Thursday, 30 July 2015

Accumulation of organic matter

It is well documented that oil accumulations are of organic origin and formed from organic matter in sediments. Methane can be formed inorganically and is found in the atmosphere of several other planets, but inorganic methane from the interior of the earth is likely to be well dispersed and thus not form major gas accumulations in the earth’s crust. The organic matter from which petroleum is derived originated through photosynthesis, i.e. storage of solar energy. Sunlight is continuously transformed into such energy on Earth but only a very small proportion of the solar energy is preserved as organic matter and petroleum. The oil and gas which forms in sedimentary basins each year is thus minute in comparison with the rate of exploitation (production) and consumption. In practice petroleum must therefore be regarded as a non-renewable resource even though some petroleum is being formed all the time. Most of the organic materials which occur in source rocks for petroleum are algae, formed by photosynthesis.The zoo plankton and higher organisms that are also represented grazed the algae and were thus indirectly dependent on photosynthesis too. The energy which we release when burning petroleum is therefore stored solar energy. Since petroleum is derived from organic matter, it is important to understand how and where sediments with a high content of organic matter are deposited. The total production of organic material in the world’s oceans is now 5×1010 tonnes/year. Nutrients for this organic production are supplied by erosion of rocks on land and transported into the ocean. The supply of nutrients is therefore greatest in coastal areas, particularly where sediment-laden rivers discharge into the sea. Plant debris is also supplied directly from the land in coastal areas. Biological production is greatest in the uppermost 20–30 m of the ocean and most of the phytoplankton growth takes place in this zone. In clear water, sunlight penetrates much deeper than in turbid water, but in clear water there is usually little nutrient supply. At about 100–150 m depth, sunlight is too weak for photosynthesis even in very clear water. Phytoplankton provides nutrition for all other marine life in the oceans. Zooplankton feed on phytoplankton and therefore proliferate only where there is vigorous phytoplankton production. Organisms sink after they have died, and may decay so that nutrients are released and recycled at greater depths. Basins with restricted water circulation will preserve more organic matter and produce good source rocks which may mature to generate oil and gas. In polar regions, cold dense water sinks to great depths and flows along the bottom of the deep oceans towards lower latitudes. This is the thermal conveyor belt transporting heat to higher latitudes and it keeps the deep ocean water oxidizing. In areas near the equator where the prevailing winds are from the east the surface water is driven away from the western coast of the continents. This generates a strong up welling of nutrient-rich water from the bottom of the sea which sustains especially high levels of primary organic production. The best examples of this are the coast of Chile and off West Africa. Through photosynthesis, low energy carbon dioxide and water are transformed into high energy carbohydrates (e.g. glucose):

CO2 + H2O → CH2O (organic matter) + O2

The production of organic matter is not limited by carbon dioxide or water, but by nutrient availability. 
Phosphorus (P) and nitrogen (N) are the most important nutrients, though the supply of iron can also be limiting for alga production. It is this process of photosynthesis, which started 4 billion years ago, that has built up an atmosphere rich in oxygen while accumulating reduced carbon in sedimentary rocks as oil, gas and coal. Most of the carbon is nevertheless finely divided within sedimentary rocks, for example shales and limestones, in concentrations too low to generate significant oil and gas. Energy stored by photosynthesis can be used directly by organisms for respiration. This is the opposite process, breaking carbohydrates down into carbon dioxide and water again, so that the organisms gain energy. This occurs in organisms at night when there is no light to drive photosynthesis. Also when we burn hydrocarbons, e.g. while driving a car, energy is obtained by oxidation, again essentially reversing the photosynthesis equation quoted above. Oxidation of 100 g glucose releases 375 kcal of energy. Carbohydrates that are produced but not consumed by respiration can be stored as glucose, cellulose or starch in the cell walls. Photosynthesis is also the biochemical source for the synthesis of lipids and proteins. Proteins are large, complex molecules built up of condensed amino acids (e.g. glycine (H2NCH2−COOH)). 
Dried phytoplankton contains 45–55% carbon, 4.5–9% nitrogen, 0.6–3.3% phosphorus and up to 25% of both silica and carbonate. Planktonic algae are the main contributors to the organic matter which gives rise to petroleum. Among the most important are diatoms, which have amorphous silica (opal A) shells.
Diatoms are most abundant in the higher latitudes and are also found in brackish and fresh water. Blue - green algae (cyanobacteria) which live on the bottom in shallow areas, also contribute to the organic material in sediments. In coastal swamps, and particularly on deltas, we have extensive production of organic matter in the form of plants and trees which may avoid being oxidised by sinking into mud or bog. The residues of these higher land plants may form peat, which with deeper burial may be converted into lignite and bituminous coal. But such deposits are also a potential source of gas and oil. Plant matter, including wood, also floats down rivers and is deposited when it sinks to the bottom, usually in a near shore deltaic environment. When the trees rot they release CO2 and consume as much oxygen as the plant produced during the whole period when it was growing. There is thus no net contribution of oxygen to the atmosphere. This also applies to the bulk of the tropical rainforests. Where trees and plants sink into black mud, preventing them from being oxidised, there is a net contribution of oxygen to the atmosphere and a corresponding reduction of CO2 in the atmosphere. All animal plankton (zooplankton) live on plant plankton, and in turn are eaten by higher organisms in the food chain. At each step in the food chain, which we call a trophic level, the amount of organic matter (the biomass) is reduced to 10%. Ninety percent of the production of organic matter is therefore from algae. This is why algae and to some extent zooplankton account for the bulk of the organic material which can be transformed into oil. Larger animals such as dinosaurs are totally irrelevant as sources of oil. The most important of the zooplankton which provide organic matter for petroleum are:
  1. Radiolaria – silica shells, wide distribution, particularly in tropical waters. 
  2. Foraminifera – shells of calcium carbonate. 
  3. Pteropods – pelagic gastropods (snails) with a foot which has been converted into wing-shaped lobes; carbonate shells.
This is the second lowest level within the marine food chain. These zooplanktonic organisms are eaten by crustaceans which themselves are eaten by fish. The total amount of organic matter that can be produced in the ocean is dependent on the nutrient supply from rivers, but river water does not only carry inorganic nutrients. It also contains significant amounts of organic matter, in particular humic acid compounds, lignin and similar substances formed by the breakdown of plant material which are weakly soluble in cold water. When the river water enters the sea, there is precipitation due to the increased pH and lower surface temperature in the ocean. Other plant materials, like waxes and resins, are more chemically resistant to breakdown and are insoluble in water. Such organic particles tend to attach themselves to mineral grains and accompany sediment out into the ocean. Most of the oil reservoirs which have been formed since the Palaeozoic have been uplifted and eroded, and over time vast quantities of oil have flowed (seeped) out onto the land or into the sea. In this sense, oil pollution is a natural process. Only a small proportion of the petroleum that has been formed in source rocks has actually become trapped in a reservoir. One might expect this seepage to have provided a source of recycled petroleum in younger sediments, but petroleum breaks down extremely rapidly when subjected to weathering, oxidising to CO2, and the nutrients (P, N) that were required to form the organic matter are released and may act like a fertilizer. On land, evaporation will remove the lighter components while bacteria will degrade the heavier components. Fossil asphalt lakes consist of heavy substances which neither evaporate nor can be easily broken down by bacteria. In the ocean, the lighter components will dissolve quite rapidly, while the heavier asphalt fraction will sink to the bottom and be degraded and recycled. In uplifted sedimentary basins like the Ventura Basin and the Los Angeles Basin in Southern California there are abundant natural oils seeps both onshore and offshore. On the beaches from Santa Barbara towards Los Angeles there are many natural oil seeps.


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