The mineral fuels—coal, petroleum, and natural gas—may be described as a special type of economic deposit. Geochemically they represent the concentration of carbon and hydrogen by processes that were initially biological in nature. Coal is essentially the product of accumulation of land plants in large amounts, and petroleum and natural gas are the products of marine organisms (although the origin of some petroleum and natural gas under nonmarine conditions cannot be entirely excluded). The origin of petroleum and natural gas presents a more difficult problem than coal because they are fluids and thus are free to migrate from their place of origin.

The formation of coal is a relatively straightforward geochemical process that can readily be traced through its successive stages. The first requirement is a geological one—the rapid accumulation of plant material under conditions that inhibit its decomposition, followed by its burial under inorganic sediments such as shales and sandstones. The great coal-forming period in the Northern Hemisphere followed the Devonian Period (345,000,000 to 395,000,000 years ago), when abundant land plants first appeared, and has been named the Carboniferous Period (280,000,000 to 345,000,000 years ago). During this period, large areas in North America and Europe were evidently low-lying swamps that supported a lush vegetation. This vegetation died, accumulated in successive layers, and was partly decomposed by bacteria and other organisms to form peat. Burial of peat deposits under inorganic sediments brought an end to the period of bacterial decomposition, and the further changes to coal were essentially a mild metamorphism caused by an increase in temperature and pressure.

Chemically, this mild metamorphism was in large part the expulsion of carbon dioxide and water from the coal-forming substance. The main trend in the change from peat through lignite to bituminous coal and anthracite is the decrease in oxygen content and the increase in carbon. If carried to its ultimate conclusion the product would be pure carbon in the form of graphite. This occurs comparatively rarely, but evidence for it is the presence of small amounts of graphite in many metamorphic rocks.

Coal also contains inorganic material that appears as ash when it is burned, and some coal ashes show a remarkable concentration of unusual elements. This was demonstrated by Goldschmidt in 1933, when he found appreciable amounts of germanium in some coal ashes. The Hartley Seam of the Durham Coalfield in England contains so much germanium that the ash has a brilliant yellow colour because of the presence of the oxide (GeO₂).

The source of these minor and trace elements and their mode of incorporation in the coal are still not fully understood. There are three possibilities: (1) these elements were taken up by the plants during growth; (2) they were carried into the coal swamp as a component of the inorganic sediments; or (3) they were absorbed during or after the coal-forming processes from circulating solutions. The first possibility is not favoured, because growing plants seldom incorporate appreciable amounts of nonorganic elements. The second possibility also is unlikely, because there is no correlation, or rather an inverse correlation, between ash content and trace element concentrations. This leaves the third possibility as the most likely one. The presence of a large amount of carbonaceous matter means that the coal-forming environment is a highly reducing one, which will favour the precipitation of some elements; the presence of hydrogen sulfide and sulfide ions will cause the precipitation of chalcophile elements (with affinity for sulfur); and complex organic compounds are noted for their absorptive, or chelating, capacity for metallic ions. Thus several individual reactions are potentially available for the fixation of foreign elements in the coal substance.

As pointed out above, the origin of petroleum is not as readily elucidated as the origin of coal, because petroleum can migrate from the region in which it was formed. Indeed, the very occurrence of a commercial oil field probably implies the concentration of the petroleum from a large volume of source rocks into a relatively much smaller reservoir.

The fact that petroleum is almost always found in marine sedimentary rocks has long been a basic argument in favour of a marine origin for this material. It is certainly true that some oil has been found in igneous and metamorphic rocks, but migration from a sedimentary source bed is a reasonable explanation for these occurrences. Proof of a marine origin has been forthcoming in recent years by the sensitive analyses of recent marine sediments, which show that they contain small amounts of petroleum hydrocarbons, evidently generated either directly by marine organisms or by their subsequent decomposition.

Natural petroleum is a complex mixture of hundreds of different hydrocarbons, but its bulk composition is remarkably constant, about 85 percent carbon and 15 percent hydrogen. It may include small amounts of organic compounds containing oxygen, sulfur, and nitrogen. Its content of other elements is exceedingly small. Petroleum ash, unlike coal ash, is not noted for its trace element content. Some petroleum ash contains appreciable amounts of vanadium, however, and has been utilized as a source of this element. A class of nitrogen-bearing organic compounds known as porphyrins include a metal atom in their molecular structure; usually this atom is iron, but other elements in this region of the periodic table, especially vanadium, nickel, and copper, may play a similar role. The vanadium content of some petroleum ash probably originates as a vanadium porphyrin in some of the organisms involved in petroleum formation.

Petroleum is always accompanied by natural gas, but many natural gas fields have no petroleum associated with them. This can probably be ascribed to greater possibility for migration for a gas as compared to a liquid. It is also possible that some natural gas is generated from coal deposits. Natural gas consists largely of methane, but small amounts of more complex hydrocarbons may be present, and it may also contain unwanted components such as nitrogen, carbon dioxide, and hydrogen sulfide. Natural gas containing hydrogen sulfide is known as “sour gas” and for long was an undesirable material because of the noxious nature of this compound; recently, however, it has been found profitable to extract the hydrogen sulfide by converting it to sulfur and then utilize the hydrocarbons.

Natural gas is the sole source of one element, helium, the industrial demand for which has steadily increased in recent years. Comparatively few occurrences of natural gas contain sufficient helium for the extraction to be commercially profitable. Currently, the Western world’s need for helium is largely met by its extraction from wells in western Texas. The explanation for this local concentration of helium in some natural gas fields is still a matter for discussion; the only reasonable source is from the disintegration of radioactive elements in the crust, but the mechanism of concentration remains something of an enigma.