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Hydrocarbons in Basement Formations
Hydrocarbons in Basement Formations
Hydrocarbons in Basement Formations
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Hydrocarbons in Basement Formations

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Petroleum and natural gas still remain the single biggest resource for energy on earth.  Even as alternative and renewable sources are developed, petroleum and natural gas continue to be, by far, the most used and, if engineering properly, the most cost-effective and efficient, source of energy on the planet.  Contrary to some beliefs, the industry can, in fact, be sustainable, from an environmental, economic, and resource perspective.  Petroleum and natural gas are, after all, natural sources of energy and do not have to be treated as pariahs.  This groundbreaking new text describes hydrocarbons in basement formations, how they can be characterized and engineered, and how they can be engineered properly, to best achieve sustainability.

Covering the basic theories and the underlying scientific concepts, the authors then go on to explain the best practices and new technologies and processes for utilizing basement formations for the petroleum and natural gas industries.  Covering all of the hottest issues in the industry, from oil shale, tar sands, and hydraulic fracturing, this book is a must-have for any engineer working in the industry. 

This textbook is an excellent resource for petroleum engineering students, reservoir engineers, supervisors & managers, researchers and environmental engineers for planning every aspect of rig operations in the most sustainable, environmentally responsible manner, using the most up-to-date technological advancements in equipment and processes.

LanguageEnglish
PublisherWiley
Release dateJan 25, 2018
ISBN9781119294481
Hydrocarbons in Basement Formations

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    Hydrocarbons in Basement Formations - M.R. Islam

    Chapter 1

    Introduction

    1.1 Summary

    Hydrocarbons and their transformations play major roles in sustaining today’s civilization. Petroleum fluids are essential for providing chemical and energy sectors with raw materials that are needed for practically all aspects of modern living ranging from transportation to health and medicine. After water, crude oil is the most abundant naturally occurring fluid on earth. However, the modern era has few direct applications of crude oil and practically none of the produced petroleum is processed, either through refining or gas processing, prior to final use. Unfortunately, all modern techniques for refining are also known to be inherently damaging to the environment. In the information age, environmental sustainability has become the most important concern and there is a growing urge to find either an alternative to petroleum fluids or any technology that ‘minimizes’ the environmental impact. While some progress has been made in developing alternate energy sources, few, if any, present a truly sustainable option. More importantly, no realistic alternate source, sustainable or otherwise, for millions of tons of chemical raw materials for the chemical/medical industries has been suggested. In this regard, basement reservoirs offer an unprecedented opportunity. However, the true benefit of the petroleum fluids produced from basement reservoirs cannot be appreciated without thorough scientific understanding of their nature. This is the first textbook that makes a scientific investigation into the nature of basement rock, the origin of the petroleum that impregnates these rocks and how to properly characterize the behavior of these rock/fluid systems. It is shown with clarity that basement fluids are amenable to sustainable petroleum usage and with careful management skills they can become the hallmark of a sustainable source of both energy and chemical raw materials. This textbook explains the fundamental features of the hydrocarbons in the basement, geological aspects of fractures and types of fractures, and a novel reservoir characterization technique. Two dominant theories of the origin of basement fluids are presented in detail and arguments made in supporting the validity of these theories within a specific domain. It covers almost all seismic techniques including geological techniques, geophysical tools, micro log analysis and borehole techniques, with a focus on fracture networks. A guideline for scientific characterization is presented in order to determine the ranking of petroleum fluids. This book deals with the interpretation and modeling of the fracture network as well as risk analysis and reserve estimation of these kinds of reservoirs.

    1.2 Is Sustainable Petroleum Technology Possible?

    Even though petroleum continues to be the world’s most diverse, efficient, and abundant energy source, due to grim climate concerns, global initiatives are pointing toward a go green mantra. When it comes to defining ‘green’, numerous schemes are being presented as ‘green’ even though all it means is the source of energy is not carbon. In fact the ‘left’, often emboldened with ‘scientific evidence’, blames carbon for everything, forgetting that carbon is the most essential component of plants. The ‘right’, on the other hand, deny climate change altogether, stating that it is all part of the natural cycle and there is nothing unusual about the current surge in CO2 in the atmosphere. Both sides ignore the real science behind the process. The left doesn’t recognize the fact that artificial chemicals added during the refining process make the petroleum inherently toxic.

    The study of sustainability is a complex science as it involves subsurface and surface, natural and artificial materials, with very high ratio of unknowns over known information (Figure 1.1). Any false step in the process shown in Figure 1.1 can trigger unsustainability. Both the science and the mathematics of the process have been deficient at best.

    Figure 1.1 Various steps involved in petroleum technology.

    In 2010, we (Islam et al., 2010) used detailed pathway analysis to identify flaws of various energy production schemes, including petroleum resource development. The source of alteration of CO2 quality that renders the CO2 unabsorbable by the ecosystem was identified for each case. CO2 emission data from the pre-industrial age all the way to the current era are then analyzed, showing a clear correlation between CO2 concentration in the atmosphere with ‘corrupt’ CO2 emission, which itself was a function of the fuel source, the path it travels, isotope numbers, and age of the fuel source. Various energy technologies were ranked based on their long-term sustainability. It was shown that petroleum is the most environmentally benign among the energy sources investigated, followed by biofuel, solar, wind, and nuclear. When the artificial chemicals are replaced with natural substitutes at various phases of petroleum processing, petroleum wastes become useful materials that can be recycled in the ecosystem in a zero-waste mode. Not only the by-products, including CO2 emissions, are benign, they are in fact beneficial to the environment. Each of these wastes can then become raw materials for value-added new products. Finally the paper offers guidelines for ‘greening’ of petroleum operations as well as the economics of zero-waste petroleum production and long-term environmental sustainability. So, if petroleum products are benign and offer the greatest hope for sustainable technology, which type of petroleum reservoirs are the best of the best? In this book, we disclose the facts about basement reservoirs and demonstrate that basement reservoir fluids are the most beneficial with the greatest possibility of value addition, as long as their processing is done targeting a particular application, uniquely suited for these fluids. Such a study was only possible after scientific characterization of the rock and fluid system.

    1.3 Why is it Important to Know the Origin of Petroleum?

    Petroleum fluids are synonymous with ‘fossil fuel’ or any fluid with organic origin. It turns out, invoking such a premise limits the ability of properly characterizing petroleum fluids, including the true source. This is particularly true for basement reservoirs that are known to have little resemblance to conventional fossil fuel. It is no surprise that oil and gas fields in crystalline basement are discovered mostly by accident, usually when the unassuming operator notices hydrocarbon shows. Yet, these reservoirs can be prolific and the overall estimate of petroleum reserve can go up with revamping of techniques to track basement reservoirs. The standard definition of crystalline basement by petroleum geologists is any metamorphic or igneous rock unconformably overlain by a sedimentary sequence. A somewhat more ‘scientific’ definition is given by Lartdes et al. (1960): the only major difference between basement rock and the overlying sedimentary rock oil deposits is that in the former case the original oil-yielding formation (source rock) cannot underlie the reservoir. This definition extends the limit of exploratory geological and geophysical studies significantly. However, this definition is still limiting as it suggests that a basement reservoir may be the result of hydrocarbon migration from sedimentary rock to older porous metamorphic or igneous rocks to form a basement reservoir, the likes of which were found in Japan, Mexico and the Maracaibo Basin of Venezuela (Schutter, 2003). As pointed out by Petford & McCafrey (2003), this narration is a mistake. The 1999 Gulf discovery of Suban gas field after penetration sufficiently deeply in the basement rocks proved this point. Similarly, literature is deficient in giving sufficient consideration to mixed convection heating from igneous rocks that can contribute to the maturation process in sediments that have been heated rapidly by magmatic intrusion (e.g., Saxby & Stephenson 1987; Stagpoole & FunnelI 200I; Schutter 2003), making excellent cap rocks (Chert et al., 1999).

    The accurate knowledge of the source of the basement oil is pivotal for two reasons. First, this would create an impetus for broadening the exploration base for basement reservoirs. Secondly, the quality of oil will likely be linked to the source and thereby would open up different opportunities for processing for environmental integrity. The possible sources of basement fluids are investigated for both organic (Chapter 2) and nonorganic (Chapter 3) origins. Even more significant discussion is presented in Chapter 5 that shows scientific characterization of these reservoirs must include the accurate source of these fluids, in order to properly identify long-term pathways of various components present as well as applicability of the hydrocarbons in question.

    1.4 What is the Likelihood of an Organic Source?

    Not long ago, an organic source was the only one considered for defining petroleum fluids. Even though igneous rocks posed an interesting dilemma in terms of how organic matters accumulated there, there was no shortage of dogmatic interpretation of geologic history. However, more questions arise than answers exist concerning hydrocarbons in and around igneous rocks. Figure 1.2 shows the distribution of hydrocarbons in and around igneous rocks. This figure shows that the highest reported occurrences are in basalts, followed by andesite and rhyolite tufts and lavas. Although volcanic rocks in this survey constitute close to three-quarters of all hydrocarbon-bearing lithotypes, the majority of production and global reserves appears to be confined predominantly to fractured and weathered granitic rocks (Petford & McCafrey, 2003).

    Figure 1.2 The distribution of hydrocarbons in and around igneous rocks according to lithology (from Schutter 2003).

    In order to make a non-controversial conclusion regarding the source of this hydrocarbon, one would need to have more data on magma composition as well as the process of hydrocarbon generation in an inorganic setting. However, logical inference allowed us to determine with moderate certainty how much oil is organic in the basement reservoirs.

    Chapter 2 establishes a systematic framework for the study of the sources of basement hydrocarbons practical applications that arise. This should include consideration of the relationship to possible source rocks, the maturation history, the possible migration pathways, the possible reservoir characteristics and the type of traps likely to be present. In Chapter 2, the fundamental features of the hydrocarbons in basement reservoirs are discussed, along with the source of hydrocarbon, mechanism of formation and types of basement reservoirs are defined and discussed. Logical explanations are provided for each aspect of the theories presented. Finally, the framework of scientific investigation of the origin of hydrocarbons is laid out in order to facilitate the study of sustainability and the true nature of hydrocarbons.

    1.5 What is the Implication of the Abiogenic Theory of Hydrocarbon?

    As stated earlier, maturation of organic-rich sediments was considered to be the only source of hydrocarbons in all types of petroleum reservoirs. As early as 1988, Abrajano et al. (1988) discussed an alternate origin in conjunction with natural gas seeps in an ophiolite in the Philippines. Under some circumstances, the serpentinization of ultramafic rocks may produce hydrogen from the reaction of olivine with water; if carbon is also present, methane may be the product. The reaction resembles the Fischer-Tropsch reaction for generating synthetic hydrocarbons (Szatmari 1989). Even though this knowledge existed among scientists of the former Soviet Union for many decades, the notion of non-organic origin of oil was dismissed in the West as marginal, ‘conspiracy theory’-like notions (Gold and Soter, 1980). Abiotic hydrocarbons from serpentinization or from the mantle may be identified by the anomalous distributions of carbon isotopes and helium isotope ratios (Abrajano et al. 1988). Giardini & Melton (1981) stated that hydrocarbons with a d¹³C value more depleted than -18 %o may be abiogenic in origin. This rediscovery of abiogenic hydrocarbons led a series of studies. Sherwood et al. (1988) discussed the origin of CH4 found in the Precambrian crystalline rocks of the Canadian Shield. They noted that the CH4 lacked the characteristic isotopic signature of either organic matter or a mantle source. Some of the CH4 was strongly depleted in deuterium, and some was accompanied by H2, leading the way to theorize about serpentinization.

    Then came the discoveries of the presence of a huge amount of water in the mantle (Guardian, 2014) leading Islam (2014) to theorize the formation of hydrocarbon under numerous conditions, virtually making it a continuous process. Islam (2014) argued that the notion of ‘clean’ energy has to be revised in view of natural processing time for various energy sources. Scientists are still grappling with the origin of the Earth or the universe, some discovering only recently that water was and remains the matrix component for all matter (Pearson et al., 2014). Figure 1.3 shows this depiction. As pointed out by Islam (2014), natural evolution on Earth involved a distinctly different departure point not previously recognized. Pearson et al. (2014) observed a ‘rough diamond’ found along a shallow riverbed in Brazil that unlocked the evidence that a vast wet zone deep inside the Earth that could hold as much water as all the world’s oceans put together. This discovery is important for two reasons. Water and carbon are both essential for living organisms. They also mark the beginning and end of a life cycle. All natural energy sources have carbon or require carbon to transform energy in usable form (e.g., photosynthesis).

    Figure 1.3 Water plays a more significant role in material production than previously anticipated (from the Guardian, March 12, 2014).

    World petroleum reserve takes on a different meaning if the possibility of abiogenic hydrocarbon is added to the equation.

    The resource picture becomes even more interesting when the recent discovery of cyanobacteria that may have been active in all known epochs of life on Earth (Sarsekeyeva et al., 2015) is added. All these considerations and discoveries had to be integrated in a logical discussion. This is done in Chapter 3.

    1.6 How Important are the Fractures for Basement Reservoirs?

    Fractures are very common objects in geological systems. This is particularly true for basement reservoirs. When open, fractures can account for 99% of the fluid flow through the reservoir, whereas closed fractures make a reservoir unproductive, despite use of massive hydraulic fracturing. There has been tremendous progress over the last decades in terms of remote sensing, with a superflux of new techniques in more recent years. In this, the role of seismic data has been phenomenal. For instance, Freudenreich et al. (2005) used 3D maps of orientation and density derived from seismic observations. Other authors use geomechanical models in which the fractures grow during the deformation process – a process that can help reconstitute geologic history. There has been a large number of remote sensing tools that can allow detection of fractures. However, an integrated reservoir characterization technique is still lacking. Chapter 4 presents a comprehensive fracture characterization technique that is also practical. It avoids using statistical processing or linearization of data, instead applying scientifically accurate non-linear filters. All available data are integrated in order to create the most likely picture of the fractured formation.

    Chapter 5 consolidates the reservoir characterization technique with case studies. It is shown that the practical reservoir characterization tool can help unlock the mysteries of many basement reservoirs and open exploratory opportunities in previously unknown target areas.

    1.7 What are we Missing Out?

    It is well known that New science has numerous contradictions and unfounded premises that make it difficult to include a new synthesis. If that is the case, how can we trust the currently used reservoir characterization tools that are based on New science?

    This aspect needs some elaboration. We used the term, ‘New science’ innumerable times in our books. The word ‘New science’ refers to post-Newtonian era that is marked by a focus on tangibles and short-term. In essence, new science promotes a myopic vision, for which the historical background of any event is ignored in favour a time slot that fits the desired outcome of a scientific process. Even though not readily recognized, new science is actually rooted in Dogma science – the ones the likes of Thomas Aquinas introduced. We have demonstrated in our recent books (e.g. Islam et al., 2013, 2015, 2016, 2016a; Islam and Khan, 2012, 2016) how dogmatic notions were preserved by Newton, who claimed to have answers to all research questions. First premises of Newton were not more logical than first premises of Thomas Aquinas, yet Newton as well as post-Newton Newtonian fanatics considered Newton’s work as the standard of real science and proceeded to claim the ultimate knowledge has been achieved for everything. In essence, New science added only ignorance and arrogance of the so-called scientists who were no closer to scientific facts and true knowledge than the likes of Thomas Aquinas.

    Figure 1.4 demonstrates how the process worked in the Eurocentric culture. In this transition, Albert Einstein and his notion of Quantum mechanics added another level of hubris. Whatever couldn’t be explained by Newtonian ‘laws’ now was claimed to be crystal clear with the arrival of the concept of Quanta. Yet, none of the claims of quantum mechanics could be verified with experiments or even logical discourse. Instead, a great deal of false confidence is added in order to create an illusion that we are climbing the knowledge ladder, while in fact we only thing we are climbing is the arrogance/ignorance curve at a ever increasing faster rate.

    Figure 1.4 New science only added more arrogance, blended with ignorance to Dogma science.

    Islam (2014) as well as Khan and Islam (2016) introduced a series of discussions of the fundamental science of mass and energy that enables readers to grasp the concept of natural energy and mass. This forms a background for characterizing basement reservoirs with true science without resorting to dogmatic assumptions. Scientific characterization involves ranking in terms of energy contents as well as diversity of applications.

    Chapter 6 introduces a scientific characterization technique that uses paradigm shift in its real sense. The outcome is a refreshing new approach that is practical and prepares one for in-depth understanding of the mechanisms involved in petroleum reservoirs in general and basement reservoirs, in particular. The technique relies heavily on whatever is available during the course of the reservoir development and minimizes spending on expensive tools that have little validity in basement reservoirs.

    1.8 Predicting the Future?

    Everyone wants to predict the future, but how good is the prediction? In reservoir simulation, the principle of GIGO (garbage in and garbage out) is well known (Rose, 2000). This principle implies that the input data have to be accurate for the simulation results to be acceptable. The petroleum industry has established itself as the pioneer of subsurface data collection (Abou-Kassem et al., 2006). Historically, no other discipline has taken so much care in making sure input data are as accurate as the latest technology would allow. The recent superflux of technologies dealing with subsurface mapping, real-time monitoring, and high-speed data transfer is an evidence of the fact that input data in reservoir simulation are not the weak link of reservoir modeling. However, for a modeling process to be meaningful, it must fulfill two criteria, namely, the source has to be true (or real) and the subsequent processing has to be true (Islam et al., 2016). Even though not commonly perceived, modeling comes before execution of any engineering project. The petroleum engineering industry is a champion of modeling. Today, it has the ability to model a reservoir with no less than trillion cells and solve the governing equation within minutes. Only a decade ago, such performance was unthinkable even from supercomputers. The problem is not with the speed or the ability to model billions of grid blocks. The problem is not in collecting data and processing them. In fact, Saudi Arabia has set up massive 4D seismic in reservoirs that don’t even employ waterflooding. The problem lies within the fact that none of the unconventional or basement reservoirs follows Darcy’s law – the only equation petroleum engineers have used in the last 160 years. Chapter 7 shows how people tried to cope with this crisis and presents a way out, with practical advice on how to model basement reservoirs.

    1.9 What is the Actual Potential of Basement Hydrocarbons?

    All the chapters lead to answering this question. It places basement reservoirs within the big picture of petroleum resources and provides one with a guideline for exploration, exploitation and final environmental impact of basement reservoirs.

    The book closes with a list of references and bibliography. This list contains hundreds of entries spanning over 40 pages.

    Chapter 2

    Organic Origin of Basement Hydrocarbons

    2.0 Introduction

    The majority of hydrocarbons found on Earth naturally occur in the form of crude oil or natural gas. After water, petroleum fluids are the most abundant compounds on Earth (Islam, 2014). When organic matters are decomposed naturally they provide for an abundant source of hydrocarbons. It is recognized in the literature that there are several specific forms of hydrocarbons:

    Dry gas: contains largely methane

    Wet gas: contains ethane propane, butane.

    Condensates: Hydrocarbon with a molecular weight such that they are gas in the subsurface where temperatures are high, but condense to liquid when they reach cooler, surface temperatures.

    Liquid hydrocarbons: commonly known as oil, or crude oil before refining

    Plastic hydrocarbons: asphalt

    Solid hydrocarbons: coal and kerogen, matter in sediments that is insoluble in normal petroleum solvents.

    Gas hydrates: Solids composed of water molecules surrounding gas molecules, usually methane, but also H2S, CO2, and other less common gases.

    More than 100,000 types of hydrocarbons are known. The main reason for this diversity is that carbon atoms can unite in many different ways to form complex chains or ring frameworks. Different arrangements of atoms yield different molecules.

    Basement reservoirs can be found all over the world, but the following countries have significant proven reserve in the basement reservoirs (Figure 2.1).

    Figure 2.1 Basement reservoirs are distributed around the world.

    Algeria, Argentina, Brazil, Canada, Chile, China, Egypt, Former USSR, India, Indonesia, Japan, Korea, Libya, Malaysia, Mexico, Morocco, New Zealand, Peru, Thailand, United Kingdom, United States, Venezuela, Vietnam, and Yemen.

    Basement rock can be very old, up to 2.5 billion years of age. It is largely hard rock such as granite. The basement rocks are often highly metamorphosed and complex, with many different types of rock – volcanic, intrusive igneous and metamorphic. They are considered to be older than the time frame of formation of hydrocarbons in petroleum reservoirs. There are several theories on how hydrocarbons ended up in the basement rocks. Each theory has its shortcomings that will be discussed in this chapter.

    New igneous rock may freshly intrude into the crust from underneath, or may form underplating, where the new igneous rock forms a layer on the underside of the crust. It is said that the majority of continental crust on the planet is around 1-3 billion years old, and it is theorized that there was at least one period of rapid expansion and accretion to the continents during the Precambrian. The natural position in geological time for the oil-producing layer would be above the basement, but this conclusion has the assumption that basement and non-basement reservoirs have the same source of hydrocarbons. Over millions of years, movement caused by tectonic forces can cause disruption in the layers of rock. The basement can be forced up by as much as a kilometre. This process itself can cause an extensive fracture network. Consequently, it can also move the oil-producing layer being at a lower level than the basement. Often, this is followed by the trapping of the oil by the structural trap that itself can have a seal of muds and clays above. As the oil-producing rock forces out hydrocarbons they move up the flank and into the basement through the fracture network.

    Islam (2014) outlined how mixed convection within crystalline basement rocks affect the final lithology of the rock as well as oil composition. Often a high-temperature bubble can be formed due to the presence of thermal insulation, similar to the lithological traps. The energy for such convective system can come from shallow mantle, bodies of hot rock in the upper crust, and/or from radiogenic heat produced by elements in the rock.

    2.1 Sources of Hydrocarbon

    The main constituents of petroleum are hydrogen and carbon. Carbon molecules are bound to hydrogen molecules to form hydrocarbons that form the main matrix of all petroleum fluids. The simplest configuration is depicted in Figure 2.2. This steady state depiction shows how petroleum products range from simplest (e.g., methane) to most complex (e.g., asphaletene) forms of hydrocarbons. While methane molecules have only one carbon atom, asphaltenes have over hundred carbon atoms bound to equivalent (C:H ratio is approximately 1:1.2) number of hydrogen atoms. In addition, an asphaltene molecule would have three nitrogen atoms, two oxygen atoms, and two sulfur atoms. In the hydrocarbon spectrum of crude oil and gas, natural gas consists mainly of methane with smaller amounts of longer-chains up to pentane. Liquid petroleum is referred to as crude oil and consists of a wide range of more complex hydrocarbons and minor quantities of asphaltenes. Tars, on the other hand, are semisolid that has mostly longer-chain hydrocarbons and asphaltenes (Figure 2.2).

    Figure 2.2 Schematic of crude oil molecular composition (from USGS website 1).

    Hydrocarbons of organic sources are formed organically by two pathways:

    Through generation of hydrocarbons directly by organisms. This constitutes perhaps 10 to 20% of the hydrocarbons in the crust. They generally contain more than 15 C atoms, and are easily recognized structures (biomarkers).

    Through conversion of organic matter (lipids, proteins, and carbohydrates) into kerogen, then to bitumen, and finally to petroleum as it gets buried to higher temperatures.

    The thermal alteration of hydrocarbons continues with continued burial depth. The maturation and degradation follows two pathways again:

    One where the H/C ratio decreases i.e., hydrogen stripped from compounds and number of carbon atoms in compounds increase. Ultimately this H/C ratio reaches to 0 (i.e., graphite, and coal).

    One where the H/C ratio increase which ultimately reaches to a ratio of 4 (i.e., the compound is methane).

    Hydrocarbon generation is the natural result of the maturation of buried organic matter. Organic matter (organic carbon) in sediments underlying the oceans is derived from different sources (Emeis and Kvenvolden, 1986), including marine phytoplankton, Phytobentos in shallow water with sufficient light, bacteria, and allochtonous (i.e., land derived) material. The organic carbon produced in the water column varies from 0.1% to 5% depending on various factors such as: (i) oxygen depletion in bottom waters or in sediment as a result of high organic input, (ii) adsorption of certain compounds to mineral particles, (iii) preservation of organic compounds as shell constituents, (iv) changes in the rate of deposition of sediment organic matter, (v) high input of terrigenous organic compounds, which are more stable than organic matter, and (vi) dominant input of argillaceous sediments where oxygenation of pore water is restricted.

    Organic matters undergo changes in composition with increasing burial depth and temperature. The three steps in the transformation of organic matter to petroleum hydrocarbons are termed diagenesis, catagenesis, and metagenesis. The general scheme of evolution of the organic fraction and the hydrocarbon produced is depicted in Figure 2.3 (Tissot and Welte, 1984). Petroleum hydrocarbons exist as gaseous, liquid, and solid phases, depending on temperature, pressure, burial time, and composition of the system.

    Figure 2.3 General scheme of the evolution of the organic fraction and the hydrocarbon produced (Tissot and Welte, 1984).

    Assessments of global coal, oil, and natural gas occurrences usually focus on conventional hydrocarbon reserves, i.e., those occurrences that can be exploited with current technology and present market conditions. The focus on reserves seriously underestimates long-term global hydrocarbon availability. Greenhouse gas emissions based on these estimates may convey the message that the world is running out of fossil fuels. As a result, emissions would be reduced automatically. If the vast unconventional hydrocarbon occurrences are included in the resource estimates and historically observed rates of technology change are applied to their mobilization, the potential accessibility of fossil sources increases dramatically with long-term production costs. They are not significantly higher than present market prices. Although the geographical hydrocarbon resource distribution varies significantly, a regional breakdown for 11 world regions indicates that neither hydrocarbon resource availability nor costs are likely to become forces.

    Natural products are found in nature and usually have a pharmacological or biological activity for use in pharmaceutical drug design. A natural product can be considered as such even if it can be prepared by total synthesis in the laboratory or in an industrial setting. In the more general sense, fossil fuels are natural products insofar as the precursors to the fossil fuels were originally derived from living organisms. Finally, the natural forces (i.e., including but not limited to temperature, pressure, aerial oxidation bacteria etc.) caused the starting materials to be converted to fossil fuel.

    The predominant theory assumes the development of stagnant water conditions in some of the expanded oceans caused the bottom waters to be depleted in oxygen (anoxic), which allowed portions of decaying plankton (e.g., algae, copepods, bacteria, and archaea) that originally lived in the upper oxygen-bearing (oxic) waters to be preserved as a sediment layer enriched in organic matter. Such condition is necessary for anaerobic decomposition of organic matter (Figure 2.4). In a laboratory setting such process is called pyrolysis, which is a typical thermolysis, and is most commonly observed in organic materials exposed to high temperatures. In a laboratory, such decomposion takes place starting at 200–300°C (390–570 °F). In nature, a similar incident occurs when organic matters come into contact with lava in volcanic eruptions. A general composition of biomass is presented in Table 2.1. Recently, Liu et al. (2004) determined composition for specific organic matters. This is presented in Table 2.2.

    Figure 2.4 Product distribution with temperature (redrawn from Luo et al., 2014).

    Table 2.1 General composition of biomass (from Liaw, 2014).

    Table 2.2 Typical properties of wood derived crude bio-oil (from Luo et al., 2004).

    Table 2.4 shows the effect of temperature on pyrolysis products. With an increase in temperature, the relative amount of char and condensable liquid fraction decreases continuously, whereas the fraction of gas formed increases.

    Table 2.3 Composition of specific organic matters (from Liu et al., 2004).

    Table 2.4 Effect of temperature on pyrolysis (from Liaw, 2014).

    Because different types of reactions get activated at different temperature values, an optimum temperature value emerges. Figure 2.4 shows product distribution with temperature. These results would be affected under a different set pressure condition, as is often the case for natural decomposition of organic matters in geologic time. In addition, secondary reaction of volatile components would also influence the composition of final products. Figure 2.5 shows how the composition of incondensable gas is influenced by temperature. As the temperature is increased, higher proportion of CO and CH4, while a lower proportion of CO2 emerge. During the pyrolysis process, CO2 is produced at a relatively low temperature. As higher temperature conditions prevail, secondary thermal cracking of volatile produces CO and CH4 rather than CO2.

    Figure 2.5 Incondensable gas composition with temperature (Reconstructed from Neven et al., 2011 and Liu et al., 2004).

    In a geologic setting, organic-rich sediment layers are buried by deposition of overlying sediments in the subsiding basin, the sediments are compressed and eventually lithified into rocks referred to as black shale, bituminous limestone, or coal. Over millions of years of digenesis, new organisms come in contact with the sedimentary rock and often enrich preexisting deposits. These microorganisms consume portions of the organic matter as a food source and generate methane as a by-product. This methane, which is typically the main hydrocarbon in natural gas, has a distinct neutron deficiency in its carbon nuclei (i.e., carbon isotopes), which allows microbial natural gas to be readily distinguished from methane generated by thermal processes later in a basin’s subsidence history. The microbial methane may remain in the organic-rich layer or it may bubble up into the overlying sediment layers and escape into the ocean waters or atmosphere. If impermeable sediment layers hinder the upward migration of microbial gas, the gas may collect in underlying porous sediments that end up being the reservoir (Figure 2.6).

    Figure 2.6 Formation of organic-rich sediment layer (from USGS website 1).

    Economically significant accumulations of microbial natural gas have been estimated to account for 20% of the world’s produced natural gas (USGS Website 1). This microbial methane often forms the basis for accumulations referred to as coal-bed methane and shale gas. During the course of digenesis, burial of the organic-rich rock layer may continue in some subsiding basins to depths of 6,000 to 18,000 feet (1830 to 5490 m). At these depths, the organic-rich rock layer is exposed to temperatures of 150 to 350 °F (66 to 177 °C) for a few million to tens of millions of years. The organic matter within the organic-rich rock layer begins to cook during this period of heating and portions of it thermally decompose into crude oil and natural gas (i.e., thermogenic gas). This is illustrated in Figure 2.7.

    Figure 2.7 Early burial of sediment layers in basin (from USGS website 1).

    Classical views for the deposition of oil-prone and organic-rich sediments in deep environments invoke two principal types of sedimentologic settings. The first is confined basins in which stratified oxygen-depleted waters lead to anoxic preservation of organic matter in the water column and in underlying sediments (de Graciansky et al., 1984; Demaison and Moore, 1980). The second is an open ocean setting where episodic mass transfers due to slope sediment instability lead to the rapid burial of outer-shelf- and upper slope-derived organic matter and its consequent preservation due to limited oxic or anoxic degradation (Huc, 1988; Stow, 1987). Other studies have shown, however, that organic matter in modern deep-sea sediments may occur in high amounts where oxygen is not significantly depleted (Pedersen and Calvert, 1990; Martinez et al., 1996; Prakash Babu et al., 1999).

    Another mechanism may account for the occurrence of organic-rich deposits, namely relative variations in the magnitude of nonorganic burial fluxes. This one forms the basis of the work published by Bertrand et al. (2003).

    The overall process of hydrocarbon generation through thermal maturation is highly affected by the nature of organic matter. If the original source of the organic matter is mostly higher plants (e.g., trees, shrubs, and grasses), natural gas will be the dominant petroleum generated with lesser amounts of crude oil generation. If the original source of the organic matter is plankton (e.g., algae, copepods, and bacteria), crude oil will be the dominant petroleum generated with lesser amounts of natural gas generation. It turns out that the Earth has much more volume of plankton material than higher plants (Figure 2.8).

    Figure 2.8 The volume of biomass increases as the size of the living object decreases.

    It is well known that phytoplankton is central to the pelagic ecosystem due to the fact that it traps almost all the energy used by the ecosystem. The biomass of phytoplankton is a subject of intense studies dealing with aquatic ecological research. Phytoplankton forms the basis of fundamental fodder of the food chain in nature (Harris, 1986). Phytoplankton are the main primary producers at the bottom of the marine food chain. Phytoplankton use photosynthesis to convert inorganic carbon into protoplasm. They are then consumed by microscopic animals called zooplankton. Zooplankton comprise the second level in the food chain, and includes small crustaceans, such as copepods and krill, and the larva of fish, squid, lobsters and crabs. In turn, small zooplankton are consumed by both larger predatory zooplankters, such as krill, and by forage fish, which are small, schooling, filter-feeding fish. This makes up the third level in the food chain.

    It is known that algal carbon content is extremely difficult to determine directly and is therefore usually estimated from other parameters (Geider et al., 1997). Counting and volume assessment of cells, and measurement of pigment concentration, are widely used to estimate algal biomass (Smayda, 1978; Jeffrey et al., 1997). However, both methods have technical limitations. Direct cell counting and species volume measurement is laborious, requiring specialists in taxonomy and the use of preserved samples. Chlorophyll a is common to all photosynthetic organisms. Furthermore, it is the most abundant photosynthetic pigment and it is relatively easy and rapid to quantify. Consequently, its concentration is used extensively for estimating phytoplankton biomass. A variety of techniques is at present available offering varying degrees of accuracy. However, the ratio of chlorophyll a to cell carbon depends on external and internal factors, such as phytoplankton taxonomic composition, cell physiological conditions, temperature, nutrient concentrations and light intensity (Meeks, 1974; Desortová, 1981; Reynolds, 1984; Riemann et al., 1989; Vörös and Padisák, 1991).

    The effects of phytoplankton taxonomic composition and external factors on the decoupling between chlorophyll and biovolume were evaluated by Felip and Catalan (2000). These correlations identified the importance of light and temperature that eventually would impact maturation of any organic matter. Table 2.5 shows the relevant data used and Table 2.6. shows the results. Table 2.6 shows that the low chlorophyll content related to phytoplankton biovolume (residual negative) was significantly related to high light and temperature values and a predominance of dinoflagellates, reflecting the characteristics of the epilimnion during the summer stratification. In contrast, large amounts of chlorophyll per unit biovolume were related to low light and temperature values, and to the predominance of small cells such as some chlorophyte species. This study indicates the nature of carbohydrate generation that would impact the generation of hydrocarbons.

    Table 2.5 Statistical descriptors of some phytoplankton parameters observed during the seasonal cycle studied in Lake Redó (from Felip and Catalan, 2000).

    Table 2.6 Chlorophyll content and phytoplankton biovolume for two biomass estimators. Factors were selected from the literature. The percentage of biovolume of each phytoplanktonic group was used as a descriptor of sample taxonomic composition (from Felip and Catalan, 2000).

    The global volume of growing stock was estimated at 386 billion cubic metres in 2000. The regions with the largest volume were Europe (including the Russian Federation) with 30% (116 billion cubic metres) and South America with 29% (111 billion cubic metres) (Table 2.7). Oceania shows the lowest growing stock with 11 billion cubic metres or 3% of the global volume.

    Table 2.7 Forest volume and above-ground biomass by region (from FAO, 2012).

    Globally, terrestrial and oceanic habitats produce a similar amount of new biomass each year (56.4 billion tonnes C terrestrial and 48.5 billion tonnes C oceanic). The amount of biomass is order of magnitude higher for smaller species (Whitman et al., 1998).

    Organic-rich rocks that have not been thermally matured are referred to as being thermally immature. Even before they are identified as crude oil, they can become energy sources. It is evidenced from the fact that oil shales economic quantifies of oil if they are heated at around 540 C. Oil shale is sedimentary rock containing up to 50% mostly immature organic matter. Once extracted from the ground, the rock can either be used directly as fuel for a power plant, or be processed to produce shale oil and other chemicals and materials. Similar to crude oil and gas, oil shales are widely distributed around the world – some 600 deposits are known, with resources of the associated shale oil totalling almost 500 billion tonnes, or approximately 3.2 trillion barrels (EASAC, 2007). Yet, these deposits are vastly unexploited – the exceptions being Estonia and Brazil.

    Table 2.8 Global biomass production (Data from Ricklefs and Miller, 2000 and Park, 2001).

    Because petroleum has a lower density than the water that occupies pores, voids, and cracks in the source rock and the overlying rock and sediment layers, the density difference leads to upward migration of petroleum due to buoyancy forces. Such migration continues until a trap is reached. Often, such migration may not take place due to lack of permeable channels, in which case source rocks remain impregnated with petroleum. The Barnett Shale in the Fort Worth basin of Texas is a good example of this type of accumulation, where the natural gas generated over geological eras are found within the source rock.

    On the other extreme, in some basins, petroleum may not encounter a trap and continue migrating upward into the overlying water or atmosphere as petroleum seeps. This petroleum would seep through the surface or ocean floor, leaving behind a residual tar enriched in large complex hydrocarbons and asphaltenes (Figure 2.9). Tar deposits range in size from small local seeps like the La Brea tar pits of California to regionally extensive occurrences as observed in the Athabasca tar sands of Alberta, where a 50,000-square-mile reservoir of heavy crude oil possibly holds 2 trillion barrels of recoverable oil.

    Figure 2.9 Continued burial of sediment and rock layers in subsiding basin (from USGS website 1).

    Burial of the source rock may continue to depths greater than 20,000 ft. (6100 m) in some sedimentary basins. At these depths, temperatures greater than 350°F (177°C) and pressures greater than 15,000 psi (103 MPa) begin to transform the remaining organic matter into more natural gas and a residual carbon referred to as char. This char itself is a function of swelling, surface area, porosity, mass release, true density, and chemical compositions and may lead to changes in the rock properties, thus altering the overall characteristic of the formation. Oil trapped in reservoirs that are sometimes buried to these depths also decomposes to natural gas and char. The char, which is also called pyrobitumen, remains in the original reservoir while the generated natural gas may migrate upward to shallower traps within the overlying rock layers of the basin. The Gulf Coast basin that extends into the offshore of Louisiana and the Anadarko basin of the U.S. mid-continent are good examples of these deep basins (Figure 2.10).

    Figure 2.10 Deeper burial of rock layers in subsiding basin (from USGS website 2).

    Further burial to temperatures and pressures in excess of 600 °F (316 °C) and 60,000 psi (414 MPa), respectively, represent metamorphic conditions in which the residual char converts to graphite with the emission of molecular hydrogen gas. In this process, it is important to understand the mobility of inorganic elements on the char or biomass surface because if the metals are active sites for exothermic reactions then the temperature at the metal sites might be higher which may increase mobility of the metals. It also unlocks the key to understanding the role of catalysts in both natural process as well as artificial refining. In particular, air gasification is exothermic whereas gasification with steam or CO2 is endothermic, which could result in significant temperature differences at the site where the reaction takes place. The more mobile the particle is, the more likely that it will agglomerate on the surface. Figure 2.11 shows the relationship between

    Figure 2.11 Relationship between mobility of particles supported on graphite and their bulk melting temperatures (From Baker, 1982).

    The resulting metamorphic rocks of this process of maturation are graphitic slate, schist or marble. The prevailing thermal and pressure conditions dictate that water remaining in these rocks should react with the graphite to form either methane or carbon dioxide depending on the amount of molecular hydrogen present. Similarly, a crystalline metamorphic rock composed primarily of calcium carbonate (CaCO3), is susceptible to further decomposition, especially under thermal stress. It is recognized that high-grade metamorphism typically breaks down and destroys carbonate minerals. Schist rocks are formed in presence of moderate level of heat and pressure. As schist rocks are formed through metamorphosis of mudstone / shale, or some types of igneous rock, traces of chars and petroleum residue work as a cementing material, thus impacting rock properties.

    Currently, the deepest wells in sedimentary basins do not exceed 32,000 ft (9760 m). Therefore, the significance of natural gas generation under these extreme conditions remains uncertain. Sedimentary basins vary considerably in size, shape, and depth all over the Earth’s crust (Figure 2.12).

    Figure 2.12 General outline of major sedimentary basins (from USGS website 1).

    The extraction of liquid hydrocarbon fuel from a number of sedimentary basins has been the integral part of modern energy development. Hydrocarbons are mined from tar sands and oil shale. These reserves require distillation and upgrading to produce synthetic crude and petroleum. A future source of methane may be methane hydrates found on ocean floors. There are two possible sources for the hydrocarbons such as inorganic and organic. Inorganic hydrocarbons form from reduction of primordial carbon or oxidized forms at high temperatures in the Earth. Organic accumulation of hydrocarbons is produced directly by living organisms as well as the thermal alteration of biologically formed organic matter. It is generally recognized that most hydrocarbons are produced by the organic method. A few hydrocarbons in the crust may be from inorganic sources; however, the majority of them are from organic. We discuss the non-organic sources of hydrocarbon in the next chapter.

    2.2 Non-Conventional Sources of Petroleum Fluids

    Even though it has been long recognized that every theory depends on a set of fundamental assumptions and in a case where those assumptions are not true (Davis, 1926), the theory has no validity, few theories have challenged mainstream theories. In particular, geological theories are all based on the assumption that the Earth was entirely inhabitable without a life form and all life evolved from a single cell organism. Such a sequence of events comes from the linear thinking that created a flurry of cosmic theories, including the Big Bang that assumes that the initial superflux of matter was all hydrogen atoms that eventually evolved into other elements. Only recently have such notions been challenged from multiple fronts.

    In 2014, Islam presented the origin of the universe from water, making water ubiquitous in the cosmos. Similarly, the possibility of Earth being an entity of its own (rather than being formed of ‘star dusts’) was discussed. In 2009, Biello (2009) explored the possibility of the existence of organisms. Biello argued that even if the hypothesis that the Earth was part of the superdense core of starts, the fact that the oxygen element is the third most abundant element in the universe despite being highly reactive with all elements in nature explains that the breathable air of today originated from tiny organisms. Organisms known as cyanobacteria, or blue-green algae are considered to be responsible for maintaining a high percentage (21%) of elemental oxygen in the atmosphere. Cynobacteria are considered to be the most primitive photosynthetic prokaryotes which are supposed to have appeared on this planet during the Precambrian period (Ash and Jenkins, 2006). Possibly, these are the first photosynthetic microorganisms which persisted over a period of 2 to 3 billion years, performing an important role in evolution of higher forms. Cyanobacteria are a unique assemblage of organisms which occupy and predominate a vast array of habitats as a result of several general characteristics; some belonging to bacteria and others unique to higher plants (Wilmotte, 1991, AbdAllah, 2006, Haande et al., 2010).

    Cyanobacteria, also known as Cyanophyta, is a phylum of bacteria that obtain their energy through photosynthesis, and are the only photosynthetic prokaryotes able to produce oxygen (Singh et al., 2016). The name cyanobacteria comes from the color of the bacteria. Singh et al. (2016) point out several unique features of cyanobacteria such as oxygenic photosynthesis, high biomass yield, growth on non-arable lands and a wide variety of water sources (contaminated and polluted waters), generation of useful by-products and bio-fuels, enhancing the soil fertility and reducing green house gas emissions, have collectively offered these bio-agents as the precious bio-resource for sustainable development. Cyanobacterial biomass is the effective bio-fertilizer source to improve soil physico-chemical characteristics such as water-holding capacity and mineral nutrient status of the degraded lands. The unique characteristics of cyanobacteria include their ubiquity presence, short generation time and capability to fix the atmospheric nitrogen. While genetically engineered cyanobacteria have been devised with the novel genes for the production of a number of bio-fuels such as bio-diesel, bio-hydrogen, bio-methane, synga, etc., the relevance of these bacteria in this chapter is their ability to produce hydrocarbon directly from the non-organic sources.

    The unique features of these microbes is that they conduct photosynthesis, converting sunlight, water and carbon dioxide into carbohydrates and oxygen. These bacteria perform photosynthesis for all the plants, as part of the continuous cycle, similar to Figure 2.13.

    Figure 2.13 Usefulness of cyanobacteria (From Singh et al., 2016).

    Sarsekeyeva et al. (2015) identified the role of cyanobacteria that, by virtue of being a part of marine and freshwater phytoplankton, significantly contribute to the fixation of atmospheric carbon via photosynthesis. It is reasonably inferred that ancient cyanobacteria participated in the formation of Earth’s oil deposits. While the biomass of modern cyanobacteria may be converted into bio-oil by pyrolysis, in geologic time, hydrocarbons produced by cyanobacteria can also form the basis of so-called fossil fuel. Modern cyanobacteria grow fast; they do not compete for agricultural lands and resources; they efficiently convert excessive amounts of CO2 into biomass, thus participating in both carbon fixation and organic chemical

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