Search USGSSearch

Geology topics

H. E. Lerch

Publications and source records attributed to H. E. Lerch.

4 recordsLinked to original sources

Organic geochemical studies of the transformation of gymnospermous xylem during peatification and coalification to subbituminous coal

Organic geochemical investigations of peatified and coalified xylem from gymnosperms have provided useful information on the organic transformational processes collectively known as coalification. The combined use of solid-state 13 C nuclear magnetic resonance (NMR) and pyrolysis/gas chromatography/mass spectrometry (py/gc/ms) has allowed us to examine the organic composition of peatified and coalified xylem on both a bulk (average) compositional basis and on a detailed molecular basis. We conclude from our studies that coalification of gymnospermous xylem involves the following processes1. (1) early selective removal of cellulosic materials so that lignin, a primary constituent of xylem, is transformed to macromolecular aromatic components in coal;2. (2) modification of gymnospermous lignin by demethylation to form catechol-like structures, and by condensation reactions to induce a high level of cross-linking at an early stage of coalification; and (3) dehydroxylation during increasing coalification to subbituminous coal, the resultant xylem becomes more phenolic in character as the catechol-like structures decrease.

International Journal of Coal Geology

Studies of angiospermous woods in Australian brown coal by nuclear magnetic resonance and analytical pyrolysis: new insight into early coalification

Many Tertiary coals contain abundant fossilized remains of angiosperms, which commonly dominated the ancient peat-swamp environments; modern analogs of such swamps can be found in tropical and subtropical regions of the world. Comparisons of angiospermous wood from Australian brown coal with similar wood buried in modern peat swamps of Indonesia have provided some new insights into coalification reactions. These comparisons were made by using solid-state 13 C nuclear magnetic resonance (NMR) techniques and pyrolsis-gas chromatography-mass spectrometry (py-gc-ms). These two modern techniques are especially suited for detailed structural evaluation of the complex macromolecules in coal. The earliest transformation (peatification) of organic matter in angiospermous wood is the degradation and removal of cellulosic components and the concomitant selective preservation of lignin-derived components. The angiospermous lignin that becomes enriched in wood as a result of cellulose degradation also is modified by coalification reactions; this modification, however, does not involve degradation and removal of the lignin. Rather, the early coalification process transforms the lignin phenols (guiacyl and syringyl) to eventually yield the aromatic structures typically found in brown coal. One such transformation, which is determined from NMR data, involves the cleavage of aryl-ether bonds that link guaiacyl and syringyl units in lignin, and this transformation leads to the formation of free lignin phenols. Another transformation, which is also determined from the NMR data, involves the loss of methoxyl groups, probably via demethylation, to produce catechol-like structures. Coincident with ether-cleavage and demethylation, the aromatic rings derived from lignin phenols become more carbon-substituted and cross linked, as determined by dipolar-dephasing NMR studies. This cross linking is probably responsible for preventing the lignin phenols, which are freed from the lignin macromolecule by ether cleavage, from being removed from the coal by dissolution. Pyrolysis data suggest that the syringyl units are altered more readily than are guaiacyl units, and this difference in resistance leads to an enrichment of the guaiacyl units in fossil angiospermous woods. Many of the coalification reactions noted above occur to some degree in all angiospermous fossil wood examined; however, some significant differences are observed in the degree of coalification of the fossil wood samples from the same burial depth in the brown coal. These differences indicate that the depth and duration of burial are probably not entirely responsible for the variations in degree of coalification. Different rates of degradation in peat may have contributed to the variations in the apparent degree of coalification; some woods may have been altered more rapidly at the peat stage than others. Although preliminary, this systematic study of botanically related wood in peat and coal results in a more detailed differentiation of coalification reactions than have previous investigations. The combined use of solid-state 13 C NMR and py-gc-ms has facilitated this detailed insight into the coalification of angiospermous wood.

International Journal of Coal Geology

1,3,5-Hydroxybenzene structures in mosses

A number of mosses from widely different families have been studied by cross polarization solid state 13 C NMR spectroscopy. Although polysaccharide-type materials dominate the NMR spectra, significant amounts of aromatic carbons are observed in some mosses. Some of this material can be removed by ultrasonic bath treatment, and is lignin derived, probably from impurities from fine root material from associated higher plants. However other material is truly moss-derived and appears to be from 1,3,5-hydroxybenzene structures. This is inconsistent with lignin as being a component of mosses, and suggests a tannin or hydroxybenzofuran polymer is responsible for moss rigidity.

Phytochemistry

Pyrolysis g.c.-m.s. of a series of degraded woods and coalified logs that increase in rank from peat to subbituminous coal

Xylem tissue from degraded wood and coalified logs or stems was examined by pyrolysis g.c.-m.s. to improve understanding of the coalification process. The pyrolysis data, when combined with solid-state 13 C n.m.r. data for the same samples, show several stages of evolution during coalification. The first stage, microbial degradation in peat, involves the selective degradation of cellulosic components and preservation of lignin-like components. As coalification increases, the lignin structural units undergo a series of defunctionalization reactions. The first of these involve loss of methoxyl groups, with replacement by phenolic hydroxyls such that catechol-like structures are produced. As the xylem tissue is converted to subbituminous coal, the persistence of phenols and methylated phenols in pyrolysis g.c.-m.s. data of subbituminous coal suggests that the catechol-like structures are being converted to phenol-like structures. The ability to discern detailed changes in the chemical structural composition of a genetically and histologically related series of samples provides an ideal method for developing models of coal structure, especially that of low-rank coal.

Fuel