganic compounds and elements. For the most part, however, methods that directly measure the hydrocarbon content of soils or soil atmospheres have met with the most acceptance Principles of Surface Geochemical Exploration of Hydrocarbons The underlying principle of surface geochemical exploration of hydrocarbons is that hydrocarbons generated and trapped beneath the surface seep or leak to the surface in varying but detectable quantities. These phenomena occur because processes and mechanisms such as diffusion, effusion and buoyancy allow hydrocarbons to escape from reservoirs and migrate to the surface where they may be retained in the sediments and soils or diffuse into atmosphere or water columns (Jones and Drodz, 1983; Klusman, 1993; Schumacher & Abrams, 1996). The geochemical techniques use the assumption that the oil and gas accumulations are dynamic and their seals are imperfect leading to seepage of minute amounts of liquids and gases through the seal. The areas where subsurface hydrocarbons seep in large concentrations within and above the surface soils/sediments are called macroseeps. Macroseeps are the visible presence of oil and gas seeping to the surface and these have been documented from various parts of the world (Tedesco, 1995). About 90% of all major oil fields in the world were discovered because of macro seeps (Chilingar, 1969).The microseeps are hydrocarbons seeping mostly vertically or near-vertically from the reservoir to the surface. Microseeps are identified by elevated concentrations of analytically detectable volatile or semi-volatile hydrocarbons or hydrocarbon induced changes in soils or sediments Surface Geochemical Exploration Methods: The surface geochemical methods for detecting the near surface manifestations (microseeps) are direct or indirect indicators of hydrocarbons and can indicate the presence of subsurface petroleum occurrences. Direct indicators are mostly light gaseous hydrocarbons (methane, ethane, propane and butane), which get adsorbed, in the near surface soils while seeping from the subsurface to surface. Direct detection methods also involve analysis of volatile and semi-volatile heavier hydrocarbons such as aromatic compounds, gasoline range hydrocarbons in soils where migration occurs along fault and fracture pathways. Indirect geochemical methods detect seepage induced soil alteration such as microbiological anomalies, mineralogical changes such as formation

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of calcite, pyrite, elemental sulfur and certain magnetic iron oxides and sulfides, clay mineral alteration, helium emanometry, electrochemical changes, radiation anomalies, biogeochemical and geobotanical anomalies. A generalized model of hydrocarbon microseepage and their varied geochemical and geophysical effects on soils and sediments Soil gas surveys: The hydrocarbon gases migrating through soil pore spaces are not dissipated and diluted to the same extent as those in the atmosphere. There are, however, problems posed by the very low levels of hydrocarbon gases and by the diurnal "breathing" of many near-surface soils. In order to overcome these problems, soil gas techniques which integrate the hydrocarbon signal were introduced by Pirson Adsorbed soil gas surveys for geochemical exploration of hydrocarbons involves the measurement of light gaseous hydrocarbons (C-C) in near surface soils. The adsorbed soil gas surveycomprises of designing of sample locations, soil sample collection, acid extraction of adsorbed gases, gas chromatographic analysis of desorbed soil gases (C to C) and carbon isotopic analysis of Ccomponents by Gas Chromatograph Combustion- Isotope Ratio Mass Spectrometry (GC-CIRMS).Sampling strategy plays a crucial role in the surface geochemical surveys. The most cost effective sampling program includes a low density regional survey along existing roads at an interval of 4-5Km to high grade the area, followed by a higher density survey of grid sampling at 1-2Km interval with in the Canomalous area. Soil samples are collected using a hollow metal pipe by manual hammering from 2-5 m depth along existing roads or in grid patterns. The cores collected are wrapped in aluminum foils and sealed in poly-metal packs for analyses in the laboratory. The soil sample is treated with ortho phosphoric acid to desorb the soil gases. The CO is trapped in KOH solution and the light gaseous hydrocarbons are collected by water displacement. The desorbed gases are analyzed using gas chromatograph equipped with flame ionization detector and the concentrations of methane, ethane, propane, i-butane and n-butane are obtained by external standardization. Carbon isotopic analyses o are carried out by Gas Chromatography-Combustion-Isotope Ratio Mass Spectrometer (GC-CIRMS) which gives information about the source of the gases i.e. biogenic or thermogenic. The lightgaseous hydrocarbon data are used to prepare a series of maps of concentration of methane (C ) and ethane plus higher hydrocarbons (C) with oil and gas producing zones with the help of Geological Information System (GIS) to demarcate the potential areas for future hydrocarbon exploration Fluorescence Based Method: UV fluorescence spectroscopy is used to measure the oil potential of the near-surface soil by analyzing their aromatic hydrocarbons. Fluorescence is a physical process that occurs when a compound, like aromatic hydrocarbon absorbs light at one wavelength and spontaneously emits light ata different wavelength. Trace amounts of oil range hydrocarbons (C6 C can be extracted from soilsand analyzed using the fluorescence method. The fluorescence process produces an excitation-emissionfingerprint that is unique to each aromatic hydrocarbon. The intensity of the fluorescence emission isproportional to the quantity of aromatic hydrocarbons extracted in the soils (Jones et al., 1999).

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Bitumen Based Method: This method is based on the detection of high molecular weight hydrocarbons (C30+) plus) in thesoils/sediments using whole extract gas chromatography (GC) and gas chromatographymassspectrometry (GC-MS) (Abrams, 2005). A dried soil/sediment sample is extracted with an organicsolvent using a Soxhlet or accelerated solvent extractor, concentrated and analyzed by GC. Whenanomalous high molecular weight hydrocarbons are found with the GC analysis, further molecularcharacterization is done with GC/MS which provides detailed molecular information on biologicalmarkers. Biological markers are complex organic compounds originated from formerly living organisms.Different organic source facies contain different assemblages of organisms such as bacteria, algae,marine algae and higher plants. GC/MS biomarker data can provide the information about the organicsource facies depositional environment as well as the thermal maturity of the organic matter. The keybiomarker compounds measured in surface seep extracts are correlated to subsurface oils and sourcerocks (Hunt, 1996; Peters and Moldowan, 1993). Indirect geochemical surveys in offshore environment Now the areas of offshore oil and gas extraction are steadily expanded, therefore the volumes of exploration works are naturally increased. The efficiency of these works is determined by the necessary and sufficient method set to be used. Surface geochemical survey is a direct method of exploration which represents a special interest due to its relative cheapness, rapidity and possibility of detection of all the types of hydrocarbon deposits. Complex gas geochemical investigation is a basic approach to detect concentration anomalies of gas and liquid hydrocarbons migrating upward from oil, gas and gas condensate deposits. This method can also be used for environmental monitoring of petrochemical pollution. The main objects of surface geochemical study are bottom sediments and near-bottom water. There are two kinds of survey provided: aerial and profile. Aerial surface geochemical survey is performed for estimation of petroleum potential of structures outlined by seismic acquisition, which can be associated with both kinds of traps: anticlinal and non-anticlinal. Moreover, the aerial surface geochemical survey is effective while investigating distinct regions for presence of hydrocarbon accumulation and speculative areas allocation. Profile surface geochemical survey is carried out for detection of hydrocarbon concentration anomalies in bottom sediments and near-bottom water. This method is relevant on the stage preceding geophysical works as well as on the final stage of exploration, before contouring of the deposits detected. Purpose: a. To map the presence and distribution of oil and gas seepage to identify areas with a high potential for petroleum reservoirs. b. Reduce the area to be searched by helping to focus exploration efforts on regions and structures with active seepage. c. Predict the oil versus gas potential of prospective structures. Applications: a. Regional Exploration Programs to define portions of basin of concession areas with the highest potential for production. Regional studies are often run in conjunction with regional seismic programs and may include grids or other evenly spaced tests. b. Trend Evaluation Studies can be used to evaluate the potential of regional features and plays. Sample spacing is designed to sample a prospective play without concentrating on individual structures or prospects.

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c. Prospect Evaluation studies can be used to rate the relative seepage magnitudes and compositions of individual prospects prior to drilling so that structures with the highest potential are given a higher priority. Close spaced sample grids in conjunction with high resolution geophysical studies are most effective for multiple prospects. d. Anomaly Detailing including very closely spaced samples and stratigraphic/geochemical drilling programs can be used to detail oil source and maturity of individual high magnitude seeps over specific prospects of interest. Program Planning a. Regional Exploration Programs Regional exploration programs are designed to cover a large study area with evenly spaced core samples to provide a rapid and cost effective method of evaluating the potential of rank, unexplored areas. Typical studies of this type include samples on 2 to 5 km centers. Regional studies are of particular importance in large concession blocks with insufficient subsurface data to provide meaningful guidance on prospect areas or trends. The Green Canyon deepwater oil seeps in the Gulf of Mexico were first discovered by this method. b. Trend Evaluation Studies Surface geochemical exploration programs can be used to define the seepage levels and compositions of prospective structural trends. Trend studies generally include collecting cores on local grids of 2 - 4 km centers as guided by seismic data and regional structural interpretations. Surveys of this type can often confirm the existence of seeps along trend away from known reservoirs and predict the oil versus gas potential in these unexplored areas. c. Prospect Evaluation Prospect evaluation studies generally include integrated high resolution geophysical evaluation of individual structures of interest and subsequent core sampling to determine seepage levels and compositions. Results should be compared with calibration studies over known fields where seepage levels and reservoir compositions can be compared. Surveys generally include a tight grid of geophysical lines over a structure and close spaced core sampling at 1 to 2 km spacing over faults, gas charged zones and potential migration pathways from the subsurface. d. Anomaly Detailing Once a significant anomaly or macro-seep is encountered, close spaced geophysical surveying and coring can be completed to provide precise details on the seepage distribution, composition and the relationship of such seepage to specific subsurface faults. Detail evaluations are often used in deep water and frontier areas where the acquisition of free oil and gas macro-seep samples can provide significant information on the source rock type and maturity which is not available due to limited exploration wells in the area. Sampling patterns include very tight geophysical grids and pinpoint core collection with spacing often less than 1 km. Clustered core sites are often used. Additional subsurface data can be obtained from stratigraphic and geochemical borings into seep areas.

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GEOCHEMICAL ANOMALIES IDENTIFICATION THROUGH LANDSAT IMAGERY Landsat and other remote sensor systems (SPOT; JERS; radar, etc.) have been heavily used in searching for surface indicators of "leaking" subsurface oil and gas. The general approach to petroleum exploration is described. One line of investigation looks at structural analysis of space imagery in search of subsurface traps. Another, of infrequent success, seeks alteration at the surface caused by chemical changes related to surface-reaching oil or gas. In the early days of Landsat-1, a study in the Anadarko Basin of Oklahoma sought to demonstrate how alteration anomalies and lineaments analysis can aid in finding new petroleum by showing a relationship to already known fields. This pioneering program led to ambiguous but interesting results. Other examples are also considered on this page. The importance of Canadian oil sands as a major source of petroleum (oil) in the future receives special attention. Finding Oil and Gas from Space

If precious metals are not your forte, then try the petroleum industry. Exploration for oil and gas has always depended on surface maps of rock types and structures that point directly to, or at least hint at, subsurface conditions favorable to accumulating oil and gas. Thus, looking at surfaces from satellites is a practical, cost-effective way to produce appropriate maps. But verifying the presence of hydrocarbons below surface requires two essential steps: 1) doing geophysical surveys; and 2) drilling into the subsurface to actually detect and extract oil or gas or both. This Tutorial website sponsored by the Society of Exploration Geophysicists is a simplified summary of the basics of hydrocarbon exploration. Oil and gas result from the decay of organisms - mostly marine plants (especially microscopic algae and similar free-floating vegetation) and small animals such as fish - that are buried in muds that convert to shale. Heating through burial and pressure from the overlying later sediments help in the process. (Coal forms from decay of buried plants that occur mainly in swamps and lagoons which are eventually buried by younger sediments.). The decaying liquids and gases from petroleum source beds, dominantly shales after muds convert to hard rock, migrate from their sources to become trapped in a variety of structural or stratigraphic conditions shown in this illustration:

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From Physical Geology: Earth Revealed by McGeary and Plummer, First Ed., W.C. Brown Publ. The anticlinal trap, among the most common, is nicely revealed in a real world setting in this old photograph:

The oil and gas must migrate from deeper source beds into suitable reservoir rocks. These are usually porous sandstones, but limestones with solution cavities and even fractured igneous or metamorphic rocks can contain openings into which the petroleum products accumulate. An essential condition: the reservoir rocks must be surrounded (at least above) by impermeable (refers to minimal ability to allow flow through any openings - pores or fractures) rock, most commonly

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shales. The oil and gas, generally confined under some pressure, will escape to the surface - either naturally when the trap is intersected by downward moving erosional surfaces or by being penetrated by a drill. If pressure is high the oil and/or gas moves of its own accord to the surface but if pressure is initially low or drops over time, pumping is required. Exploration for new petroleum sources begins with a search for surface manifestations of suitable traps (but many times these are hidden by burial and other factors govern the decision to explore). Mapping of surface conditions begins with reconnaissance, and if that indicates the presence of hydrocarbons, then detailed mapping begins. Originally, both of these maps required field work. Often, the mapping job became easier by using aerial photos. After the mapping, much of the more intensive exploration depends on geophysical methods (principally, seismic) that can give 3-D constructions of subsurface structural and stratigraphic traps for the hydrocarbons. Then, the potential traps are sampled by exploratory drilling and their properties measured. Remote sensing from satellites or aircraft strives to find one or more indicators of surface anomalies. This diagram sets the framework for the approach used; this is the so-called microseepage model, which leads to specific geochemical anomalies:

The surface geochemical expression of petroleum seepage can take many forms: (1) anomalous hydrocarbon concentrations in sediment, soil, water, and even atmosphere (2) microbiological anomalies and the formation of "paraffin dirt" (3) anomalous non-hydrocarbon gases such as helium and radon (4) mineralogical changes such as the formation of calcite, pyrite, uranium, elemental sulfur, and certain magnetic iron oxides and sulfides (5) clay mineral alterations (6) radiation anomalies (7) geothermal and hydrologic anomalies (8) bleaching of redbeds (9) geobotanical anomalies (10) altered acoustical, electrical, and magnetic properties of soils and sediments. Landsat, and other space imaging systems, serve as mega-photos that depict large areas, within which clues to subsurface conditions may be evident. In general, most of the obvious structures that have surface expression had been discovered and mapped (to varying extents) over much of

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the world. Some regions, however, were not adequately mapped even in the 1970s, so that the advent of higher-resolution space imagery proved a boon to energy companies seeking new sources of fossil fuels. Sometimes the imagery proved especially sensitive to subtle indications of interior structures. For instance, fractures around structures in known oil/gas fields may extend further, as seen in the coherent space images, than suspected from ground work. Also, drainage patterns at broader scales may reflect control by underlying rocks involved in suitable traps. And even vegetation distribution may disclose signs of structure. These and other indicators discernible in space imagery appealed to exploration geologists as another means to survey large areas. The two most useful indicators discernible in airborne or spacecraft remote sensors data are fracture systems (mainly lineaments) which can control or affect the migration of gas and oil to the surface and geochemical alterations of surficial rocks by hydrocarbons which lead to compositional and color changes. This second effect is reviewed on a website that deals with hydrocarbon detection. We will now illustrate these ideas by examining and evaluating one of the first case studies using Landsat-1 to demonstrate the feasibility of direct exploration from space. This pilot study, conducted jointly by the Eason Oil Corp. and the Earth Satellite Corp. of Rockville, MD, sheds considerable light on effective criteria for recognizing conditions that might relate to buried hydrocarbons. In addition, some of the pitfalls associated with the space approach were also discovered by carefully assessing the results reported by these investigators. The strategy behind the study was to look at Landsat imagery of a region already established as a petroleum province, giving special attention to telltale surface indications of the presence of known underlying fields. The investigators used standard-processed and computer-enhanced versions. Rather than test capabilities in a region where there is obvious structural control and other clearcut evidence, they selected producing areas where the surface does not give clear indication of subsurface conditions. If they could succeed in detecting hydrocarbons under such difficult circumstances, then Landsat would increase in stature as an oil/gas discriminator . The Anadarko Basin of south-central Oklahoma fits this requirement well. Located in the eastern Great Plains, with most of the land used for farming and ranching, the Basin is one of the great producers of the mid-continent petroleum province, which also includes much of Texas, as well.

The Basin is a down-sag in the crust that has allowed up to 15,200 m (50,000 ft) of Paleozoic sedimentary rock to accumulate. Structurally, the Basin is an asymmetrical geosyncline (a regionalscale downfold), with the deepest part near the south edge. Oil and gas are present in porous rocks

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associated with structural (anticlines; fault blocks) and stratigraphic traps. Large gas fields occur mainly along the Basin's western half, whereas oil is more common in the eastern half. Wells as deep as 7,600 m (25,000 ft) have recovered both hydrocarbons, although most pay zones are between 2,750-5,250 m (9,000-15,000 ft). Generally, surface expression of underlying oil or gas traps in the Basin is meager, because first, there are few structural indicators in the flat-lying sediments atop older folded units and second,there is overprinting of geologic features by vegetation and land use (grasslands; hilly sagecovered terrain; and wheat farmlands). The Eason Oil/Earthsat investigators decided to focus on two search elements: previously undiscovered fractures and subtle chemical alterations of surface rocks by escaping hydrocarbons. Lineaments analysis was conducted by Eason Oil using Landsat image transparencies backlighted on a light table. The linear features they picked are shown by lightweight black lines on the map below. Superposed as brown and green-black heavier lines are faults that had previously been discovered and mapped. As a geographic reference, note the meander bends (curved segments) of the Canadian River, traced in blue. The majority of the Landsat-mapped linear features are inconspicuous in the imagery. Many of them are suspect, i.e., they could be non-geological or some type of lighting artifacts.

As first mentioned in Section 2, a group of four geologists, including this writer (NMS), at Goddard Space Flight Center, decided to check on the reproducibility of these map results, using the same April, 1973 Landsat MSS full scene (see below). Each person used the same transparencies (mostly winter images) as Eason Oil and worked independently of one another to minimize bias. When done, we registered the tracings to a base map, on which the Eason Oil lineaments were also plotted, as seen below. The comparison disclosed rather startling discrepancies in terms of variance between the two groups. We found only about 20% of the total linear features in common. Eason Oil chose approximately 35% of the questionable features, exclusively, while Goddard geologists chose the remaining 45%, which represented those "missed" by Eason Oil. We immediately suspected that this kind of result is partially due to considerable subjectivity in deciding whether a given linear feature a) really exists, b) is geological in nature, and c) means anything.

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This suspicion was reinforced by comparing the linear features selected by the four Goddard geologists. Here are the results - a mishmash that requires the following interpretation:

Of the 785 linear features identified by all four combined, only 4 (0.5%) were noted by every operator. From the remainder, 3 operators mutually selected 37 (4.7%), two operators agreed on 140 (17.8%), and the rest, 604 (77%), each operator found exclusively. This type of result has been reported in similar studies, although the above scores were particularly discouraging. Each geologist had ample experience in photointerpretation and special skills in analyzing Landsat imagery. Their choices were justifiable but overall, our results were questionable. 5-10: In this experiment, and in the technique of picking linear features in space imagery, what do you think was really going on behind the end result of some many linears being found but not consistently by multiple interpreters? ANSWER

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The bottom line here is that there often is a strong tendency towards overkill in choosing features that appear to be meaningful lineaments. So many are drawn that it would take a monumental field effort to check them out. If plotted as rose diagrams (see page 2-9), they may reveal valid trends for the orientations of regional fractures, because statistically lineaments of non-geological nature should be in the minority. (A study of obvious lineaments in the Adirondacks confirmed this result.) Of the 200+ prominent ones in the Anadarko Basin that were field-checked, geological fractures directly or indirectly controlled most of them, but about 20% related to human factors, such as fence lines, roads, etc. Thus, we conclude that we should combine lineaments analysis with other indicators of mineralization or hydrocarbons. This combining would encourage geologists to fieldcheck particular sites to verify the lineament presence and nature and their possible correlation with these indicators. The Eason Oil study sought to recognize such indicators. Their interpreters delineated certain geomorphic anomalies, such as circular patterns and unusual drainage. In the course of their image appraisals, they noticed unexpected tonal patterns that looked a bit like light-colored smudges on the images, such as evident in the April, 1973 full Landsat MSS scene that became the reference base for the study. These they called "hazy" features, as seen here:

We labeled three typical hazy patterns A, B, and C. The one at A, at a bend in the Canadian River, is especially prominent, and occurs over a known oil field. A standard false color subscene (computer-enhanced) around A shows the hazy to have a bluishwhite color similar to soils in barren fields. Note the road pattern and white blotches which are accesses to producing wellheads. The yellowish areas coincide with unaltered Permian (late Paleozoic) red beds.

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When we process this April Multispectral Scanner image into three ratio bands that we then combine into a color image (4/5 = Blue; 5/6 = Green; 7/5 = Red), the hazy feature at A takes on a unique yellow-green, and the red beds become orangish.

The signature for the hazy area, seen in darker orange-brown, is conspicuously different from its surroundings. It is associated with a small oil field that was developed after the Oil and Gas Map of the U.S. was published (see below). An aerial photo shows the roads that cross the hazy patch (inside the large meander loop of the Canadian River):

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One might argue that the activities from the drilling had somehow lightened the whole immediate area, accounting for the "hazy". But, this is unlikely, especially since other hazies usually do not have active oil fields associated with them. The lighter tone is more likely to be a condition within the soil. From the multiseasonal data sets, only those scenes imaged in late winter to early spring show hazies. At other times of the year, vegetation masks the phenomenon. To understand their explanation of the features, we look now at this photograph of two rock types:

The rock on the far left is a sample from the red beds (sandstones) of Permian age. Next to it is the same material that has been color bleached to yellow-brown by converting iron oxide cement into hydrated iron oxides (analogous to rust). The gray rock on the far right is a limestone (calcium carbonate). To its left is a gypsum rock (hydrated calcium sulphate). Both interior rocks appear to be altered equivalents of the primary exterior rocks. In the field, comparable altered rocks can occupy many square miles. To account for these hazy features, the Eason Oil people postulated that chemical reactions affected the iron cement, bleaching it out, and/or transformed the carbonates into sulphates. This, they surmise, happens when sulphur-laden gases or fluids leaked out of petroleum traps and rose towards the surface, interacted with susceptible rocks, and brought about compositional changes. Microseeps along lineament would be particularly effective. About the time of their conclusion, evidence for such changes was reported as the Doctoral thesis of Terrence Donovan (later of the U.S.G.S.), in which escaping hydrocarbons drastically altered rocks above the Cement Field, at the southeast edge of the Anadarko Basin. Dr. Donovan found a pronounced set of anomalous values of the ratio of C13 to C12 in samples collected over both producing zones in the field, shown as contoured areas below:

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These values represent some of the highest departures from normal ratios known anywhere in the world. He attributed them to the effects of chemical action by carbon-rich fluids on the rocks which, as a consequence, appear bleached. The Cement Field does not show any evident hazy-type anomaly in the imagery Eason Oil used. But an image processed by EarthSat did show a whitening about where the Cement Field is located, seen as a lighter tone near the center of the image (this is a winter scene, and a trace of snow is found around a reservoir to the northwest, but appears absent in the vicinity of the Cement Field).

Accepting this alteration hypothesis, the Eason Oil group looked for at least partial coincidence between these hazies and the surface projections of subsurface oil or gas fields. Of the 57 anomalies they mapped in a control segment of the imagery, they claimed an association with 42 producing fields. Another six occurred above or near non-producing structures, and only 9 showed no coincidence. If this observation remained true, then detecting hazies, sometimes correlative with lineament concentrations, could promise a powerful new way to hunt for oil and gas using space imagery.

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The present writer (NMS), being skeptical in habit, decided to challenge these findings. The begging question: To what extent do the hazy anomalies correspond to known oil and gas field distributions. Here is a part of the Oil and Gas Map of the U.S. published by the American Association of Petroleum Geologists (AAPG):

On this map, the Cement Field is shown in a unique color - a purplish-brown. Next, here is the Eason Oil Map of the hazies shown in purple-blue:

It's hard to check the degree of correspondence by shifting between the two maps. So, I traced the outlines of the Eason Oil hazy features (in a hachured pattern) on a transparency and then overlaid and registered it to the oil (greens) and gas (reds) AAPG map of Oklahoma. The resulting combination is shown here:

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Visually, the coincidence between hazies and fields does not appear strong. This was supported by a spatial correlation analysis, which demonstrated there is no statistical significance to the pattern distribution, i.e., the coincidence is random rather than associative. In practical terms, there would be at least as much chance of striking oil by drilling into points selected by throwing darts at the map, as there would be in drilling into the centers of hazies. (That is not facetious: I did drop the overlay randomly several times onto the AAPG map - a few hazies always landed on a few oil fields.) Based on a quick field trip to the A hazy, the writer (NMS) believes hazy features are areas where wind has blown away much of the soil fines, leaving reflective quartz grains behind. Of course, if escaping hydrocarbons affect the soil, that may be degraded enough to foster the wind removal. However, at one locality designated as a hazy feature, the writer did find convincing evidence of what appears to be distinct color difference attributable to hydrocarbon alteration of red beds. In a dirt road, the reddish-orange of unaltered Permian rocks gives way to a yellow-white color representing hydrocarbon "bleaching" as proposed by EarthSat/Eason Oil. Here is a photo taken at that point:

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The Goddard geologists under my direction didn't perform these studies to discredit the Eason Oil study, which provided some valuable insights into the discerning power of space imagery for petroleum exploration and the potential shortcomings of the apparent results. We did them to independently evaluate this approach and to inject caution into any beliefs that this technique might become a panacea for finding petroleum. 5-11: Critique the Eason Oil study, devising if appropriate a defense of their approach. In general, what do you believe to be the most effective use of remote sensing in exploring for hydrocarbons. ANSWER Our bottom line: "The Jury is still out" on making positive claims about oil and gas exploration if based solely on the Eason Oil/EarthSat report. At the time of the Anadarko study, several other investigators claimed to have found similar evidence that appeared to indicate that leaking oil and gas reservoirs could indeed be altering surface rock and soil. One that seemed to confirm this was the Beaver Creek Oil Field in the Wind River Basin of Wyoming. Dr. Robert Vincent presented this evidence, an MSS Band 5 (red) to 4 (green) ratio image in which a prominent oval shaped anomaly (shown here in tan) coincided very closely with the outline of the field as determined by subsurface drilling:

The writer (NMS) visited this field while engaged in his Wyoming investigation work. The area consisted of Lower Tertiary sedimentary rocks that were strongly dissected into gullies. Many of these beds were reddish and could in themselves account for some of the anomaly. A rather quick search for obvious signs of alteration by escaping gases or fluids failed to find any convincing evidence. But the remarkable co-incidence of the 5/4 anomaly with the outline of the Beaver Creek field suggest that this may be a valid example of the concept of alteration by petroleum compounds. Landsat results in geological applications excited many in the petroleum and mining industries. Various companies banded together as a consortium, starting in 1976, in what became known as The Geosat Committee. Their avowed aims were along three lines: 1) to share information and conduct studies using space imagery to search for petroleum and minerals (mainly metallic ores); 2) to "lobby" NASA and Congress for a continuation and expansion of the Earth-Observing Satellite program; and 3) to provide inputs in determining and improving sensors in future satellites. One of their principal study sites was the Patrick Draw oil field near the Beaver Creek field in Wyoming. (see summary online at this website: Patrick Draw oil field). Hydrocarbons appear to be leaking as gases at various points above the oil field. This map shows the results of a field study (ground cored typically to depths of 3-4 m) that retrieved samples analyzed for propane:

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When the Patrick Draw field was overflown by an airborne UV sensor, this map of fluorescence anomalies was constructed; these results seem to confirm detectability of hydrocarbon-related gases at or above surfaces where leakage of the gases occurs:

Two discoveries stemming from the Geosat study of Patrick Draw are significant: 1) a map of lineaments shows microseeps at several intersections, and 2) there is a distinct geobotanical anomaly in and near Patrick Draw - sage plants are damaged, presumably by escaping hydrocarbons, and this is detectable in hyperspectral imagery. Unfortunately, key illustrations supporting this have not been made public. Earth Satellite Corp. (now renamed MDA Federal, Inc), and another group, Earth Search Sciences, have continued to validate data obtained from sensors on satellites and aircraft as potentially decisive indicators of subsurface oil/gas fields. This next diagram summarizes recent thinking:

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Airborne hyperspectral sensors that were flown over known hydrocarbon leaks (in some settings, called microseeps) have found that an absorption feature near 2.31 m (one of several in the near IR) is very sensitive to the amount of a specific component of the hydrocarbons. A ratio of two reflectance values on either side of that absorption feature divided by the value of the decreased reflectance in the spectral curve at the feature's low point enhances the detectability of the hydrocarbon and quantifies its magnitude.

This next image display shows an actual field case conducted jointly by the HJW GeoSpatial, Inc, the Geosat Committee and Earth Search Sciences in which an oil seep that corresponds to a specific pixel (red) in the Probe-1 hyperspectral scanner image shows the 2.31 m diagnostic anomaly (strong absorption bands at 1.4 and 2.0 m are related to other materials):

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Leaks of oil from fields below the ocean can serve both as an exploration indicator and as a source of environmental damage. Prospecting for oil beneath the open ocean requires some different techniques as well as use of some of the conventional land methods. Oil seeps and slicks can remain intact on the surface and may be detectable in Vis/NIR and radar imagery. The Earth Satellite Corporation has developed SEP - the Seep Enhancement Algorithm - to bring out an oil signature using radar imagery. Here are two examples:

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Oil slicks can be both natural or due to manmade oil spills. This EarthSat image shows a slick off the coast from Kuwait as rendered in a natural color Landsat image.

Specialized remote sensing can monitor another aspect of petroleum withdrawal not necessarily expressed as leaks. In time, as the oil is removed from pores leaving a partially filled void, the rock units bearing the oil start to contract or crush inward into the voids as support diminishes. This is commonly expressed by all the overlying units pushing downward on the now compressed reservoir rocks, giving rise to progressive surface subsidence. This lowering of elevation can be monitored by radar interferometry (see page 11-10 This next illustration, made from ESA radar data, shows interferometry rings, which can be computed into elevations, at the Lost Hills oil field in the San Joaquin Valley of California. The field is subsiding now at a rate of about 3 cm (1.2 inch) per month, with a cumulative drop since 1989 of 3 meters (10 ft). Subsidence is greater at the two ends of this 1.5 x 6 km (~1 x 4 miles) elongate field.

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At the time of this writing (February, 2007) the intensity of the economic and political aspects of the availability and costs of oil and gas as still the principal energy sources for such multiple uses as transportation, heating, and plastics is at a "dangerously" high level. Prices are rising everywhere because of OPEC decisions, rapidly growing markets (e.g., China), and threats of cutting production (Iran's nuclear program). Alternate sources of energy, including oil in non-conventional modes of recovery, are being pushed. Two huge potential suppliers are Canada (tar sands) and Venezuela (heavy oil; requires pumping in hot water to release the oil from its host rock). Estimates of available oil from these types of deposits in Alberta, Canada approach, or may exceed, two trillion barrels (Venezuelan heavy oil is at least one trillion barrels). The Canadian oil sands were first discovered in the late 1700s. The sand units outcrop at the surface in the northeast part of the province of Alberta but have a wider distribution subsurface, as seen in this map:.

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The Cretaceous sandstones that contain sticky, near-solid bitumens (up to 20%) filling interstitial pores have been called Athabasca Tar Sands or now more commonly Alberta Oil Sands. Here is a surface photo of an outcrop rich in the blackish tar that pervades the rock.

As seen by the Space Shuttle astronauts in 1989, the area along the Athabasca River where surface stripping of the oil sands is active, is shown in the middle. The town of Fort McMurray, which has since grown considerably in anticipation of greatly increased production, appears to its south:

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Here are two aerial views of this main strip mine complex;

The oil sands after surface removal are further broken up and then extracted from the rock pores by subjecting the material to hot water and other chemicals. A barrel of thick oil requires processing of about a ton of the oil sand. Here is a processing plant where this is accomplished:

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For decades the cost of obtaining liquid products from the sands for further refining had been too high to turn a profit. But that has now rapidly changed as prices of oil and gasoline in the U.S. and worldwide climb in response to demand. This has convinced various companies to set up greatly expanded operations. If stripping becomes impractical, the cost of subsurface mining must be weighed against expected increases in price and demand. In time recovery is likely to include underground mining. One plan is to confine stripping recovery to the summer months and go underground when the snow cover impedes surface mining. The reserves in Alberta are huge comparable to that known in the Arabian Peninsula. There may be enough tar sands in Alberta to place Canada in "the driver's seat" in the 21st Century; for North America alone there could be sufficient oil sand reserves to last a century. As of 2009, the U.S. gets 22% of its oil (about 1.5 million barrels a day) from these Canadian deposits; China is becoming another major customer. The Canadian government is carefully monitoring and controlling the expansion of the oil sand industry. Waste at the surface, as seen below, must in a reasonable time be reworked to form a smooth surface and then replanted with trees and grass. Here is where space imagery will play a leading role - determining that the reclamation requirements are being met.

Among other uses of remote sensing for applications related to oil and gas exploration and production include: 1) monitoring pipeline location and possible breaks (leaks), 2) monitoring environmental damage from drilling for oil/gas, 3) monitoring recovery of the natural terrain after a field is no longer producing, and 4) producing land use/land cover maps of a region where new or increased development is anticipated.

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An example of item 2 is offered by this photo taken from the International Space Station. It shows the barren ground patches around individual drilling sites and developed wells in the West Texas Permian Basin - a major producer in the U.S.:

Astronaut photography is occasional and target-selective. Environmental effects in areas immediately around drilling sites need more frequent monitoring. This SPOT-5 image shows multiple sites near Carthage in west Texas. There appears to be almost no adverse impact on areas surrounding the white scars that result from land cover clearing at each site.

This EO-1 satellite image also has environmental significance. It shows the markings saturating the hills of southern California's Coast ranges at the Elk Hills oil field, which first started producing in 1912 and is still active. It has yielded more than 1.3 billion barrels of oil and some natural gas. For many years it was the kingpin of the Naval Petroleum Reserve before being sold to Occidental Petroleum Co. in 1997.

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Regarding item 4 - land use mapping of a developed or developing natural energy-rich region - is done in compliance with regulations for managing all of the resources. The writer (NMS) participated in a singular example of this requirement, which engendered an outcome of some notoreity. Here is the story: Landsat-1 started to send back images in late July of 1972. The writer (NMS) was then a coinvestigator with Dr. Robert S. Houston and Dr. Ronald Marrs of the Geology Dept., University of Wyoming (Laramie) in the NASA-funded Wyoming Geology program. I received the first images of Wyoming in mid-August and left at once for the field there. I spent a week roaming the state to check out what I could relate between image features and ground truth. Upon return to Laramie, Drs. Houston and Marrs and myself drove to the state capital, Cheyenne, to meet with state officials about possible uses of Landsat imagery in environmental and land use projects. A big one was in the offing - 8 million dollars to prepare land use maps of the Powder River Basin. That basin is one of the richest energy sources in all the U.S. - huge (and thick) deposits of coal, active uranium mining, and some oil and gas productions. The maps were needed within 3 years. The state officials decided to gamble and earmark $60000 for the University of Wyoming to "try" to produce some preliminary maps using Landsat. The project began in September. On January 13, 1973 the faculty and students who worked on Landsat imagery presented a large (30 inches by 16 inches) folio with a series of maps - all patiently colored by hand using student help - that addressed several themes. Most important was the land use map, a portion of which is reproduced here:

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The State was so impressed, it accepted these folio maps as adequate in meeting its multi-million dollar objectives. No further work was done. A copy of the folio was soon sent to me. I too was impressed. I brought this copy down to the Earth Observations program office at NASA Headquarter for the managers to see. Their reaction was almost boisterous. This is just what they were looking for when they went to the U.S. Congress in just a few weeks to an Appropriations Committee hearing. The NASA chief, Dr. Len Jaffe, just commandeered (syn., confiscated) the folio and told its story to the congresspersons. (Never got the folio back; students had to color another one for me.) But a small price to pay to get the overall program in high gear. Suffice to close this page with the remark that since the launch of ERTS-1, the petroleum industry has found new oil and gas fields with the aid of space data and has developed criteria from the images that continue to prove worthwhile in planning and conducting exploration programs, which are leading to payoffs. Most of the successes have come by using space imagery (as has been done before with aerial photography) in the tried-and-true (conventional) way of using the pictures as base maps on which to analyze and plot structural patterns and trends, often supplemented by recognition of stratigraphic units. (Detection of surface alteration, while it happens sometimes, remains a rather rare event. In sum, remote sensing aids in exploration for oil and gas by 1) providing overviews of the regional geologic setting in which oil and gas is being sought; 2) helping to define existing fold/fault structures; 3) demarcating linear features that are usually fractures along which hydrocarbons migrate; 4) detecting alteration of rocks by escaping hydrocarbons; 5) finding other signatures indicated by fluorescent anomalies in the UV and compositional anomalies in the IR; 6) noting oil directly as leaks, spills, and seepage in the oceans/lakes or on land; and 7) observing environmental damage associated with drilling, pumping, pipeline transfer, and refining of hydrocarbon magnetic alteration of oil seepage signature.