Green River Oil Shale—Concept of Origin Extended

Abstract

A much fuller understanding of the Green River oil shale and its organic chemistry will emerge when the geologists, paleontologists, organic chemists, biologists, paleolimnologists, and biogeochemists, who are now working on it, integrate their findings with those of the others. We know from the geology, paleontology, and paleolimnology that the biologic progenitors of the organic substance in the Green River oil shale could only have been microscopic algae, and other micro-organisms, that grew and accumulated in the central parts of large, shallow lakes that existed under a subtropical climate. The only nonlacustrine organic components were wind-blown, or water borne, pollens and waxy spores. These, however, made up a large and important part of the organic-rich sediment. The geology of the Green River Formation shows that as the algal and pollen-rich sediment was buried deeper and deeper, progressively more of its pore water and dissolved constituents were expressed. Static pressures may have reached as much as 210 kg cm−2, and the ambient temperature rose, with depth, to somewhere within the range between 90° and 125° C. Beneath the ancient lakes a tectonically quiescent environment persisted for tens of millions of years after their organic sediments had been deeply buried. The organic material of the Green River oil shale can be divided into three fractions—a small bitumen fraction that is extractable with common organic solvents, a major fraction called koerogen that consists of insoluble pyrobitumens, and a somewhat smaller inert fraction that is neither soluble nor does it yield oil on pyrolysis. As all three fractions originated in the same algal, pollen-rich sediment, an explanation for their marked differences must be sought in their geochemical history or from a study of the modern analogues of their progenitors. The components of the bitumen fraction consisted of “biological markers” that were inherited from the Eocene plants and animals in which they originally formed. Diagenesis has changed these hydrogen-rich compounds, but not enough to obscure their provenance. Kerogen presumably became insoluble because its hydrogen-rich components polymerized. My speculation is that the inert fraction was derived from a polyphenolic substance produced in the original algal ooze by “non-enzymatic browning.” Only three Classes of non-marine algae need be considered as progenitors of the Green River oil shale; the Xanthophyceae, the Chlorophyceae, and the Cyanophyceae. Only the Cyanophyceae (the blue-green algae) meet the biologic and paleontologic requirements to have served as the dominant precursors of the Green River oil shale. Several other oil shales clearly were derived from the Xanthophyceae, specifically Botryococcus. The blue-green algal ooze now forming, and accumulating, in Mud Lake, Florida, has been studied biologically and chemically as a possible present-day analogue of the Green River oil shale precursor. In this small lake we have established the fact that a bacterial inhibitor is produced, which inhibits decay of the algae and thereby permits the accumulation of energy-rich organic compounds. We infer that a similar indigenous inhibitor must have acted in the Eocene lakes to permit them to become the huge energy sinks they were. Studies of the organic chemistry of living blue-green algae show that they contain appreciable percentages of fatty acids, hydrocarbons, and very large percentages of proteins. These promising, energy-rich compounds could serve as source materials for potential conversion into oil shale in the geologic future. Certain marine anaerobic bacteria convert fatty acids into aliphatic hydrocarbons. Fresh-water obligate anaerobes should be investigated to see if they also convert fatty acids into hydrocarbons. The part played by aquatic animals that live in, or on, freshwater algal ooze in synthesizing hydrocarbons has not been investigated, but deserves attention. Pollen grains, of course, must be considered an important precursor of hydrocarbons produced on pyrolysis. They contain far higher percentages of long chain hydrocarbons and alcohols than most plant materials. The major problem ahead is to account for the progressive hydrogenation and subsequent polymerization of the relatively oxygen-rich constituents of algae such as the polysaccharides, amino acids, ammo sugars, and fatty acids into the insoluble pyrobitumens that constitute, particularly, the kerogen fraction of the Green River oil shale.