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Origins of organic geochemistry

When organic geochemistry actually began as a recognized geoscience is a matter of definition and perspective. Constraints on its beginning are placed by the historical development of its parent disciplines, geology and organic chemistry. These disciplines originated independently and developed in parallel, starting in the latter half of the 18th century and flourishing thereafter into the 21st century. Organic geochemistry began sometime between 1860 and 1983; I argue that 1930 is the best year to mark its origin.

Organic Geochemistry↗

Organic geochemistry - A retrospective of its first 70 years

Organic geochemistry had its origin in the early part of the 20th century when organic chemists and geologists realized that detailed information on the organic materials in sediments and rocks was scientifically interesting and of practical importance. The generally acknowledged "father" of organic geochemistry is Alfred E. Treibs (1899-1983), who discovered and described, in 1936, porphyrin pigments in shale, coal, and crude oil, and traced the source of these molecules to their biological precursors. Thus, the year 1936 marks the beginning of organic geochemistry. However, formal organization of organic geochemistry dates from 1959 when the Organic Geochemistry Division (OGD) of The Geochemical Society was founded in the United States, followed 22 years later (1981) by the establishment of the European Association of Organic Geochemists (EAOG). Organic geochemistry (1) has its own journal, Organic Geochemistry (beginning in 1979) which, since 1988, is the official journal of the EAOG, (2) convenes two major conferences [International Meeting on Organic Geochemistry (IMOG), since 1962, and Gordon Research Conferences on Organic Geochemistry (GRC), since 1968] in alternate years, and (3) is the subject matter of several textbooks. Organic geochemistry is now a widely recognized geoscience in which organic chemistry has contributed significantly not only to geology (i.e., petroleum geochemistry, molecular stratigraphy) and biology (i.e., biogeochemistry), but also to other disciplines, such as chemical oceanography, environmental science, hydrology, biochemical ecology, archaeology, and cosmochemistry.

Conference Paper↗

History of the recognition of organic geochemistry in geoscience

The discipline of organic geochemistry is an outgrowth of the application of the principles and methods of organic chemistry to sedimentary geology. Its origin goes back to the last part of the nineteenth century and the first part of the twentieth century concurrent with the evolution of the applied discipline of petroleum geochemistry. In fact, organic geochemistry was strongly influenced by developments in petroleum geochemistry. Now, however, organic geochemistry is considered an umbrella geoscience discipline of which petroleum geochemistry is an important component.

Organic Geochemistry↗

Fifty years of IMOG (International Meetings on Organic Geochemistry)

IMOG2011 is the 25th of a series of international meetings on organic geochemistry that began in 1962. Thus, this 25th meeting marks the 50th anniversary year of IMOG, which has (a) had a rich history with meetings taking place in 11 different countries, (b) published Proceedings, titled “Advances in Organic Geochemistry,” from each meeting that now number 24 volumes totaling almost 18,000 pages, and (c) documented the content and development of the science of organic geochemistry. IMOG2011 adds a new milestone to the progress of organic geochemistry through time.

Organic Geochemistry↗

Organic geochemistry on Leg 104

The Leg 104 organic geochemistry program consisted of monitoring (a) hydrocarbon gases, (b) organic and inorganic carbon, and (c) parameters resulting from Rock-Eval pyrolysis at three sites on the Vdring Plateau. The results amplify some of those obtained earlier on Deep Sea Drilling Project (DSDP) Leg 38. In a regional sense there is an inverse correlation between amounts of hydrocarbon gas and organic carbon. For example, significant concentrations of methane are present only at Site 644 in the inner part of the plateau where organic carbon contents are always less than 1%; in contrast, at Site 642 on the outer plateau, methane concentrations are very low (ppm range) whereas amounts of organic carbon approach 2%. Only at Site 644 are the environmental conditions such that methanogenesis is an active diagenetic process. Because of the importance of routine gas analyses to the Ocean Drilling Program (ODP), a procedure was devised to improve the use of Vacutainers for collection of gas samples. Comparison of methods for determining organic carbon showed that at Sites 643 and 644 Rock-Eval TOC could be used as a measure of organic carbon, but not at Site 642. Although no liquid or solid hydrocarbons were encountered at any of the sites, a catalog of potential organic geochemical contaminants was developed in anticipation of such a discovery.

Proceedings of the Ocean Drilling Program: Scienti↗

Organic geochemistry applied to environmental assessments of Prince William Sound, Alaska, after the Exxon Valdez oil spill—a review

Organic geochemistry played a major role in the environmental assessments conducted following the Exxon Valdez oil spill, which occurred on March 24, 1989, and released about 258,000 bbls (41 million liters) of Alaska North Slope crude oil into Prince William Sound. Geochemical analyses of more than 15,000 sediment, tar, and biological samples and about 5000 water samples provide the largest database yet collected on oil-spill chemistry, and we review the results here. The marine environment of the Sound has a complex background of petrogenic, pyrogenic, and biogenic hydrocarbons from natural and anthropogenic sources. Geochemical evaluation of the fate and effects of the spilled oil required that this oil and its residues be distinguished from the background. A variety of molecular and isotopic techniques were employed to identify various hydrocarbon sources and to distinguish quantitatively among mixed sources in the samples. Although the specific criteria used to distinguish multiple sources in the region affected by the Exxon Valdez spill are not necessarily applicable to all spill situations, the principles that governed their selection are. Distributions of polycyclic aromatic hydrocarbons (PAH) and dibenzothiophenes distinguish Exxon Valdez oil and its weathered residues from background hydrocarbons in benthic sediments. Ratios of C 2 -dibenzothiophene C 2 -phenanthrene "> C 2 -dibenzothiopheneC 2 -phenanthrene and C 3 -dibenzothiophene C 3 -phenanthrene "> C 3 -dibenzothiopheneC 3 -phenanthrene were particularly useful. Carbon isotopes and terpane distributions distinguished Exxon Valdez residues found on shorelines from tars from other sources. Diesel and diesel soot were identified by the absence of alkylated chrysenes and a narrow distribution of n -alkanes, whereas pyrogenic products were distinguished by the dominance of 4- to 6-ring PAH over 2- to 3-ring PAH and by the dominance of non-alkylated over alkylated homologues of each PAH series. The presence of 18α(H)-oleanane in benthic sediments, coupled with its absence in Exxon Valdez oil and its residues, confirm another petrogenic source. Results of geochemical studies suggest that the petrogenic component in the background of benthic sediments is derived from oil seeps in the eastern Gulf of Alaska. In 1990 and 1991, Exxon Valdez residues, generally forming a small increment to the pre-spill background, were found to be only sporadically distributed in some shallow, near shore sediments adjacent to shorelines that had been heavily oiled in 1989. In 1994, occurrences of Exxon Valdez tars on shoreline surfaces were rare, although residues could be found buried in shoreline sediments at some isolated locations along the spill path where they were protected from wave action. Spilled oil residues collected 16 months after the spill were degraded, on average, by nearly 50%. Shoreline residues from sources other than the spill were also identified and are widespread throughout the Sound. These residues include (1) geochemically distinct tars and oils imported from California oil fields to Alaska for fuel and construction purposes prior to the discovery of the Cook Inlet and North Slope oil fields, (2) diesel and diesel soot, and (3) more highly refined products. Of the more than 2700 chemical analyses of biological samples of higher life forms (fish, birds, and mammals) about 150 (6%) indicate recognizable residues of Exxon Valdez oil, which were identified by their distribution of polycyclic aromatic hydrocarbons (PAH). Most of these samples (138) were collected in 1989 and most were associated with external surfaces or the gastrointestinal tract. Rarely do internal tissues or fluids contain recognizable fingerprints of spilled oil. This observation includes samples from marine mammals that were visibly oiled externally. Other hydrocarbon sources, including diesel and a non-petroleum artifact that occurs when concentrations of individual PAH are at or near their method detection limit, are also identified in biological samples.

Alaska↗

Molecular markers and their use in environmental organic geochemistry

Molecular markers are organic substances that carry information about sources of organic matter or contamination. The source/marker relation can be used to indicate the presence of a given source material (qualitative), or, under appropriate conditions, to estimate the amount of a source material (quantitative source apportionment) in the environment. Assemblages of markers can also be used as process probes. In this instance, systematic differences and/or similarities in the physical-chemical properties of markers are coupled with compositional changes in marker composition to infer the operation of natural processes. This paper provides an overview of what molecular markers are, what types of markers are present in the environment, the requirements for the use of markers, and some common applications. To illustrate how molecular markers can answer specific environmental questions, three case studies are presented. The first case study examines the impact of municipal waste on a large urban harbor (Boston Harbor). Linear alkylbenzenes (unreacted residues of linear alkylbenzenesulfonate surfactants) and coprostanol (a fecal indicator) provide information on the sources and likely transport pathways of municipal wastes in a complex hydrologic system. The marker data are also used to estimate the proportion of sewage-derived poly chlorinated biphenyls (PCBs) in polluted harbor sediments. The second case study concerns a portion of the continental shelf off southern California (Palos Verdes) where discharge of municipal wastewaters has led to extensive contamination of sediments and biota. Long-chain alkylbenzenes (surfactant residues), PCBs and the pesticide, DDT (dichlorodiphenyltrichloroethane), are used to develop sedimentation rate estimates for several time periods by molecular stratigraphy. These results, when combined with other information, allow conclusions to be drawn about the most likely transport pathway of sediments at the study site and to predict the fate of historically deposited contaminants. Finally, an investigation of a crude-oil spill in Bemidji, MN illustrates how monoaromatic hydrocarbons can be exploited as process probes, providing insights into the relative importance of different attenuation processes in a contaminated aquifer. The results show that natural attenuation of the monoaromatic hydrocarbons is occurring at this site and is dominated, not by physical and/or chemical processes, but by biodegradation.

Book chapter↗

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↗

A 450-year record of environmental change from Castle Lake, California (USA), inferred from diatoms and organic geochemistry

A 39-cm sediment core from Castle Lake, California (USA) spans the last ~ 450 years and was analyzed for diatoms and organic geochemistry (δ 15 N, δ 13 C, and C:N), with the goal of determining sensitivity to natural climate variation and twentieth century anthropogenic effects. Castle Lake is a subalpine, nitrogen-limited lake with ~ 5 months of annual ice cover. Human impacts include light recreational use, past fish stocking, and experimental use by the Castle Lake Research Station. The base of the core (below 32 cm; pre mid-1700s) represents the period of maximum ice cover. In contrast, the end of the Little Ice Age (mid 1700s–early 1800s) is dominated by cyclotelloids (mostly Discostella stelligera ), indicating significant open-water periods, a condition that persisted into the early 1900s. Cyclotelloids began to decline in the 1960s and were replaced by the Fragilaria tenera grp. (peak in 1970s), succeeded by Asterionella formosa (peak ~ 2010), and accompanied by a reduction in δ 15 N values and a decrease in C:N that may represent increased atmospheric nitrogen deposition. Another anthropogenic signal was discerned in the core and was interpreted to be the result of an ammonium nitrate fertilization experiment of the epilimnion that was conducted in 1980 and 1981. This signal was manifested in the core largely by a negative excursion in δ 15 N, possibly caused by fractionation during denitrification in surface sediment. A phytoplankton monitoring dataset collected by the Castle Lake Research Station from 1967 to 1984 corroborates the timing of increased araphid euplanktonic species in the 1970s, and increases in two benthic diatoms ( Staurosirella pinnata and Tabellaria fenestrata) , entrained in the phytoplankton tows during the experimentation years. Both ice cover and nitrogen addition appear to be strong drivers that affected the lake diatoms, although additional drivers, such as fish stocking and associated cascade effects need further exploration. These data will be helpful for interpreting longer core records from Castle Lake, should the opportunity arise, as well as cores from similar systems in the region.

California↗

Method of analysis and quality-assurance practices by the U.S. Geological Survey Organic Geochemistry Research Group: Determination of geosmin and methylisoborneol in water using solid-phase microextraction and gas chromatography/mass spectrometry

A method for the determination of two common odor-causing compounds in water, geosmin and 2-methylisoborneol, was modified and verified by the U.S. Geological Survey's Organic Geochemistry Research Group in Lawrence, Kansas. The optimized method involves the extraction of odor-causing compounds from filtered water samples using a divinylbenzene-carboxen-polydimethylsiloxane cross-link coated solid-phase microextraction (SPME) fiber. Detection of the compounds is accomplished using capillary-column gas chromatography/mass spectrometry (GC/MS). Precision and accuracy were demonstrated using reagent-water, surface-water, and ground-water samples. The mean accuracies as percentages of the true compound concentrations from water samples spiked at 10 and 35 nanograms per liter ranged from 60 to 123 percent for geosmin and from 90 to 96 percent for 2-methylisoborneol. Method detection limits were 1.9 nanograms per liter for geosmin and 2.0 nanograms per liter for 2-methylisoborneol in 45-milliliter samples. Typically, concentrations of 30 and 10 nanograms per liter of geosmin and 2-methylisoborneol, respectively, can be detected by the general public. The calibration range for the method is equivalent to concentrations from 5 to 100 nanograms per liter without dilution. The method is valuable for acquiring information about the production and fate of these odor-causing compounds in water.

Open-File Report↗

Methods of analysis by the U.S. Geological Survey Organic Geochemistry Research Group--Determination of dissolved isoxaflutole and its sequential degradation products, diketonitrile and benzoic acid, in water using solid-phase extraction and liquid chromatography/tandem mass spectrometry

An analytical method for the determination of isoxaflutole and its sequential degradation products, diketonitrile and a benzoic acid analogue, in filtered water with varying matrices was developed by the U.S. Geological Survey Organic Geochemistry Research Group in Lawrence, Kansas. Four different water-sample matrices fortified at 0.02 and 0.10 ug/L (micrograms per liter) are extracted by vacuum manifold solid-phase extraction and analyzed by liquid chromatography/tandem mass spectrometry using electrospray ionization in negative-ion mode with multiple-reaction monitoring (MRM). Analytical conditions for mass spectrometry detection are optimized, and quantitation is carried out using the following MRM molecular-hydrogen (precursor) ion and product (p) ion transition pairs: 357.9 (precursor), 78.9 (p), and 277.6 (p) for isoxaflutole and diketonitrile, and 267.0 (precursor), 159.0 (p), and 223.1 (p) for benzoic acid. 2,4-dichlorophenoxyacetic acid-d3 is used as the internal standard, and alachlor ethanesulfonic acid-d5 is used as the surrogate standard. Compound detection limits and reporting levels are calculated using U.S. Environmental Protection Agency procedures. The mean solid-phase extraction recovery values ranged from 104 to 108 percent with relative standard deviation percentages ranging from 4.0 to 10.6 percent. The combined mean percentage concentration normalized to the theoretical spiked concentration of four water matrices analyzed eight times at 0.02 and 0.10 ug/L (seven times for the reagent-water matrix at 0.02 ug/L) ranged from approximately 75 to 101 percent with relative standard deviation percentages ranging from approximately 3 to 26 percent for isoxaflutole, diketonitrile, and benzoic acid. The method detection limit (MDL) for isoxaflutole and diketonitrile is 0.003 ug/L and 0.004 ug/L for benzoic acid. Method reporting levels (MRLs) are 0.011, 0.010, and 0.012 ug/L for isoxaflutole, diketonitrile, and benzoic acid, respectively. On the basis of the calculated MRLs and MDLs and evaluation of the signal-to-noise ratios for each compound, the MRLs and MDLs are set at 0.010 and 0.003 ug/L, respectively, for all three compounds.

Techniques and Methods↗

Methods of analysis by the U.S. Geological Survey Organic Geochemistry Research Group: Determination of selected herbicides and their degradation products in water using solid-phase extraction and gas chromatography/mass spectrometry

A method for the extraction and analysis of eight herbicides and five degradation products using solid-phase extraction from natural water samples followed by gas chromatography/mass spectrometry is presented in this report. This method was developed for dimethenamid; flufenacet; fluometuron and its degradation products, demethylfluometuron (DMFM), 3-(trifluromethyl) phenylurea (TFMPU), 3-(trifluromethyl)-aniline (TFMA); molinate; norflurazon and its degradation product, demethylnorflurazon; pendamethalin; the degradation product of prometryn, deisopropylprometryn; propanil; and trifluralin. The eight herbicides are used primarily in the southern United States where cotton, rice, and soybeans are produced. The exceptions are dimethenamid and flufenacet, which are used on corn in the Midwest. Water samples received by the U.S. Geological Survey's Organic Geochemistry Research Group in Lawrence, Kansas, are filtered to remove suspended particulate matter and then passed through disposable solid-phase extraction columns containing octadecyl-bonded porous silica (C-18) to extract the compounds. The herbicides and their degradation products are removed from the column by ethyl acetate elution. The eluate is evaporated under nitrogen, and components then are separated, identified, and quantified by injecting an aliquot of the concentrated extract into a high-resolution, fused-silica capillary column of a gas chromatograph/mass spectrometer under selected-ion mode. Method detection limits ranged from 0.02 to 0.05 μg/L for all compounds with the exception of TFMPU, which has a method detection limit of 0.32 μg/L. The mean absolute recovery is 107 percent. This method for the determination of herbicides and their degradation products is valuable for acquiring information about water quality and compound fate and transport in water.

Open-File Report↗

Organic geochemistry of the 9.6 km Bertha Rogers No. 1. well, Oklahoma

Organic geochemical analyses of fine-grained rocks from the 9.590 km Bertha Rogers No. 1 well have been carried out: total organic carbon, Soxhlet extraction and silica gel chromatography, C 15+ saturated and aromatic hydrocarbon gas chromatography and mass spectrometry, pyrolysis, kerogen analysis, X-ray diffraction and visual kerogen analysis. Rocks ranged in age from Permian to Ordovician; the well has an estimated bottom hole temperature of 225°C. Some data from this study are inconsistent with conventional theories concerning the generation and thermal destruction of hydrocarbons. For example, appreciable amounts of C 15+ gas-condensate-like hydrocarbons are present in very old rocks currently at temperatures where current theory predicts that only methane and graphite should remain. Also, substantial amounts of pyrolyzable C 15+ hydrocarbons remain on the kerogen in these deeply buried Paleozoic rocks. This suggests, at least in somes cases, that temperatures much higher than those predicted by current theory are required for generation and thermal destruction of hydrocarbons. The data from this well also suggest that original composition of organic matter and environment of deposition may have a much stronger influence on the organic geochemical characteristics of fine-grained sediments than has previously been ascribed to them. The results from this well, from other deep hot wells in which temperatures exceed 200°C, and from laboratory experiments, suggest that some of the basic concepts of the generation and maturation of petroleum hydrocarbons may be in error and perhaps should be reexamined.

Oklahoma↗

Organic geochemistry and petrology of oil source rocks, Carpathian Overthrust region, southeastern Poland - Implications for petroleum generation

The organic mailer rich Oligocene Menilite black shales and mudstones are widely distributed in the Carpathian Overthrust region of southeastern Poland and have excellent hydrocarbon generation potential, according to TOC, Rock-Eval, and petrographic data. Extractable organic matter was characterized by an equable distribution of steranes by carbon number, by varying amounts of 28,30-dinor-hopane, 18??(H)-oleanane and by a distinctive group of C24 ring-A degraded triterpanes. The Menilite samples ranged in maturity from pre-generative to mid-oil window levels, with the most mature in the southeastern portion of the study area. Carpathian petroleum samples from Campanian Oligocene sandstone reservoirs were similar in biomarker composition to the Menilite rock extracts. Similarities in aliphatic and aromatic hydrocarbon distributions between petroleum asphaltene and source rock pyrolyzates provided further evidence genetically linking Menilite kerogens with Carpathian oils.

Organic Geochemistry↗

Organic geochemistry of sediments in nearshore areas of the Mississippi and Atchafalaya Rivers: I. General organic characterization

This report presents results on the general organic characteristics of sediment cores collected from the coastal zone of the Mississippi River system, including distributions of the important nutrient elements (C, N, P, and S). This was part of a larger study conducted from 2001-2005 to examine the delivery of sediment-associated contaminants to the Gulf of Mexico by the Mississippi River system, funded by the USGS Coastal and Marine Geology Program. Companion reports emphasize organic contaminants (Rosenbauer and others, 2006), and metals (Swarzenski and others, 2006). The level of contamination within the deltaic system of the Mississippi River system was determined through the collection of sediment cores from interdistributary bays, and offshore in the Gulf of Mexico, including the zone of hypoxia. Results provide the basis for reconstructing contaminant inventories from which to develop historic perspectives on nutrient loading and hypoxia, and to better understand how sediment-hosted contaminants either directly or indirectly move through biota and ultimately affect ecosystem health. Concentrations of C, N, P, and S in sediments varied by a factor of 10 between sites, and in down core profiles. Nearshore cores collected in 2001 proved to have erratic downcore C, N, P, and S profiles and sediment deposition rates, suggesting a high energy regime controlled more by variability in river flow rather than by geochemical processes and reactions within the system. These results focused further coring activities further offshore. Atomic C/N ratios suggest that organic matter deposited at all sites is a mix of microbial (algal) and terrestrial (vascular plant) remains, but with algal material dominant. Concentrations of total sulfur in sediments from cores in the zone of hypoxia were often higher than those in nearby zones with oxic water columns. Corresponding atomic C/S ratios were typically lower in sediments from sites in the zone of hypoxia compared to nearby sites with oxic water columns, and thus atomic C/S values may be useful as a proxy for identifying sites impacted by hypoxic conditions in the water column and for examining historical trends in hypoxia. At one site examined in this study, maximum hypoxic conditions were observed in the mid 1960's. The organic elemental composition (C, N, P, and S) of sediments was also used to guide sample selection for contaminant analysis, and to normalize the contaminant data to organic C content of the sediments. Dissolved hydrocarbon gases in sediments showed a dominance of methane, but identifiable concentrations of ethane and hexane, and trace concentrations of propane, butane, and pentane were also detected. All dissolved gases except hexane were dominated by 'bound' gas, gas released only after agitation of the sediment in a blender. Hexane, in contrast was observed mostly as free gas, determined by headspace analysis.

Louisiana↗

Organic geochemistry in Pennsylvanian tidally influenced sediments from SW Indiana

Tidal rhythmites are vertically stacked small-scale sedimentary structures that record daily variations in tidal current energy and are known to overlie some low-sulfur coals in the Illinois Basin. Tidal rhythmites from the Pennsylvanian Brazil Formation in Indiana have been analyzed sedimentologically, petrographically, and geochemically in order to understand the character and distribution of organic matter (OM) preserved in an environment of daily interactions between marine and fresh waters. The concentration of organic matter (TOC) ranges from traces to 6.9% and sulfur rarely exceeds 0.1% in individual laminae. Angular vitrinite is the major organic matter type, accounting for 50-90% of total OM. The C/S ratio decreases as the verfical distance from the underlying coal increases. A decreasing C/S ratio coupled with decreases in Pr/Ph, Pr/n-C17, Ph/n-C18 ratios and a shift of carbon isotopic composition towards less negative values suggest an increase in salinity from freshwater in the mudflat tidal rhythmite facies close to the coal to brackish/marine in the sandflat tidal rhythmite facies further above from the coal. Within an interval spanning one year of deposition, TOC and S values show monthly variability. On a daily scale, TOC and S oscillations are still detectable but they are of lower magnitude than on a monthly scale. These small-scale variations are believed to reflect oscillations in water salinity related to tidal cycles.Tidal rhythmites are vertically stacked small-scale sedimentary structures that record daily variations in tidal current energy and are known to overlie some low-sulfur coals in the Illinois Basin. Tidal rhythmites from the Pennsylvanian Brazil Formation in Indiana have been analyzed sedimentologically, petrographically, and geochemically in order to understand the character and distribution of organic matter (OM) preserved in an environment of daily interactions between marine and fresh waters. The concentration of organic matter (TOC) ranges from traces to 6.9% and sulfur rarely exceeds 0.1% in individual laminae. Angular vitrinite is the major organic matter type, accounting for 50-90% of total OM. The C/S ratio decreases as the vertical distance from the underlying coal increases. A decreasing C/S ratio coupled with decreases in Pr/Ph, Pr/n-C17, Ph/n-C18 ratios and a shift of carbon isotopic composition towards less negative values suggest an increase in salinity from freshwater in the mudflat tidal rhythmite facies close to the coal to brackish/marine in the sandflat tidal rhythmite facies further above from the coal. Within an interval spanning one year of deposition, TOC and S values show monthly variability. On a daily scale, TOC and S oscillations are still detectable but they are of lower magnitude than on a monthly scale. These small-scale variations are believed to reflect oscillations in water salinity related to tidal cycles.

Organic Geochemistry↗

The organic geochemistry of black sedimentary barite: Significance and implications of trapped fatty acids

Fatty acids isolated in sedimentary black barite (BaSO 4 ) from Arkansas and Nevada were identified by gas chromatography-mass spectroscopy. The dominant or major fatty acids found in these beds of barite are C 16:0 , C 18:0 , and C 18:1 . The occurrence and distribution of these acids in this type of rock may serve as “molecular fingerprints” of microbial biogeochemical processes. The organic matter and associated microorganisms are shown to be trapped within the finely crystalline barite, thus forming a closed system for microbial diagenesis. Important differences that occur in the distribution of the lesser or minor fatty acids probably result from: (1) the nature of the progenitor organic detritus in the environment of barite deposition: and (2) the subsequent degree of microbiological alteration of the parent organic debris swept into and trapped in the depositional environment. Three general models of sedimentary environments are proposed in which anoxic conditions may prevail and where barium sulfate (BaSO 4 ) may precipitate: (1) in a silled basin with semi-restricted circulation; (2) on an outer continental shelf where the slope is encroached upon by water of the oxygen minimum layer; (3) on a low-energy, inner shelf or semi-restricted embayment impinged by a wedge of anoxic water. The major geochemical and geological parameters which are believed to be the significant factors controlling the formation and high grade of these organic-rich, black bedded barites are: (1) a unique source of barium-rich fluid that only contains trace amounts of other elements; (2) the presence of an anoxic bottom environment within the depositional basin; (3) a reflux source of sulfate ion; (4) an adequate source of organic matter. The results of this study may serve as guidelines for future exploration in similar, untested sedimentary basins, especially those with rocks of middle Paleozoic age.

Arkansas, Nevada↗

Organic geochemistry and petrology of subsurface Paleocene-Eocene Wilcox and Claiborne Group coal beds, Zavala County, Maverick Basin, Texas, USA

Coal samples from a coalbed methane exploration well in northern Zavala County, Maverick Basin, Texas, were characterized through an integrated analytical program. The well was drilled in February, 2006 and shut in after coal core desorption indicated negligible gas content. Cuttings samples from two levels in the Eocene Claiborne Group were evaluated by way of petrographic techniques and Rock–Eval pyrolysis. Core samples from the Paleocene–Eocene Indio Formation (Wilcox Group) were characterized via proximate–ultimate analysis in addition to petrography and pyrolysis. Two Indio Formation coal samples were selected for detailed evaluation via gas chromatography, and Fourier transform infrared (FTIR) and 13 C CPMAS NMR spectroscopy. Samples are subbituminous rank as determined from multiple thermal maturity parameters. Elevated rank (relative to similar age coal beds elsewhere in the Gulf Coast Basin) in the study area is interpreted to be a result of stratigraphic and/or structural thickening related to Laramide compression and construction of the Sierra Madre Oriental to the southwest. Vitrinite reflectance data, along with extant data, suggest the presence of an erosional unconformity or change in regional heat flow between the Cretaceous and Tertiary sections and erosion of up to >5 km over the Cretaceous. The presence of liptinite-rich coals in the Claiborne at the well site may indicate moderately persistent or recurring coal-forming paleoenvironments, interpreted as perennially submerged peat in shallow ephemeral lakes with herbaceous and/or flotant vegetation. However, significant continuity of individual Eocene coal beds in the subsurface is not suggested. Indio Formation coal samples contain abundant telovitrinite interpreted to be preserved from arborescent, above-ground woody vegetation that developed during the middle portion of mire development in forested swamps. Other petrographic criteria suggest enhanced biological, chemical and physical degradation at the beginning and end of Indio mire development. Fluorescence spectra of sporinite and resinite are consistent and distinctly different from each other, attributed to the presence of a greater proportion of complex asphaltene and polar molecules in resinite. Gas chromatography of resinite-rich coal shows sesquiterpenoid and diterpenoid peaks in the C 14–17 range, which are not present in resinite-poor coal. Quantities of extracts suggest bitumen concentration below the threshold for effective source rocks [30–50 mg hydrocarbon/g total organic carbon (HC/g TOC)]. Saturate/aromatic and pristane/phytane (Pr/Ph) ratios are different from values for nearby Tertiary-reservoired crude oil, suggesting that the Indio coals are too immature to source liquid hydrocarbons in the area. However, moderately high HI values (200–400 mg HC/g rock) may suggest some potential for naphthenic–paraffinic oil generation where buried more deeply down stratigraphic/structural dip. Extractable phenols and C 20+ alkanes are suggested as possible intermediates for acetate fermentation in microbial methanogenesis which may, however, be limited by poor nutrient supply related to low rainfall and meteoric recharge rate or high local sulfate concentration.

Texas↗