Diagenesis , Catagenesis and Petroleum; The Carbon Cycle

1. Diagenesis, Catagenesis and Petroleum;The Carbon Cycle Lecture 50

2. Diagenesis Diagenesis in the context of organic matter refers to biologically induced changes in organic matter composition that occur in recently deposited sediment.

3. Summary of Diagenetic Changes • Functional groups are preferentially removed from their parent molecules, decreasing the oxygen, and to a lesser degree, the hydrogen. • The abundance of readily metabolized organic compounds decreases. • Unsaturated compounds decrease in abundance compared with their saturated equivalents due to hydrogenation of double carbon bonds. • Aliphatic compounds decrease in abundance compared with aromatic ones. This results partly from aromatization of unsaturated aliphatic compounds and partly from the more resistant nature of aromatics. • Short-chained molecules (e.g., alkanes, fatty acids), decrease in abundance relative to their long-chain equivalents. • Hydrolysis of complex molecules produces a variety of molecular fragments that subsequently recombine with other molecules to produce new ones not present in the original biota. • In high-sulfur environments, such as marine sediments, H2S is incorporated into carbon double bonds in long-chain compounds to produce thiol functional groups. This process is known as natural vulcanization. • Condensation of a variety of molecules and molecular fragments into complex macromolecules.

4. Kerogen • The principal product of these processes is kerogen, which forms from humus, humic and fulvic acids through condensation reactions. It appears to consist of nuclei cross-linked by chain bridges. • Kerogen is an inhomogeneous macromolecular aggregate that is insoluble in water, alkali, non-oxidizing acids, and organic solvents. • Upon heating, a procedure known as pyrolysis, it breaks down to produce a variety of hydrocarbons similar to those found in natural petroleum. • Carbon and hydrogen are the main constituents of kerogen. Hydrogen concentrations range from 5 to 18% (atomic). Oxygen concentrations typically range from 0.25 to 3%, again depending on type and degree of evolution. Besides C, H, and O, kerogen typically contains 1–3% N and 0.25–1.5% S, and small amounts of trace transition metals.

5. Kerogen Macerals I • Microscopic examination reveals that kerogen consists of identifiable plant remains, amorphous material, and rare animal remains. The amorphous material in kerogen may occur as mottled networks, small dense rounded grains, or clumps. The microscopically identifiable constituents are called macerals. • Inertiteconsists of carbonized remains formed by rapid oxidation under aerobic conditions. One mechanism of inertite formation is wildfires in peat-producing environments(e.g., Okefenokee Swamp where wild fires occur periodically. • Vitriniteis preserved woody tissue. • Exiniteincludes lipid-rich materials derived from leaf cuticle, spores, pollen, algae, plant waxes, resins, fats, and oils. • Liptinitesare derived primarily from algal remains and usually have higher H/C ratios than exinites. II III

6. Evolution of Kerogen • As sedimentary organic matter is buried, it experiences progressively higher temperatures and pressures. • As bacterial activity ceases, a number of new reactions begin as the organic matter attempts to come to equilibrium with higher temperature and pressures. These reactions, in which kerogen breaks down into a variety of hydrocarbons and a refractory residue, are collectively calledcatagenesis. • One of the principal effects of diagenesis is the condensation of complex macromolecules from simpler ones. • During catagenesis, this process is reversed as kerogen breaks down into comparatively simple hydrogen-rich molecules (hydrocarbons) and a hydrogen-depleted carbon residue. The hydrogen-rich phase is mobile and will migrate out of the source rock if a migration pathway exists. • During diagenesis, kerogen evolves mainly toward lower O content through biological processes. It evolves toward lower H during catagenesis, as light, H-rich hydrocarbons are generated and lost.

7. Catagenesis • As temperatures in the range of 100–150°C are reached, a complex mixture of hydrocarbons, petroleum, is produced, along with lesser amounts of asphaltenes and resins. Collectively, this bitumen fraction is called oil or crude oil. • As temperatures approach 150°C, smaller hydrocarbons (≤C5) become dominant. These are gases at surface temperature and pressure. Dissolved in them, however, are lesser amounts of longer chains (≥C6). These condense to liquids upon reaching the surface and hence are called condensates. • At temperatures above 150–175°C, methane and graphite are the ultimate products, created in a process called metagenesis. • The degree of thermal maturation of kerogen can be monitored from its H/C and O/C ratios. • In the “oil window”, the point where maximum hydrocarbon generation occurs, the H/C ratio in the residual kerogen is less than 1 and the O/C ratio less than 0.1. • Kerogen with H/C ratios lower than 0.5 is over-mature, that is, it has already entered the metagenesis stage where methane is the principal hydrocarbon product. black is solid composition, grey is fluid composition

8. Composition of Petroleum natural gas gasoline kerosene diesel fuel heating oil lubricants →

9. The Carbon Cycle and Climate

10. Greenhouse Warming • In 1896, building on the 1824 work of Joseph Fourier, SvanteArrhenius published a paper entitled “On the influence of carbonic acid in the air upon the temperature of the ground” in which he suggested that the concentration of atmospheric CO2 might be increasing as a result of the extensive burning of coal that began with the industrial revolution. Taking note of the way in which CO2 absorbs infrared radiation, he supposed that increasing atmospheric CO2 variations would result in warming of the Earth’s surface temperature.

11. Greenhouse Gases • The principal gases in the modern Earth’s atmosphere, N2, O2, and Ar; they do not absorb in the infrared part of the spectrum. • Certain trace gases in the atmosphere, notably H2O, CO2, CH4, and N2O infrared radiation different wavelengths. • Notice any systematic differences between these?

12. Greenhouse Effect • Absorption scales with the log of concentration. Thus, for example, small changes in the abundance of CH4 have a greater relative effect on the energy balance than do small changes in more abundant CO2, even though CO2 absorbs at frequencies close to the Earth’s maximum spectral emittance and is thus inherently a more effective greenhouse gas. • The combined effect of these gases is to absorb much of the infrared radiated from the Earth’s surface and to raise the average temperature of the Earth’s surface from 254 K (-19°C) to 286 K (+13°C). • H2O is the most powerful of the greenhouse gases, because it absorbs over a relatively wide range of frequencies and because its concentration is relatively high (its atmospheric concentration can be up to 4% on a very hot, humid day). However, the residence time of water in the atmosphere is quite short, so that its effect alone can only be limited. • On long time-scales variations in the concentration of CO2 and the other greenhouse gases control climate. Variations in atmospheric greenhouse gas concentrations are a result of how carbon is cycled between the atmosphere and other reservoirs and how the Earth and life have evolved over the last 4.5 Ga.

13. The Carbon Cycle

14. Short Term Cycle • On short geologic time-scales(≤100,000 yrs), atmospheric CO2 levels are controlled by the balance of carbon fluxes into and out of the oceans and the terrestrial biosphere and soils in response Milankovitch forcing resulting CO2.

15. Glacial Cycling • Glacial cycles affect CO2 fluxes by: • Changing the volume and temperature of the oceans: The smaller the volume of the ocean, the less CO2 it can hold; CO2is more soluble in water at lower temperature. The effect of glacial cycles on these two factors is thus opposite. • Glacial cycles affect the terrestrial biota, but, again, with opposing effects: sea-level drops and the land expands, but expansion of glaciers also reduces this area. Precipitation patterns also change. This affects both the biomass the mass of dead organic matter in soils, etc. • The most important changes in CO2 fluxes to climate-driven changes in ocean circulation and hence the storage of CO2 in the deep ocean. The key ocean circulation changes appears to be a climate-driven migration of the westerly winds in the Southern Ocean. In the present interglacial climate, the most intense westerly winds are located south of the Antarctic polar front. As a result of a phenomenon called Ekman transport, these winds drive water away from Antarctica, and as a result, water rises, or “upwells” from depth, allowing CO2built-up in the deep ocean to vent to the atmosphere, keeping atmospheric CO2 concentrations high. During glacial times, these westerlies shifted equatorward allowing for build-up of CO2 in circum-Antarctic deep water. In addition, changes in the efficiency of the biologic pump affect the balance of CO2 between ocean and atmosphere.

16. The Deep Carbon Cycle • On longer terms, atmospheric CO2 is controlled by cycling of carbon between the ‘exogene’ and the solid Earth. • This is accomplished by: • silicate weathering, which consumes CO2 • sedimentary organic matter weathering, which produces CO2 • metamorphism and volcanism, which produces CO2 • burial of organic matter, which consumes CO2. • Climate, evolution of life, and plate tectonics all impact these processes. • These observations form the basis of the ‘BLAG’ model of Berner and others from Yale, now called the GEOCARB model.

17. Evolution of the Carbon Cycle • A steady increase in brightness of the Sun. The Sun is now about 30% brighter than it was 4.5 billion years ago when it first became a main sequence star. This increase in insolation would result in a surface temperature increase of nearly 22°C (the present mean global surface temperature is now about 13°C) if greenhouse forcing were constant. • Energy to drive tectonic activity comes from two sources: radioactive decay of U, Th, and K, and initial heat. The activity of these radionuclides has, of course, decreased exponentially over time. • Evolution of life has had a profound effect on the nature of the atmosphere, and, as a result, on climate. The Earth’s atmosphere in Hadean and early Archean times would have had no oxygen and CO2 would have been the dominant component(e.g., Mars and Venus). It may well have been modestly reducing, with some CH4 present. • Since CO2 and CH4 are greenhouse gases, the greenhouse effect would have been much greater – perhaps resolving the faint young Sun paradox.

18. Role of Silicate Weathering • When dissolved in water, CO2 forms carbonic acid and dissociates (Chapter 6), providing hydrogen ions that then attack silicate minerals: • CO2 + H2O ⇌ H+ + HCO3- • 2H+ + CaAl2Si3O8 ⇌ Al2Si2O5(OH)4 + Ca2+ • Calcium released in this way is carried by rivers to the sea along with bicarbonate ions where they precipitate as calcite: • Ca2+ + HCO3-⇌ H+ + CaCO3 • Much of the calcite redissolves in the deep water or sediment, but some is buried as part of the carbonate sediment. • Metamorphism tends to release CO2, as will volcanism with CO2 subducted into the mantle.

19. Phanerozoic GEOCARB Model • The GEOCARB model is based on the relationships illustrated here and the record of carbon isotope ratios in marine carbonate sediments. • The overall picture suggested by this model is one of declining atmospheric CO2 • A decline through the Ordovician led to a glacial epoch in the Late Ordovician–Early Silurian. The model suggests this was due to weathering of silicate rock. Continental position likely also played a role, as most evidence of glaciation comes from areas positioned near the South Pole at the time. • CO2recovered in the Silurian and Devonian, but declined again in the Carboniferous, leading to the Permo-Carboniferous glaciation. This time the cause appears to be burial of vast amounts of organic carbon in bogs, swamps, and mires that was ultimately transformed into coal. • Atmospheric CO2 recovered in the Mesozoic, but not to levels seen in the early Paleozoic (remember, however, that less CO2 was needed to maintain the same temperature). After reaching concentrations perhaps 5 times greater than present ones, atmospheric CO2 declined in the late Cretaceous and early Tertiary periods. • Long-term atmospheric CO2 levels have remained low throughout the late Tertiary (the Neogene) into the Quaternary, although shorter term variations have occurred as a result of perturbations of the exogenous carbon cycle driven by Milkankovitchcycling.

20. The Precambrian and the GOE • Knowing how atmospheric CO2 and climate varied in the Precambrian is a much more difficult proposition. • There is some sparse and equivocal evidence for glaciation around 2.8 Ga. • There is strong evidence of glaciations in roughly between 2.4 to 2.2 Ga and roughly between 0.8 to 0.6 Ga. • In both the Proterozoic events, glacial sediments (diamictites) appear to have been deposited at tropical, rather than polar, latitudes and at low elevation. • The Paleoproterozoicdiamictites in the Huronianformation occur stratigraphically above an older conglomerate containing abundant detrital pyrite (FeS2) and uraninite (UO2). That reduced minerals could survive erosion, transport, and deposition suggests they were deposited in an oxygen-free atmosphere. They are overlain by redbedsindicative of an oxidizing atmosphere. This period is known as the Great Oxidation Event (GOE). Oxygen levels in the atmosphere before the GOE were rose from 10-5lower than present to 5–15% of present atmospheric levels. • Huronian glaciation might have resulted from a decrease in atmospheric CH4 at this time.

21. Paleoproterozoic (Cryogenian) Glaciations • Followed the break-up of the Rodiniasupercontinentaround 800 Ma. Rodiniawas located at low latitude at the time and the fragments remained at low latitude. • All models involve significant disturbances to the carbon cycle and a consequent crash in greenhouse gas inventory. • Models: • Rising oxygen levels around this time greatly reduced the methane flux from oxygen-poor oceans. That in turn reduced the CO2 levels in the atmosphere (because the methane eventually oxidizes to CO2. • High rates of tropical weathering as Rodinia broke up led to enhanced ocean nutrient levels and productivity, and efficient burial of organic carbon. • In all the models, once glaciation begins, the Earth “whitens” and the much greater albedo provides a powerful feedback driving further cooling.

22. Climate Change Today • IPCC) estimates that the carbon emitted by fossil-fuel burning increased from an average of 6.4 ± 0.4 gigatons of carbon (GtC) per year in the 1990s to 7.2 ± 3 GtC per year in 2000–2005. • In addition, the IPCC estimates that an additional 1.9 GtC per year is being added to the atmosphere through cutting of tropical forests. • The actual increase in atmospheric CO2 is only around 4 GtC/yr. This difference reflects carbon transfer into other exogenous reservoirs. • The remaining 2–3 GtC/yr being released by fossil-fuel burning and tropical deforestation is apparently being taken up by the northern hemisphere biosphere. • IPCC 2013 report concludes that “It is extremely likely that human influence has been the dominant cause of the observed warming since the mid-20th century”

23. Predicted Consequences From the Summary for Policy Makers of the 5th Assessment Report of the Intergovernmental Panel on Climate Change (IPCC). Get it yourself at http://www.ipcc.ch/.