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Geology topics

Patrick G. Hatcher

Publications and source records attributed to Patrick G. Hatcher.

At least 37 records · Page 2Linked to original sources

Detection of tannins in modern and fossil barks and in plant residues by high-resolution solid-state 13C nuclear magnetic resonance

Bark samples isolated from brown coal deposits in Victoria, Australia, and buried wood from Rhizophora mangle have been studies by high-resolution solid-state nuclear magnetic resonance (NMR) techniques. Dipolar dephasing 13 C NMR appears to be a useful method of detecting the presence of tannins in geochemical samples including barks, buried woods, peats and leaf litter. It is shown that tannins are selectively preserved in bark during coalification to the brown coal stage.

Organic Geochemistry

Evidence of land plant affinity for the Devonian fossil Protosalvinia (Foerstia)

The Devonian plant fossil Protosalvinia (Foerstia) has been examined by solid-state 13 C nuclear magnetic resonance spectroscopy (NMR) and pyrolysis-gas chromatography-mass spectrometry (PY-GC-MS). Results of these studies reveal that the chemical structure of Protosalvinia is remarkably similar to that of coalified wood. A well-defined phenolic carbon peak in the NMR spectra and the appearance of phenol and alkylated phenols in pyrolysis products are clearly indicative of lignin-like compounds. These data represent significant new information on the chemical nature of Protosalvinia and provide the first substantial organic geochemical evidence for land plant affinity. Protosalvinia, Foerstia, Upper Devonian, biostratigraphy, carbon-13 NMR, PY-GC-MS, lignin.

Lethaia

Solid-state 13C NMR studies of dissolved organic matter in pore waters from different depositional environments

Dissolved organic matter (DOM) in pore waters from sediments of a number of different depositional environments was isolated by ultrafiltration using membranes with a nominal molecular weight cutoff of 500. This > 500 molecular weight DOM represents 70–98% of the total DOM in these pore waters. We determined the gross chemical structure of this material using both solid-state 13 C nuclear magnetic resonance spectroscopy and elemental analysis. Our results show that the DOM in these pore waters appears to exist as two major types: one type dominated by carbohydrates and paraffinic structures and the second dominated by paraffinic and aromatic structures. We suggest that the dominance of one or the other structural type of DOM in the pore water depends on the relative oxidizing/reducing nature of the sediments as well as the source of the detrital organic matter. Under dominantly anaerobic conditions carbohydrates in the sediments are degraded by bacteria and accumulate in the pore water as DOM. However, little or no degradation of lignin occurs under these conditions. In contrast, sediments thought to be predominantly aerobic in character have DOM with diminished carbohydrate and enhanced aromatic character. The aromatic structures in the DOM from these sediments are thought to arise from the degradation of lignin. The large amounts of paraffinic structures in both types of DOM may be due to the degradation of unidentified paraffinic materials in algal or bacterial remains.

Organic Geochemistry

Early diagenesis of organic matter in a Sawgrass peat from the Everglades, Florida

The transformation of plant biopolymers to humic substances in peats during early diagenesis is a critical but poorly understood step in the formation of coal. This paper presents results concerning the structural interrelationships among various fractions of the organic matter in peat and the dissolved organic matter in the pore water from a site in The Everglades, relying primarily on elemental analysis and 13 C nuclear magnetic resonance for structural elucidation. Our goal was to obtaine some insight into the sequence of steps involved in the formation of humic substances Results show that the major change occurring in the whole peat during diagenesis is loss of carbohydrates. The components of the peat which are more resistant to microbial degradation become concentrated in the humin fraction. This resistant fraction of the organic matter includes aliphatic and aromatic components. The aromatic components are thought to be derived from lignin while the aliphatic moieties may represent decomposed algal remains. The carbohydrates lost from the whole peat appear to be concentrated in the fulvic acids and the dissolved organic matter in the pore water. The humic acids consist predominantly of aromatic and aliphatic structures, and may represent partially degraded lignin-like structures and aliphatic compounds from algae. The data presented here suggest that humic and fulvic acids are the partially degraded fractions of the peat while the humin contains the resistant or preserved portion of the organic matter. The proposition that humic substances are formed by the condensation of amino acids and sugars is not supported by the results of this study.

International Journal of Coal Geology

PYROLYSIS/GAS CHROMATOGRAPHY/MASS SPECTROMETRY OF A SERIES OF BURIED WOODS AND COALIFIED LOGS THAT INCREASE IN RANK FROM PEAT TO SUBBITUMINOUS COAL.

To better understand the coalification process, we have conducted numerous studies of the chemical structural composition of xylem tissue from gymosperm wood and related woods that has been coalified to varying degrees. The studies presented here, examine the chemical nature of buried and coalified xylem tissue at the molecular level. To achieve this, we employed pyrolysis/gas chromatography (py/gc) and pyrolysis/gas chromotography/mass spectrometry (py/gc/ms). Pyrolysis techniques have been used to examine peat, coal, coalified wood, and related substances. However, the technique has not been previously applied to a systematic and histologically-related series of coalified woods. It is particularly useful to compare the results from pyrolytic studies with the data obtained from solid-state **1**3C NMR.

Conference Paper

Secretinite: A proposed new maceral of the inertinite maceral group

The new maceral secritinite (name derived from the word ‘secretory’) is proposed for subcircular, ovoid, crescent-shaped or oblong, commonly round on one or more sides, noncellular, highly reflective components of the inertinite maceral group. This maceral of secretory origin, known from many bituminous coals throughout the world, has been confused with cellular, opaque fungal masses of high reflectance. It is suggested that these fungal masses be assigned to the previously proposed maceral funginite of the inertinite maceral group. The maceral term ‘sclerotinite’ and maceral-varietal terms ‘fungo-sclerotinite’ and ‘resinosclerotinite’ should be abandoned because they confuse the natural botanical relations and because they are unnecessary if the proposed maceral names, secretinite and funginite, are accepted. The maceral-varietal terms secreto-macrinite and secreto-inertodetrinite are proposed for angular to irregular constituents whose properties are physically gradational from secretinite into the macerals macrinite and inertodetrinite.

Fuel

Cyclic terpenoids of contemporary resinous plant detritus and of fossil woods, ambers and coals

Cyclic terpenoids present in the solvent extractable material of fossil woods, ambers and brown coals have been analyzed. The sample series chosen consisted of wood remains preserved in Holocene to Jurassic sediments and a set of of ambers from the Philippines (copalite), Israel, Canada and Dominican Republic. The brown coals selected were from the Fortuna Garsdorf Mine and Miocene formations on Fiji. The fossil wood extracts contained dominant diterpenoid or sesquiterpenoid skeletons, and aromatized species were present at high concentrations, with a major amount of two-ring aromatic compounds. Tricyclic diterpenoids were the predominant compounds in the ambers. Aromatized derivatives were the major components, consisting of one or two aromatic ring species with the abietane and occasionally pimarane skeletons. The saturated structures were comprised primarily of the abietane and pimarane skeletons having from three to five carbon (C 1 , C 2 , etc.) substituents. Kaurane and phyllocladane isomers were present in only minor amounts. Bicyclic sesquiterpenoids as saturated and partial or fully aromatized forms were also common in these samples, but only traces of sesterterpenoids and triterpenoid derivatives were found. The brown coal extracts were composed of major amounts of one- and two-ring aromatized terpenoids, with a greater proportion of triterpenoid derivatives than in the case of the woods and ambers. This was especially noticeable for the German coal, where the triterpenoids were predominant. Open C-ring aromatized structures were also present in this coal. Steroid compounds were not detectable, but some hopanes were found as minor components in the German brown coal. An overview of the skeletal structure classes identified in each sample, as well as the general mass spectrometric characteristics of the unknown compounds are included in the present paper. It can be concluded from these structural distributions that aromatization is the main process for the transformation of terrestrial cyclic terpenoids during diagenesis, constituting a general pathway for all terpenoids.

Organic Geochemistry

Degradation of carbohydrates and lignins in buried woods

Spruce, alder, and oak woods deposited in coastal sediments were characterized versus their modern counterparts by quantification of individual neutral sugars and lignin-derived phenols as well as by scanning electron microscopy, 13 C NMR, and elemental analysis. The buried spruce wood from a 2500 yr old deposit was unaltered whereas an alder wood from the same horizon and an oak wood from an open ocean sediment were profoundly degraded. Individual sugar and lignin phenol analyses indicate that at least 90 and 98 wt% of the initial total polysaccharides in the buried alder and oak woods, respectively, have been degraded along with 15–25 wt% of the lignin. At least 75% of the degraded biopolymer has been physically lost from these samples. This evidence is supported by the SEM, 13 C NMR and elemental analyses, all of which indicate selective loss of the carbohydrate moiety. The following order of stability was observed for the major biochemical constituents of both buried hardwoods: vanillyl and p- hydroxyl "> p-hydroxyl lignin structural units > syringyl and lignin structural units > pectin > α-cellulose > hemicellulose. This sequence can be explained by selective preservation of the compound middle lamella regions of the wood cell walls. The magnitude and selectivity of the indicated diagenetic reactions are sufficient to cause major changes in the chemical compositions of wood-rich sedimentary organic mixtures and to provide a potentially large in situ nutrient source.

Geochimica et Cosmochimica Acta

GELIFICATION OF WOOD DURING COALIFICATION.

Coalified wood was examined by SEM and CPMAS**1**3C NMR to delineate chemical and physical alterations responsible for gelification. Early coalification selectively degrades cellulosic components, preserving lignin-like components that are eventually transformed to coal. Cellular morphology persists until the chemical composition becomes uniform, at which point the cells coalesce under compaction and gelify.

Conference Paper

Coalification of organic matter in coal balls of the Pennsylvanian (upper Carboniferous) of the Illinois Basin, United States

An evaluation was made of the degree of coalification of two coal balls from the Illinois Basin of the Pennsylvanian (upper Carboniferous) of the United States. Previous interpretations are mainly misleading and contradictory, primarily because of the assumption that the brown color and exceptional cellular and subcellular preservation typical of American coal balls imply chemical preservation of cellulose and lignin, the primary components of peat. Xylem tissue from a medullosan seed fern contained in a coal ball and the coal attached to the coal ball from the Calhoun coal bed, Mattoon Formation, Illinois, was analyzed by elemental, petrographic, and nuclear magnetic resonance (NMR) techniques to determine the degree of coalification. The NMR and elemental data indicate the lack of cellulose and lignin and a probable rank of high-volatile C bituminous coal. These data corroborate data for a coal ball from the Herrin (No. 6) coal bed (Carbondale Formation, Middle Pennsylvanian) and support our hypothesis that the organic matter in coal balls of the Pennsylvanian strata of the United States is coalified to about the same degree as the surrounding coal. Data presented show a range of lower reflectances for xylem tissue and vitrinite in the analyzed coal balls compared with vitrinite in the attached coal. The data reported indicate that physical preservation of organic matter in coal balls does not imply chemical preservation. Also our study supports the hypothesis that compactional (static load) pressure is not a prerequisite for coalification up to a rank of high-volatile C bituminous coal. A whole-rock analysis of the Calhoun coal ball indicates a similarity to other carbonate coal balls from the United States. It consists primarily of calcium carbonate and 1–2% organic matter; silica and alumina together make up less than 0.5%, indicating the lack of minerals such as quartz and clays.

Illinois, Indiana, Kentucky

Carbon isotope fractionation of sapropelic organic matter during early diagenesis

Study of an algal, sapropelic sediment from Mangrove Lake, Bermuda shows that the mass balance of carbon and stable carbon isotopes in the major organic constituents is accounted for by a relatively straightforward model of selective preservation during diagenesis. The loss of 13 C-enriched carbohydrates is the principal factor controlling the intermolecular mass balance of 13 C in the sapropel. Results indicate that labile components are decomposed leaving as a residual concentrate in the sediment an insoluble humic substance that may be an original biochemical component of algae and associated bacteria. An overall decrease of up to about 4‰ in the δ 13 C values of the organic matter is observed as a result of early diagenesis.

Mangrove Lake

Resin rodlets in shale and coal (Lower Cretaceous), Baltimore Canyon Trough

Rodlets, occurring in shale and coal (uppermost Berriasian to middle Aptian, Lower Cretaceous), were identified from drill cuttings taken from depths between 9330 ft (2844 m) and 11, 460 ft (3493 m) in the Texaco et al., Federal Block 598, No. 2 well, in the Baltimore Canyon Trough. Under the binocular microscope, most of the rodlets appear black, but a few are reddish brown, or brownish and translucent on thin edges. They range in diameter from about 0.4 to 1.7 mm and are commonly flattened. The rodlets break with a conchoidal fracture, and some show an apparent cellular cast on their longitudinal surfaces. When polished and viewed in reflected light, the rodlets appear dark gray and have an average random reflectance of less than 0.1% whereas mean maximum reflectances are 0.48–0.55% for vitrinite in the associated shale and coal. These vitrinite reflectances indicate either subbituminous A or high-volatile C bituminous coal. The rodlets fluoresce dull gray yellow to dull yellow. The scanning electron microscope (SEM) and light microscope reveal the presence of swirl-like features in the rodlet interiors. Minerals associated with the rodlets occur as sand-size grains attached to the outer surface, as finely disseminated interior grains, and as fracture fillings. Electron microprobe and SEM-energy-dispersive X-ray (EDX) anlayses indicate that the minerals are dominantly clays (probably illite and chlorite) and iron disulfide; calcium carbonate, silicon dioxide, potassium aluminum silicate (feldspar), titanium dioxide, zinc sulfide, and iron sulfate minerals have been also identified. The rodlets were analyzed directly for C, H, N, O, and total S and are interpreted as true resins on the basis of C and H contents that range from 75.6 to 80.3 and from 7.4 to 8.7 wt. % (dry, ash-free basis), respectively. Elemental and infrared data support a composition similar to that of resinite from bituminous coal. Elements determined to be organically associated in the rodlets include S (0.2–0.5 wt.%), Cl (0.03–0.1 wt.%), and Si (0.05–0.08 wt.%). The ash content of the resin rodlets ranges from 4 to 24 wt.% and averages 12 wt.%. Total sulfur contents range from 1.7 to 3.6 wt.%. Resins of fossil plants are known to have little or no sulfur and ash; therefore, these data and the presence of minerals in fractures indicate that most of the sulfur and mineral matter were introduced into the resin partly or wholly after the time of brittle fracture of the resin. The probable source of the resin rodlets is fossil pinaceous conifer cones, which are known to have resin canals as much as 2400 μm in diameter.

International Journal of Coal Geology

Selective preservation and origin of petroleum-forming aquatic kerogen

Studies of a marine algal sapropel from Mangrove Lake, Bermuda, by 13C NMR and stable carbon isotopic methods show that precursors of aquatic kerogen (insoluble, macromolecular, paraffinic humic substances) are primary components of algae and possibly associated bacteria and that these substances survive microbial decomposition and are selectively preserved during early diagenesis. ?? 1983 Nature Publishing Group.

Nature

Eastern Devonian shales: Organic geochemical studies, past and present

The Eastern Devonian shales are represented by a sequence of sediments extending from New York state, south to the northern regions of Georgia and Alabama, and west into Ohio and to the Michigan and Ilinois Basins. Correlatives are known in Texas. The shale is regionally known by a number of names: Chattanooga, Dunkirk, Rhinestreet, Huron, Antrim, Ohio, Woodford, etc. These shales, other than those in Texas, have elicited much interest because they have been a source of unassociated natural gas. It is of particular interest, however, that most of these shales have no associated crude oil, in spite of the fact that they have some of the characteristics normally attributed to source beds. This paper addresses some of the organic geochemical aspects of the kerogen in these shales, in relation to their oil generating potential. Past organic geochemical studies on Eastern Devonian shales will be reviewed. Recent solid state 13C NMR studies on the nature of the organic matter in Eastern Devonian shales show that Eastern Devonian shales contain a larger fraction of aromatic carbon in their chemical composition. Thus, despite their high organic matter contents, their potential as a petroleum source rock is low, because the kerogen in these shales is of a "coaly" nature and hence more prone to producing natural gas.

Conference Paper

Organic geochemistry and pore water chemistry of sediments from Mangrove Lake, Bermuda

Mangrove Lake, Bermuda, is a small coastal, brackish-water lake that has accumulated 14 m of banded, gelatinous, sapropelic sediments in less than 10 4 yr. Stratigraphic evidence indicates that Mangrove Lake's sedimentary environment has undergone three major depositional changes (peat, freshwater gel, brackish-water gel) as a result of sea level changes. The deposits were examined geochemically in an effort to delineate sedimentological and diagenetic changes. Gas and pore water studies include measurements of sulfides, ammonia, methane, nitrogen gas, calcium, magnesium, chloride, alkalinity, and pH. Results indicate that sulfate reduction is complete, and some evidence is presented for bacterial denitrification and metal sulfide precipitation. The organic-rich sapropel is predominantly algal in origin, composed mostly of carbohydrates and insoluble macromolecular organic matter called humin with minor amounts of proteins, lipids, and humic acids. Carbohydrates and proteins undergo hydrolysis with depth in the marine sapropel but tend to be preserved in the freshwater sapropel. The humin, which has a predominantly aliphatic structure, increases linearly with depth and composes the greatest fraction of the organic matter. Humic acids are minor components and are more like polysaccharides than typical marine humic acids. Fatty acid distributions reveal that the lipids are of an algal and/or terrestrial plant source. Normal alkanes with a total concentration of 75 ppm exhibit two distribution maxima. One is centered about n -C 22 with no odd/even predominance, suggestive of a degraded algal source. The other is centered at n -C 31 with a distinct odd/even predominance indicative of a vascular plant origin. Stratigraphic changes in the sediment correlate to observed changes in the gas and pore water chemistry and the organic geochemistry.

Mangrove Lake

Organic matter in a coal ball: Peat or coal?

Chemical analyses of morphologically preserved organic matter in a Carboniferous coal ball reveal that the material is coalified to a rank approximately equal to that of the surrounding coal. Hence, the plant tissues in the coal ball were chemically altered by coalification processes and were not preserved as peat.

Science

Aliphatic structure of humic acids; a clue to their origin

Nuclear magnetic resonance spectra (both 1 H and 13 C) of humic acids from diverse depositional environments indicate the presence of aromatic chemical structures, most likely derived from lignin of vascular plants, and complex, paraffinic structures, most likely derived from algal or microbial sources. The latter components account for a major fraction of humic acid structures in both terrestrial and aquatic environments, suggesting that algae or microbes play a large role in humification of organic remains from both systems.

Organic Geochemistry