Irving A. Breger

Nuclear magnetic resonance studies of ancient buried wood—II. Observations on the origin of coal from lignite to bituminous coal

Coalified logs ranging in age from Late Pennsylvania to Miocene and in rank from lignite B to bituminous coal were analyzed by 13C nuclear magnetic resonance (NMR) utilizing the cross-polarization, magic-angle spinning technique, as well as by infrared spectroscopy. The results of this study indicate that at least three major stages of coalification can be observed as wood gradually undergoes transformation to bituminous coal. The first stage involves hydrolysis and loss of cellulose from wood with retention and differential concentration of the resistant lignin. The second stage involves conversion of the lignin residues directly to coalified wood of lignitic rank, during which the oxygen content of intermediate diagenetic products remains constant as the hydrogen content and the carbon content increases. These changes are thought to involve loss of methoxyl groups, water, and C3 side chains from the lignin. In the third major stage of coalification, the coalified wood increases in rank to subbituminous and bituminous coal; during this stage the oxygen content decreases, hydrogen remains constant, and the carbon content increases. These changes are thought to result from loss of soluble humic acids that are rich in oxygen and that are mobilized during compaction and dewatering. Relatively resistant resinous substances are differentially concentrated in the coal during this stage. The hypothesis that humic acids are formed as mobile by-products of the coalification of lignin and function only as vehicles for removal of oxygen represents a dramatic departure from commonly accepted views that they are relatively low-molecular-weight intermediates formed during the degradation of lignin that then condense to form high-molecular-weight coal structures.

Nuclear magnetic resonance studies of ancient buried wood-I. Observations on the origin of coal to the brown coal stage

Various wood fragments buried in sediments under anaerobic conditions for from 450 yr to approximately 8 Myr have been examined by solid-state 13C nuclear magnetic resonance. Cellulose and other carbohydrates, the major components of Holocene wood, have been shown to be gradually hydrolyzed or otherwise lost under the conditions of burial. Lignin structures, however, are preserved relatively unchanged and become concentrated by difference as the carbohydrates disappear. Thus, a fragment of coalified wood isolated from a Miocene brown coal was found to be still composed of approximately 75% lignin and 25% cellulose. On the basis of our observations, we suggest that coalification of woody tissue progresses directly from lignin to coal and that such coalification may be retarded until most of the cellulose disappears.

Geochemistry of lipids

Lipids, particularly the glycerides, terpenes, sterols, and hydrocarbons, have properties conducive to their preservation either in original or transformed state and are significant constitutents of the geochemical biomass. The occurrence of phytane, pristane, and fatty acids in Precambrian sedimentary rocks 2.7 billion years old has been interpreted to indicate the existence of life processes similar to those that are operative today.The stability of lipids is highly variable. Sterols, terpenes, fatty acids, esters, and hydrocarbons have been isolated from ancient sedimentary rocks; there is evidence, however, that esters may hydrolyze. Under certain conditions, highly unsaturated fatty acids may undergo combined biochemical and chemical transformations that lead to the formation of petroleum hydrocarbons.Lipids found in geological environments are derived from contributing organisms, which represent specific ecologies. Study of the ultimate products derived from these lipids permits an understanding of the geochemical environments in which they were produced, and of the transformations that occurred.

Diagenesis of metabolites and a discussion of the origin of petroleum hydrocarbons

Abstract Proteins and carbohydrates are rapidly degraded to compounds of no direct interest in the problem of the origin of petroleum. Lignin, if carried into marine basins in the form of humic substances, is probably the major progenitor of kerogen rather than the precursor of petroleum. Pigments are but minor contributors to petroleum. The fate of fatty acids in a marine environment is not completely understood. Although they may not be directly decarboxylated biochemically, it is shown how they can be converted into oxygenated or dehydrogenated acids more reactive than the parent compounds. Illustrations are also given for Diels-Alder reactions that could account for the formation from these compounds of the alicyclic and aromatic hydrocarbons in petroleum. It is most likely that crude oil is generated in sediments containing concentrations of lipids, the character of which governs the nature of the oil that is formed.

Germanium and uranium in coalified wood bom upper Devonian black shale

Abstract Microscopic study of black, vitreous, carbonaceous material occurring in the Chattanooga shale in Tennessee and in the Cleveland member of the Ohio shale in Ohio has revealed coalified woody plant tissue. Some samples have shown sufficient detail to be identified with the genus Cauixylon. Similar material has been reported in the literature as “bituminous” or “asphaltic” stringers. Spectrographic analyses of the ash from the coalified wood have shown unusually high percentages of germanium, uranium, vanadium, and nickel. The inverse relationship between uranium and germanium in the ash and the ash content of various samples shows an association of these elements with the organic constituents of the coal. On the basis of geochemical considerations, it seems most probable that the wood or coalified wood was germanium-bearing at the time logs or woody fragmenta were floated into the basins of deposition of the Chattanooga shale and the Cleveland member of the Ohio shale. Once within the marine environment, the material probably absorbed uranium with the formation of organo-uranium compounds such as exist in coals. It is suggested that a more systematic search for germaniferous coals in the vicinity of the Chattanooga shale and the Cleveland member of the Ohio shale might be rewarding.

Search for Organic Compounds in the Lunar Dust from the Sea of Tranquiblity

A sample of lunar dust was examined for organic compounds. Carbon detected in concentrations of 157 micrograms per gram had a δ13C per mil (PDB) value of + 20. Treatment with hydrochloric acid yielded hydrocarbons of low molecular weight, suggesting the presence of carbides. The gas chromatogram of the acylated and esterified derivatives of the hydrolyzate was similar to that obtained for the Pueblito de Allende meteorite. There were no detectable amounts of extractable high-molecular-weight alkanes, aromatic hydrocarbons, isoprenoid hydrocarbons, normal alkanes, fatty acids, amino acids, sugars, or nucleic acid bases. Traces of porphyrins were found, perhaps arising from rocket exhaust materials.

Kerogen in the Chattanooga Shale

The Chattanooga shale contains insoluble organic matter (kerogen) derived from terrestrial (humic) and from marine (sapropelic) sources. Kerogen from sapropelic sources contains more hydrogen than kerogen from humic sources. Thus the hydrogen content of the sapropelic contribution, and of the kerogen, increases toward that part of a shale most likely to be a source bed for petroleum. Uranium in the shale is derived from the adjoining land mass.

Potentiometric titration and equivalent weight of humic acid

Abstract The “acid nature” of humic acid has been controversial for many years. Some investigators claim that humic acid is a true weak acid, while others feel that its behaviour during potentiometric titration can be accounted for by colloidal adsorption of hydrogen ions. The acid character of humic acid has been reinvestigated using newly-derived relationships for the titration of weak acids with strong base. Re-interpreting the potentiometric titration data published by Thiele and Kettner in 1953, it was found that Merck humic acid behaves as a weak polyelectrolytic acid having an equivalent weight of 150, a pKa of 6.8 to 7.0, and a titration exponent of about 4.8. Interdretation of similar data pertaining to the titration of phenol-formaldehyde and pyrogallol-formaldehyde resins, considered to be analogs for humic acid by Thiele and Kettner , leads to the conclusion that it is not possible to differentiate between adsorption and acid-base reaction for these substances.

Free-Radical Concentrations and Other Properties of Pile-Irradiated Coals

Five coals reacted quite differently when they were exposed to pileirradiation. Little or no change was found in free-radical content for the three coals of lowest carbon content, whereas the two coals of highest carbon content were found to have a considerable increase in free-radical content. The infrared spectra and the apparent hardness of the irradiated coals of higher carbon content indicate that polymerization occurred. Radiation of these coals in chemical reagents may promote reactivity.

Equivalent weight of humic acid from peat

Abstract By means of discontinuous titration, the equivalent weight of humic acid isolated from a peat was found to increase from 144 to 183 between the third and fifty-second day after the humic acid was dissolved. Infra-red studies showed that the material had probably condensed with loss of carbonyl groups.