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At least 163 records · Page 9Linked to original sources
USGS1991

Studies of a peatified angiosperm log cross section from Indonesia by nuclear magnetic resonance spectroscopy and analytical pyrolysis

Samples from a 10 cm cross-sectional radius of a peatified angiosperm log from Sumatra, Indonesia, were examined by 13 C nuclear magnetic resonance and pyrolysis-gas chromatography in order to understand chemical changes due to the peatification process. NMR results show degradation by selective loss of carbohydrates in all parts of the log section compared with fresh wood; however, the degree of degradation is less near the center of the log section. The degree of ring substitution of aromatic lignin monomeric units, as measured by dipolar dephasing NMR methods, appears to be less at the center of the log section than at the periphery. The methoxyl carbon content of lignin in the log is lower than in unaltered angiospermous lignin but does not appear to change as a function of either radial position or the degree of aromatic ring substitution. Pyrolysis-gas chromatography indicates higher yields of catechols in the outer areas relative to the heartwood. Other than the variations in catechol contents and in the yields of carbohydrate-derived pyrolysis products (e.g. levoglucosan, angelicalactones), the pyrolysis results do not show significant changes related to radial position, indicating that the lignin is not significantly altered across the log section.

Organic Geochemistry↗
USGS1991

Organic petrology of epi-impsonite at Page, Oklahoma, U.S.A.

Impsonite (asphaltic pyrobitumen) occurs as fracture-filling veins cutting massive sandstone in the frontal Ouachita Mountains near Page, Oklahoma. The Page impsonite formed from low-temperature alteration of crude oil. Mean maximum bitumen reflectance in oil immersion ( R max "> R max ) of seven samples is 1.41–1.96%. Mean apparent bireflectance of these samples is 0.15–0.54%. The Page deposit classifies at the upper end of epi-impsonite in the generic classification for solid bitumen, based on physical, chemical, and optical characteristics, and as post-oil with unlimited migration in the genetic classification for solid bitumen.

Oklahoma↗
USGS1991

The effect of sample hydration on 13C CPMAS NMR spectra of fulvic acids

Three fulvic acids, two of which have been well studied by a number of other groups (Armadale and Suwannee river fulvic acids) have been examined by high resolution solid-state 13 C-NMR techniques to delineate the effect of absorbed water. Two main effects of absorbed water were observed: (1) changes in spin lattice relaxation times in the rotating frame and cross polarization times and (2) total loss of signal so that some fulvic acid is effectively in solution. These results suggest that discrepancies in the literature concerning observed relative signal intensities from different structural groups are due to absorbed water and emphasize the necessity for proper precautionary drying before spectroscopic analysis.

Organic Geochemistry↗
USGS1991

Variation of organic sulfur in macerals of selected Illinois Basin coals

An electron microbeam technique was used to determine the distribution of organic sulfur in the main macerals of five Illinois Basin coals. On average, sporinites are the highest, inertinites the lowest, and vitrinites intermediate in organic sulfur for each coal. The observed differences are likely due to varying affinities of the different pre-maceral materials for sulfur and/or local variation in the production of H 2 S primarily during the peat stage. Investigation of molecular structures of individual macerals in relation to the findings of this study may delineate the relative abundance of organic sulfur in various organic compounds and thus lead to the development of efficient desulfurization processes.

Organic Geochemistry↗
USGS1991

Examination of micrinite concentrates from the Cannel City coal bed of eastern Kentucky: Proposed mechanism of formation

A high volatile B, micrinite-rich bituminous coal from Morgan County, Kentucky, was crushed and screened to −100 mesh, demineralized and subjected to density gradient centrifugation (DGC). In an initial density separation, micrinite concentration was increased from 52 vol% in the demineralized coal to a maximum of 67% in the 1.25–1.26 g/ml density fraction. Micrinite enriched fractions (1.21–1.29 g/ml) were combined to yield a sample containing ∼61% micrinite. This sample was crushed to −200 mesh in an attempt to enhance micrinite liberation then reprocessed by DGC. Reprocessing resulted in a slight increase in purity to 69 vol% in the 1.25–1.28 g/ml density fraction. The original −100 mesh sample was density separated a second time with the material recovered between 1.22 and 1.30 g/ml combined, crushed, screened past 325 mesh and reprocessed by DGC. Micrinite was recovered at a purity ranging up to 73% (1.27–1.28 g/ml) from the −325 mesh sample. A density of 1.26g/ml and H/C atomic ratio of 0.79 was calculated for micrinite in one of the higher purity micrinite fractions. These values are notably different than published fusinite values and are more similar to vitrinite values measured in high volatile-B coals. The results from this study suggest that the partitioning of micrinite to a density near that of vitrinite was governed by the inherent micrinite density and not particle aggregation. Transition of the micrinite precursors through a mobile liquid phase is proposed as an explanation for the discrepancy between chemical properties and reflectance as well as to account for the observed microlithological occurrences of micrinite in this sample.

Kentucky↗
USGS1991

Volcanic ash dispersed in the Wyodak-Anderson coal bed, Powder River Basin, Wyoming

Minerals derived from air-fall volcanic ash were found in two zones in the upper Paleocene Wyodak-Anderson coal bed of the Fort Union Formation in the Powder River Basin of Wyoming, and are the first reported evidence of such volcanic material in this thick (> 20 m) coal bed. The volcanic minerals occur in zones that are not visually obvious because they contain little or no clay. These zones were located by geophysical logs of the boreholes and X-ray radiography of the cores. The zones correspond to two of a series of incremental core samples of the coal bed that have anomalous concentrations of Zr, Ba, Nb, Sr, and P 2 O 5 . Two suites of minerals were found in both of the high-density zones. A primary suite (not authigenic) consists of silt-sized quartz grains, biotite, and minor zircon. A minor suite consists of authigenic minerals, including calcite, pyrite, kaolinite, quartz, anatase, barite, and an alumino-phosphate (crandallite?). The original volcanic ash is inferred to have consisted of silica glass containing phenocrysts of quartz, biotite, zircon, and possibly, associated feldspars, pyroxenes, and amphiboles. The glass, as well as the less stable minerals, probably dissolved relatively quickly and contributed to the minor authigenic mineral suite or was removed from the peat as a result of the prevailing hydrologic conditions present in a raised peat formation. This type of volcanic ash suggests that suggests that volcanic material could have rained on the peat; this fallout may have also had a fertilizing effect on the peat by providing nutrients essential for plant growth thus contributing to the thick accumulations of the Wyodak-Anderson bed. Notwithstanding, the presence of these minerals provides evidence for the contribution by volcanic sources to the mineral content of coal, but not as tonsteins.

Wyoming↗
USGS1992

The influence of pressure on petroleum generation and maturation as suggested by aqueous pyrolysis

Because fluid pressures are transient in sedimentary basins over geologic time, the effect of increasing fluid pressure on organic-matter metamorphism is difficult to determine, and conflicting opinions exist concerning its influence. Properly-performed aqueous-pyrolysis experiments can closely simulate hydrocarbon generation and maturation in nature, and thus offer an excellent way to study the influence of pressure. Such experiments, carried out on the Retort Phosphatic Shale Member of the Lower Permian Phosphoria Formation (type II-S organic matter) at different constant temperatures, demonstrated that increasing pressure significantly retards all aspects of organic matter metamorphism, including hydrocarbon generation, maturation and thermal destruction. This conclusion results from detailed quantitative and qualitative analyses of all products from hydrocarbon generation, from the C 1 to C 4 hydrocarbon gases to the asphaltenes, and also from analyses of the reacted rocks. We have documented that our aqueous-pyrolysis experiments closely simulated natural hydrocarbon generation and maturation. Thus the data taken as a function of pressure have relevance to the influence of normal and abnormal fluid pressures as related to: 1) depths and temperatures of mainstage hydrocarbon generation; 2) the thermal destruction of deposits of gas or light oil, or their preservation to unexpectedly high maturation ranks; and 3) the persistence of measurable to moderate concentrations of C 15 + hydrocarbons in fine-grained rocks even to ultra-high maturation ranks.

Organic Geochemistry↗
USGS1992

Hydrous pyrolysis of crude oil in gold-plated reactors

Crude oils from Iraq and California have been pyrolyzed under hydrous conditions at 200 and 300°C for time periods up to 210 days, in gold-plated reactors. Elemental (vanadium, nickel), stable isotopic (carbon), and molecular ( n -alkanes, acyclic isoprenoids, steranes, terpanes and aromatic steroid hydrocarbons) analyses were made on the original and pyrolyzed oils. Various conventional crude oil maturity parameters, including 20 S /(20 S + 20 R )-24-ethylcholestane ratios and the side-chain-length distribution of aliphatic and aromatic steroidal hydrocarbons, were measured in an effort to assess the modification of molecular maturity parameters in clay-free settings, similar to those encountered in “clean” reservoirs. Concentrations of vanadium and nickel in the Iraq oil decrease significantly and the V/(V + Ni) ratio decreases slightly, with increasing pyrolysis time/temperature. Whole oil carbon isotope ratios remain fairly constant during pyrolysis, as do hopane/sterane ratios and carbon number distribution of 5 α (H),14 α (H),17 α (H),20 R steranes. These latter three parameters are considered maturity-invariant. The ratios of short side-chain components to long side-chain components of the regular steranes [C 21 /(C 21 + C 29 R )] and the triaromatic steroid hydrocarbons [C 21 /(C 21 + C 28 )] vary systematically with increasing pyrolysis time, indicating that these parameters may be useful as molecular maturity parameters for crude oils in clay-free reservoir rocks. In addition, decreases in bisnorhopane/hopane ratio with increasing pyrolysis time, in a clay-free and kerogen-free environment, suggest that the distribution of these compounds is controlled by either differential thermal stabilities or preferential release from a higher-molecular weight portion of the oil.

Organic Geochemistry↗
USGS1992

Quantitative solid-state 13C nuclear magnetic resonance spectrometric analyses of wood xylen: Effect of increasing carbohydrate content

Isolated lignin with a low carbohydrate content was spiked with increasing amounts of alpha-cellulose, and then analysed by solid-state 13 C nuclear magnetic resonance (NMR) using cross-polarization with magic angle spinning (CPMAS) and dipolar dephasing methods in order to assess the quantitative reliability of CPMAS measurement of carbohydrate content and to determine how increasingly intense resonances for carbohydrate carbons affect calculations of the degree of lignin's aromatic ring substitution and methoxyl carbon content. Comparisons were made of the carbohydrate content calculated by NMR with carbohydrate concentrations obtained by phenol-sulfuric acid assay and by the calculation from the known amounts of cellulose added. The NMR methods used in this study yield overestimates for carbohydrate carbons due to resonance area overlap from the aliphatic side chain carbons of lignin. When corrections are made for these overlapping resonance areas, the NMR results agree very well with results obtained by other methods. Neither the calculated methoxyl carbon content nor the degree of aromatic ring substitution in lignin, both calculated from dipolar dephasing spectra, change with cellulose content. Likewise, lignin methoxyl content does not correlate with cellulose abundance when measured by integration of CPMAS spectra.

Organic Geochemistry↗
USGS1992

Isolation of hydrophilic organic acids from water using nonionic macroporous resins

A method has been developed for the isolation of hydrophilic organic acids from aquatic environments using Amberlite ∗ XAD-4 resin. The method uses a two column array of XAD-8 and XAD-4 resins in series. The hydrophobic organic acids, composed primarily of aquatic fulvic acid, are removed from the sample on XAD-8, followed by the isolation of the more hydrophilic organic acids on XAD-4. For samples from a number of diverse environments, more of the dissolved organic carbon was isolated on the XAD-8 resin (23–58%) than on the XAD-4 resin (7–25%). For these samples, the hydrophilic acids have lower carbon and hydrogen contents, higher oxygen and nitrogen contents, and are lower in molecular weight than the corresponding fulvic acids. 13 C NMR analyses indicate that the hydrophilic acids have a lower concentration of aromatic carbon and greater heteroaliphatic, ketone and carboxyl content than the fulvic acid.

Organic Geochemistry↗
USGS1993

Comparison of the petrography, palynology and paleobotany of the Stockton coal bed, West Virginia and implications for paleoenvironmental interpretations

The Stockton coal bed (Middle Pennsylvanian) is a relatively high ash coal composed primarily of moderately thin banded, sparsely thin banded, and nonbanded coal (splint and cannel coal). Comparisons of petrographic, palynologic, and paleobotanic data gathered from the same sample sets from a single column of the Stockton coal bed indicate that compositional correspondences among the sets exist regardless of coal type. Some correspondences are believed to exist because of original plant constituents and others because of the paleoenvironment of peat formation. Using some combination of these data is critical when interpreting paleoenvironmental conditions because (1) a direct correspondence is lacking between many of the data and (2) each of the three data sets provides a unique and important perspective on the paleomire. The Stockton paleomire in the area of this study supported a diverse flora that consisted of both small and arboreous lycopsids, small ferns and tree ferns, calamites, cordaites, and pteridosperms. There appear to have been two successions of Lycospora spore-dominated, vitrinite-rich, liptinite-poor peat formation, which were followed by inertinite-rich peat formation marked by a tree fern-dominant spore assemblage and abundant unidentifiable plant tissues. These are interpreted to be two water-laden or topogenous peat formational stages followed by slightly domed, better drained peat formation.

West Virginia↗
USGS1993

Rotational reflectance properties of Arkoma Basin dispersed vitrinite: Insights for understanding reflectance populations in high thermal maturity regions

Analysis and interpretation of dispersed vitrinite reflectance data in regions of high thermal maturity (> 2% vitrinite reflectance) have been equivocal partly because of an increase in width and complexity of reflectance histograms with increasing mean reflectance. Such complexity is illustrated by random reflectance ( R ran ) data from the Arkoma Basin that display a linear increase in standard deviation of R ran with an increase in mean R ran from 1 to 5%. Evaluating how much of the dispersion in these data is the result of vitrinite anisotropy and how much is the result of mixing of kerogen populations by sedimentary processes and/or sampling procedures has been problematic. Automated collection of reflectance data during polarizer rotation provides preliminary data for solution of this problem. Rotational reflectance data collected from a subset of Arkoma Basin samples reveal positive, linear relationships among maximum ( R ′ max ), random ( R ran ), rotational ( R rot ), and minimum ( R ′ min ) reflectance, as well as a systematic increase in bireflectance ( R ′ max – R ′ min ) with increasing reflectance. R ′ max and R rot display lower standard deviations and narrower, more nearly unimodal histograms than R ran and R ′ min , suggesting that R ′ max and R rot are superior (less ambiguous) indices of thermal maturity. These data patterns are inferred to be mostly an indication of increasing vitrinite anisotropy with increasing thermal maturity, suggesting that the linear covariance observed between mean R ran and standard deviation in dispersed organic data sets from regions of high thermal maturity may be explained mostly as the result of increasing vitrinite anisotropy with increasing thermal maturity.

Arkansas, Oklahoma↗
USGS1993

Differentiation of volcanic ash-fall and water-borne detrital layers in the Eocene Senakin coal bed, Tanjung Formation, Indonesia

The Sangsang deposit of the Eocene Senakin coal bed, Tanjung Formation, southeastern Kalimantan, Indonesia, contains 11 layers, which are thin (<5 cm) and high in ash (> 70%). These layers are characterized by their pelitic macroscopic texture. Examination of eight of the layers by scanning-electron microscopy, energy-dispersive X-ray, and X-ray diffraction analyses show that they are composed primarily of fairly well-crystallized kaolinite, much of which is vermicular. Accessory minerals include abundant Ti oxide, rare-earth element-rich Ca and A1 phosphates, quartz that luminescences in the blue color range, and euhedral to subhedral pyroxene, hornblende, zircon, and sanidine. Although this mineral suite is suggestive of volcanic ash-fall material, only the four pelitic layers in the middle of the bed are thought to be solely derived from volcanic ash-falls on the basis of diagnostic minerals, replaced glass shards, and lithostratigraphic relationships observed in core and outcrop. The three uppermost pelitic layers contain octahedral chromites, some quartz grains that luminesce in teh orange color range, and some quartz grains that contain two-phase fluid inclusions. These layers are interpreted to be derived from a combination of volcanic ash-fall material and hydrologic transport of volcaniclastic sediment. In contrast, the lowermost pelitic layer, which contains large, rounded FeMg-rich chromites, is thought to have been dominantly deposited by water. The source of the volcanic ash-fall material may have been middle Tertiary volcanism related to plate tectonic activity between Kalimantan and Sulawesi. The volcanic ash was deposited in sufficient amounts to be preserved as layers within the coal only in the northern portions of the Senakin region: the southern coal beds in the region do not contain pelitic layers.

southeastern Kalimantan↗
USGS1993

SEM-EDX and isotope characterization of the organic sulfur in macerals and chars in Illinois Basin coals

Two samples of the Herrin (Illinois No. 6) Coal and one sample of the Colchester (Illinois No. 2) Coal from the Illinois Basin were studied to evaluate the spatial distribution of organic sulfur within macerals occurring next to pyrite grains, both in the raw coal and their chars. The chars were produced by pyrolysing the coal at 250–550°C in a nitrogen atmosphere. Representative splits of the coals and their chars were mounted in epoxy and polished for optical microscopy and scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDX). Determinations of organic sulfur concentrations were made at 996 locations within macerals, mostly vitrinite, around 115 grains of pyrite and at 50 locations around 5 pores in chars. The pyrite considered here is restricted to the disseminated type within macerals. On the average, the organic sulfur content increased near pyrite grains after the coals were charred at 550°C, indicating that some of the pyritic sulfur released during charring was retained within the organic matrix rather than being emitted to the atmosphere. One of the coal samples and its chars were isotopically characterized by chemically separating the pyritic and organic sulfur fractions, followed by analyzing the isotopes of the sulfur forms with a Nuclide 6–60 ratio mass spectrometer. The sulfur isotope (δ 34 S) data confirmed the movement of pyritic sulfur into the macerals after charring to 550°C. About 18% of the organic sulfur that remained in the 550°C char had originally been pyritic sulfur in the untreated coal.

Organic Geochemistry↗
USGS1993

An empirical determination of the minimum number of measurements needed to estimate the mean random vitrinite reflectance of disseminated organic matter

In coal samples, published recommendations based on statistical methods suggest 100 measurements are needed to estimate the mean random vitrinite reflectance ( R v−r ) to within ±2%. Our survey of published thermal maturation studies indicates that those using dispersed organic matter (DOM) mostly have an objective of acquiring 50 reflectance measurements. This smaller objective size in DOM versus that for coal samples poses a statistical contradiction because the standard deviations of DOM reflectance distributions are typically larger indicating a greater sample size is needed to accurately estimate R v−r in DOM. However, in studies of thermal maturation using DOM, even 50 measurements can be an unrealistic requirement given the small amount of vitrinite often found in such samples. Furthermore, there is generally a reduced need for assuring precision like that needed for coal applications. Therefore, a key question in thermal maturation studies using DOM is how many measurements of R v−r are needed to adequately estimate the mean. Our empirical approach to this problem is to compute the reflectance distribution statistics: mean, standard deviation, skewness, and kurtosis in increments of 10 measurements. This study compares these intermediate computations of R v−r statistics with a final one computed using all measurements for that sample. Vitrinite reflectance was measured on mudstone and sandstone samples taken from borehole M-25 in the Cerro Prieto, Mexico geothermal system which was selected because the rocks have a wide range of thermal maturation and a comparable humic DOM with depth. The results of this study suggest that after only 20–30 measurements the mean R v−r is generally known to within 5% and always to within 12% of the mean R v−r calculated using all of the measured particles. Thus, even in the worst case, the precision after measuring only 20–30 particles is in good agreement with the general precision of one decimal place recommended for mean R v−r measurements on DOM. The coefficient of variation ( V = standard deviation/mean) is proposed as a statistic to indicate the reliability of the mean R v−r estimates made at n ⪡ 20. This preliminary study suggests a V < 0.1 indicates a reliable mean and a V > 0.2 suggests an unreliable mean in such small samples.

Organic Geochemistry↗
USGS1993

Rock-eval pyrolysis and vitrinite reflectance trends in the Cleveland Shale Member of the Ohio Shale, eastern Kentucky

Within eastern Kentucky, organic petrographic and geochemical data indicate a southeastwards increase in maturation of the Cleveland Shale Member of the Ohio Shale (Devonian-Mississippian). Reflectance levels of dispersed organic material in the Cleveland Shale increase from 0.5% in the outcrop belt in central Kentucky, to slightly over 1.0% in Pike County, eastern Kentucky. A decrease in fluorescence intensity of liptinitic components, such as Tasmanites , accompanies this reflectance increase, as does a shift in fluorescence color of the alginite towards the red. In the highest rank areas, fluorescence is almost absent. Groundmass fluorescence is observed also, and follows trends similar to those shown by the alginite. Kerogen in the Cleveland Shale is primarily Type II, as indicated by petrographic observations and Rock-Eval data. Total organic carbon contents of this shale decrease from over 12% in the outcrop belt, to less than 2% in the eastern-most part of the study area. Source rock potential ranges from good to very good, with the highest potentials occurring in the outcrop belt. T max values for this unit increase from under 430°C in the outcrop belt to over 450°C in the southeast, confirming the increase in maturation trends indicated by vitrinite reflectance data. Both petrographic and geochemical maturation parameters place the Cleveland Shale of eastern Kentucky within the oil window. Comparison with maturation data for Pennsylvanian-age coals upsection suggests that maturation indices are retarded, or suppressed, in the Devonian shales. The level of maturation indicated for the Cleveland may be problematical considering that the Ohio Shale is a major gas-producer in this area.

Kentucky↗
USGS1993

Geochemical evaluation of upper cretaceous fruitland formation coals, San Juan Basin, New Mexico and Colorado

Geochemical analyses of coal samples from the Upper Cretaceous Fruitland Formation in the San Juan Basin of New Mexico and Colorado were used to determine thermal maturity, type of kerogen, and hydrocarbon generation potential. Mean random vitrinite reflectance (% R m ) of the Fruitland coal ranges from 0.42 to 1.54%. Rock-Eval pyrolysis data and saturated to aromatic hydrocarbon ratio indicate that the onset of thermal hydrocarbon generation begins at about 0.60% R m and peak generation occurs at about 0.85% R m . Several samples have hydrogen index values between 200 and 400, indicating some potential for liquid hydrocarbon generation and a mixed Type III and II kerogen. Pentacyclic and tricyclic terpanes, steranes, aromatic steroids and methylphenanthrene maturity parameters were observed through the complete range of thermal maturity in the Fruitland coals. Aromatic pentacyclic terpanes, similar to those found in brown coals of Australia, were observed in low maturity samples, but not found above 0.80% R m . N -alkane depleted coal samples, which occur at a thermal maturity of approx. 0.90% R m , paralleling peak hydrocarbon generation, are fairly widespread throughout the basin. Depletion of n -alkanes in these samples may be due to gas solution stripping and migration fromthe coal seams coincident with the development of pressure induced fracturing due to hydrocarbon generation; however, biodegradation may also effect these samples.

Colorado, New Mexico↗
USGS1994

Laboratory simulation of hydrothermal petroleum formation from sediment in Escanaba Trough, offshore from northern California

Petroleum associated with sulfide-rich sediment is present in Escanaba Trough at the southern end of the Gorda Ridge spreading axis offshore from northern California within the Exclusive Economic Zone (EEZ) of the U.S. This location and occurrence are important for evaluation of the mineral and energy resource potential of the seafloor under U.S. jurisdiction. In Escanaba Trough, petroleum is believed to be formed by hydrothermal processes acting on mainly terrigenous organic material in Quaternary, river-derived sediment. To attempt to simulate these processes in the laboratory, portions of a Pleistocene gray-green mud, obtained from ∼ 1.5 m below the seafloor at a water depth of ∼ 3250 m in Escanaba Trough, were heated in the presence of water in four hydrous-pyrolysis experiments conducted at temperatures ranging from 250 to 350°C and at a pressure of 350 bar for 1.0–4.5 days. Distributions of n -alkanes, isoprenoid hydrocarbons, triterpanes, and steranes in the heated samples were compared with those in a sample of hydrothermal petroleum from the same area. Mud samples heated for less than 4.5 days at less than 350°C show changes in some, but not all, molecular marker ratios of organic compounds that are consistent with those expected during hydrothermal petroleum formation. Our results suggest that the organic matter in this type of sediment serves as one possible source for some of the compounds found in the hydrothermal petroleum.

California↗