CHAPTER

The Origin of Petroleum in the Marine Environment

26

All gures are available on the companion website in color (if applicable).

26.1 INTRODUCTION
In coastal upwelling areas, the underlying sediments are enriched in organic matter due to high biological productivity in the surface waters and relatively shallow water depths. Given appropriate environmental conditions, diagenesis and catagenesis can convert the sedimentary organic matter to petroleum over time scales of tens of millions of years. This process has been likened to cooking in the geologic kitchen. Overall the production of petroleum is highly inefcient due to the remineralization of organic carbon during microbial respiration. As shown in Figure 25.1, most of the sedimentary carbon is in the form of biogenic carbonate. Humans are rapidly returning the petroleum carbon reservoir to the atmosphere through the burning of fossil fuels. This perturbation of the crustal-ocean-atmosphere carbon cycle is the source of the gas (CO2 ) primarily responsible for the anthropogenic contribution to global warming. Nevertheless, petroleum remains the major source of energy fueling the world economy. Although most petroleum is used to generate energy, primarily for transportation, it is also an important feedstock for the manufacture of petrochemicals used in the creation of synthetic rubber, synthetic bers, drugs, detergents, and plastics. Components of petroleum also serve as lubricating oils and solvents. Because of these valuable uses, many have suggested that we are wasting a valuable feedstock resource by continuing to burn it for energy. Considerable effort continues to be directed at determining how and where petroleum has formed. As we are depleting the easily recoverable deposits of petroleum, interest is being increasingly directed at locating and recovering coal and natural gas. In this chapter, we discuss the biogeochemical conditions required for the formation of large petroleum deposits. Because these requirements are numerous, nding large petroleum deposits is akin to searching for a needle in a haystack. Whether we have found and depleted all of the large reservoirs is a matter of great controversy. Petroleum prospecting represents one of the most successful applications of the molecular biomarker approach. Ten to 20% of the organic compounds in crude oil

CHAPTER 26 The Origin of Petroleum in the Marine Environment

were formed directly from hydrocarbons synthesized by organisms. Thus, hundreds of biomarkers are present in petroleum, although they collectively represent less than 2% of the total mass of the organic carbon. These biomarkers have been use to identify: (1) the source of organic matter in petroleum deposits, (2) the environmental conditions present during deposition of the organic matter, and (3) the nature of subsequent diagenetic, catagenetic, and metagenetic transformations. Although some controversy still exists regarding the source of the organic carbon in petroleum, the presence of biomarkers provides strong evidence for a largely biotic origin. Petroleum geochemists use the molecular biomarker approach and other diverse kinds of data to evaluate the production potential of sediments in an effort to minimize the drilling of costly exploratory wells. This approach requires knowledge of the timing and locations of past conditions under which organic matter production and preservation were favored. This knowledge, in turn, relies on an understanding of the role of marine organisms in the production and destruction of organic matter and the role of the ocean-atmosphere system in controlling water circulation as the latter determines the rates of O2 and nutrient delivery. Since the processes leading to the formation of large petroleum deposits occurred tens and even hundreds of millions of years ago, understanding them is truly a paleoceanographic endeavor. In other words, this chapter, in describing the formation of petroleum in the marine environment, provides a synthesis and practical application of most of the topics previously covered in this text.

26.2 WHAT IS PETROLEUM?

Petroleum is operationally dened as any hydrocarbon mixture that can be recovered through a drill pipe. It is composed of a great variety of molecules that range in molecular weight from methane (16 g/mol) to the asphaltenes (tens of thousands of g/mol). Compounds can be present as gases, liquids, and condensates. The condensates are hydrocarbons retrieved as gases or liquids that upon cooling change into liquids or solids. The gas phase includes low-molecular-weight hydrocarbons (C4 ). These natural gases include methane, ethane, propane, and butane. The liquid phase is commonly referred to as a crude oil. Although petroleum is primarily composed of hydrocarbons, trace amounts of other chemicals are present. These include (1) gases, such as N2 , CO2 , H2 S, and He; (2) trace metals, particularly V, Zn, Ni, and Hg; and (3) organic compounds that contain N, S, and O. The liquid, or crude oil, portion of petroleum is transformed into commercial form via distillation. This process removes impurities and enables production of various fractions, such as gasoline, kerosene, and oil. The boiling point ranges of these fractions are given in Figure 26.1. These fractions are mixtures of compounds whose structure and size are similar as these factors determine their boiling points. For example, the gasoline fraction is composed of hydrocarbons that contain four to 10 carbons. The major classes of hydrocarbons found in petroleum are the parafns, isoparafns, cycloparafns, aromatics, and olens. Sample structures are provided in Figure 26.2 as skeletal formulae in which a carbon atom is present at each end or kink

26.2 What Is Petroleum?

Boiling point (8C) 100 100 200 300 400 500 600

Normal paraffins 80 Isoparaffins

Percentage of molecular types

60

Naphthenes (cycloparaffins)

40
ics

20

Ar

om

c ati

s
ht h o en ar

om

at

p Na

Nitrogen, sulfur, and oxygen compounds 100 Residuum >C40

0 Gasoline C42C10

20

40 60 Kerosine Diesel Heavy fuel gas oil C112C13 C14-C18 C19-C25

80 Lubricating oil C26-C40

FIGURE 26.1
Chemical composition of a crude oil. Source: From Hunt, J. M. (1996). Petroleum Geochemistry and Geology, 2nd edition, W. H. Freeman and Co., New York, p. 39.

of a chain and the hydrogen atoms are not shown. The parafns (also called alkanes) are straight-chain (nonaromatic) hydrocarbons. Because they do not contain any double or triple bonds, they are also categorized as saturated hydrocarbons. These molecules contain the maximum amount of hydrogen atoms possible given their number of carbon atoms. Their stoichiometry is thus Cn H2n+2 . Parafns with greater than 20 carbon atoms are solids, called parafn waxes. The high-molecular-weight parafns can contain as many as 80 carbon atoms. The isoparafns have at least one branch in their carbon chain, which leads to an increased boiling point. The cycloparafns, or naphthenes, are rings that contain 5 or 6, and sometimes 7, carbons. Napthenes compose about half of average crude oil. The high-molecular-weight

CHAPTER 26 The Origin of Petroleum in the Marine Environment

(a) Normal paraffins

Boiling point

(b) Branched-chain paraffins

Boiling point

CH4

Methane

21618C

2128C C4H10
2-Methylpropane (Isobutane)

508C C2H6 2898C

Ethane

C6H14

2,2-Dimethylbutane

2428C C3H8
Propane

588C C6H14 20.58C C4H10

Butane 2,3-Dimethylbutane

608C C6H14
2-Methylpentane

368C C5H12
Pentane

908C C7H16
2-Methylhexane (Isoalkane)

698C C6H14
Hexane

928C C7H16
3-Methylhexane (Anteisoalkane)

988C C7H16
Heptane

998C C8H18
2,2,4-Trimethylpentane (Iso-octane)

FIGURE 26.2 (Continued)

napthenes are made up of fused multiple rings. The stoichiometry of the napthenes is Cn H2n , reecting a lower hydrogen content than in the aliphatic parafns. Olens are hydrocarbons that contain one or more carbon-carbon double bonds. They are unsaturated and, hence, have a stoichiometry of Cn H2n2 . Many biomolecules, such as the terpenoids, are olens. This class of compounds is uncommon in crude oil because of their high chemical reactivity. During petroleum formation, the double bonds tend to become reduced by incorporation of hydrogen or sulfur atoms, thereby generating either parafns or nonhydrocarbons, respectively, both of which are thermodynamically very stable.

26.2 What Is Petroleum?

(d) Naphthenes (Cycloparaffins)

Boiling point,

(e) Aromatics
Boiling point,

728C C6H12
Methylcyclopentane

808C C6H6
Benzene

818C C6H12
Cyclohexane (Side View)

1118C C7H8
Toluene

1328C

1388C

C8H16

Ethylcylohexane

C8H10

Paraxylene

1378C C9H18

1528C

1,1,3-Trimethylcyclohexane

C9H12

2-Phenylpropane (Isopropylbenzene)

Trans form, C10H18

Decalin

1878C

>5008C C20H12
3,4-Benzpyrene

FIGURE 26.2
Molecular structures of (a) paraffins, (b) branched paraffins, (c) olefins, (d) cycloparaffins, and (e) aromatics. Source: From Hunt, J. M. (1996). Petroleum Geochemistry and Geology, 2nd edition, W. H. Freeman and Co., New York, p. 28 and 31.

The higher boiling-point fraction of petroleum contains hydrocarbons that tend to have high molecular weights and high degrees of unsaturation. They include the aromatics and mixed structures, such as the napthenoaromatics. The aromatics are molecules that contain benzene rings and, hence, are highly unsaturated because they contain multiple carbon-carbon double bonds. Their stoichiometry is Cn H2n6 . The highest molecular-weight aromatics have fused rings and are termed polynuclear aromatic hydrocarbons (PAHs). These compounds tends to be very carcinogenic. The residue left at the end of the distillation process is composed of very high molecular-weight hydrocarbons, called asphaltenes, and nonhydrocarbons, called asphaltics. The latter contain varying amounts of either oxygen, nitrogen, or sulfur. The

CHAPTER 26 The Origin of Petroleum in the Marine Environment

Table 26.1 Percent Elemental Composition of Oil, Asphalt, and Kerogen.

Gas Carbon Hydrogen Sulfur Nitrogen Oxygen 76 24 0 0 0 100 Oil 84.5 13 1.5 0.5 0.5 100 Asphalt 84 10 3 1 2 100 Coal 83 5 1 1 10 100 Kerogen 79 6 5 2 8 100

Source: From Hunt, J. M. (1996). Petroleum Geochemistry and Geology, 2nd edition. W. H. Freeman and Co., New York, p. 24.

structures of asphaltenes typically have lots of fused hexane and benzene rings along with parafn side chains. The distillation residue can range from resinous to solid at room temperature. Solid residues are termed asphalts and can be somewhat liqueed with heating. The term asphalt is also used to describe the solid residue created in a geologic deposition during the formation of petroleum. The collective mass of organic matter represented by the petroleum and asphalt in a geologic deposit is referred to as bitumen. Commercially desirable fractions of petroleum are nearly pure mixtures of hydrocarbons and contain little sulfur, nitrogen, and oxygen. Sulfur and nitrogen are undesirable because their combustion generates nitric and sulfuric acid, both of which contribute to acid rain. As shown in Table 26.1, all of the petroleum fractions have a much higher hydrogen content than coal. (Coal is a highly combustible rock containing more than 50% by weight organic material of biogenic origin.) This difference reects the chemical composition of their source materials. As discussed further in the next section, the source matter for petroleum is marine and aquatic organic matter, whereas coal is generated from the remains of terrestrial plants. These source materials can be identied from unique molecular biomarkers preserved in petroleum and coal. As with petroleum, the most desirable coals are the ones with the lowest nitrogen and sulfur contents. These levels are highly dependent on the depositional history and cooking conditions and, hence, vary from deposit to deposit.

26.3 CARBON SOURCES AND BIOMARKERS

About 10 to 20% of petroleum is composed of hydrocarbons either synthesized by organisms or generated from biogenic organic matter during diagenesis. The rest is formed via the catagenesis and metagenesis of the residual biogenic organic matter. (A minor amount may have formed abiogenically from CO2 or methane). Thus, living

26.3 Carbon Sources and Biomarkers

organisms are the ultimate source of petroleum (and coal). Since plants produce most of the biomass, they are the largest source of organic matter to the soils and sediment. Their biomolecules are predominantly proteins, carbohydrates, and lipids. Although the kinds of organisms present on Earth have evolved over time, the fundamental metabolic pathways appear to have been rather constant, making the modern-day biomolecules similar to those that gave rise to petroleum and coal. As shown in Table 26.2, the biomolecules with the highest degree of chemical similarity to petroleum are the lipids. They have a high hydrogen content and are low in sulfur, nitrogen, and oxygen. The lipid content of representative marine and terrestrial biota is shown in Table 26.3. As compared to terrestrial vascular plants, marine plankton have high lipid contents. Another striking difference is the high percentage of lignin in terrestrial plants, which is absent in marine plankton. Because lignins have low hydrogen contents, they generate coal, whereas organic matter derived from aquatic or marine plankton yields gas and oil. As discussed in Chapter 23.6.6, vascular plants use lignin and cellulose as structural materials. These biomolecules are relatively stable and, hence, are well preserved in soils and sediment. Petroleum deposits typically contains hundreds of compounds that can serve as biomarkers. Some examples are shown in Table 26.4. Although the biomarkers collectively compose a small mass fraction of the petroleum hydrocarbons, they provide information on the source of the organic matter in the deposit, its depositional environment, and its cooking and migration histories. For example, odd-numbered short-chain (C15 to C21 ) parafns are characteristic of marine organisms, whereas land plants tend to generate longer odd-numbered chains (C25 to C37 ). The longer chains tend to be waxes. These compounds help land plants control water loss from their leaves and provide protection from mechanical and parasite damage. The shorter chains are generally liquids (fats) and are used by marine organisms for energy storage, insulation, and buoyancy. Plants tend to generate hydrocarbons with odd numbers of carbons, whereas bacteria and higher organisms do not exhibit this selectivity. Another
Table 26.2 Average Chemical Composition of Biochemicals as Compared to Petroleum.
Elemental Composition in Weight Percent C Carbohydrates Lignin Proteins Lipids Petroleum 44 63 53 76 85 H 6 5 7 12 13 1 0.5 0.1 1 0.3 17 S N O 50 31.6 22 12 0.5

Source: From Hunt, J. M. (1996). Petroleum Geochemistry and Geology, 2nd edition. W. H. Freeman and Co., New York, p. 63.

CHAPTER 26 The Origin of Petroleum in the Marine Environment

Table 26.3 Elemental Composition of Living Matter.

Substance Weight Precent of Major Constituents Proteins Plants Spruce wood Oak leaves Scots-pine needles Phytoplankton Diatoms Lycopodium spores Animals Zooplankton (mixed) Copepods Oysters Higher invertebrates 1 6 8 23 29 8 60 65 55 70 Carbohydrates 66 52 47 66 63 42 22 25 33 20 Lipids 4 5 28 11 8 50 18 10 12 10 Lignin 29 37 17 0 0 0 0 0 0 0

Note: Dry ash-free basis. There is great variability for different species of each organism. For example, Blumer et al. (1964) reported Calanus copepods to contain 27 to 57% lipids. Lipid variability is partly due to the nutrient availability and health of the organisms. If the food supply is limited or there is crowding during growth, the organism will increase its lipids. For example, Chlorella grown in a favorable environment contains 20% lipids, but in an unfavorable environment, 60% lipids (Blumer, M., M. M. Mullin, and D. W. Thomas. (1964). Pristane in the marine environment. Helgolander Wissenschaftliche Meeresuntersuchungen 10: 187200). Source: From Hunt, J. M. (1996). Petroleum Geochemistry and Geology, 2nd edition. W. H. Freeman and Co., New York, p. 64.

readily identiable set of biomarkers are the degradation products of chlorophyll. As illustrated in Figure 26.3, diagenesis acts to remove the phytyl side chain. Under anoxic conditions the phytyl side chain is released as phytane and under oxic conditions, as pristane. The central magnesium atom in the porphyrin ring is replaced by metals such as V, Ni, Fe, Cu, or Mn. These metals are present in high concentrations in the organic-rich sediments as they have high enrichment factors (EFs) in planktonic biomass (Table 11.5). The most useful terpenoid biomarkers are the steroids, carotenoids, and hopanoids ( Figures 22.19 and 22.8f). As described in Chapter 22.4.3, some steroids are unique metabolites, such as fucosterol (brown algae), dinosterol (dinoagellates), sitosterol (higher plants), and stigmasterol (terrestrial plants). Steroids generate degradation products that reect the redox conditions under which diagenesis took place. These degradation products are readily identiable as stanols, sterenes, and steranes. The most commonly used biomarkers are the hopanoids, with several hundred of these compounds having been isolated from bacteria and sediments. The hopanoids are highly resistant to degradation and, hence, are well preserved molecular fossils. This is also true for the six-ring terpenoid, gammacerane (Figure 22.19c), which is thought to be synthesized by cyanobacteria and protozoans. Even the sulfur content of the organic matter is diagnostic of diagenetic redox conditions as reduction of the carbon-carbon double bonds in olens by reaction with H2 S produces unique and stable products.

26.3 Carbon Sources and Biomarkers

Table 26.4 Biological Markers as Source and Paleoenvironmental Indicators.

Biomarker n-Alkanes CPI>5 C Range C9 C21 C25 C37 CPI<1 C12 C24 C20 C32 Acyclic isoprenoids Head to tail Pristane Phytane Head to head Botrycoccane Sesquiterpenoids Cadalene, eudesmane Diterpenoids Abietane, pimarane, kaurane, retene Tricyclic terpanes Tetracyclic terpanes Hopanes Norhopanes 2- and 3-methylhopanes Benzohopanoids Hexahydrobenzohopenoids Gammacerane Oleananes, lupanes Bicadinane Indication Marine, lacustrine algal source, C15 , C17 , C19 dominant Terrestrial plant wax source, C27 , C29 , C31 dominant Bacterial source: oxic, anoxic, marine, lacustrine Saline, anoxic environment: carbonates, evaporites

C19 C20 C25 , C30 , C40 C34 C15

Chlorophyll, -tocopherol, oxic, suboxic environments Chlorophyll, phytanylethers of methanogens, anoxic, saline Archaebacteria, bacterial cell-wall lipids Lacustrine, brackish Terrestrial plants

C19 , C20 C19 C45 C24 C27 C27 C40 C27 C28 C28 C36 C32 C35 C32 C35 C30 C30 C30 C40

Higher plant resins Diagenetic products of bacterial and algal cell-wall lipids Degradation of pentacyclic triterpenoids Bacteria Anoxic marine Carbonate rocks Carbonate environments Anoxic, carbonate-anhydrite Hypersaline environments Late Cretaceous and Tertiary flowering plants Gymnosperm tree resins Arid, hypersaline

-Carotane

(Continued)