Geochemistry Commons^™

A Biogeochemical Comparison Of Fossil (Carboniferous) And Modern Crustose Red Algae, Michael A. Kruge, John E. Utgaard, William Ferry

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The nature of the contribution of the various types of algae to sedimentary organic matter continues to be a topic of research interest. Crustose red algae have however received less attention than other types. The fossil calcareous red algae (Rhodophyta) analyzed in this study are two relatively unrecrystallized specimens of Parachaetetes (Family Solenoporacea) from the lower part of the Ste. Genevieve Formation (Carboniferous, Visean) in Union County, Illinois, USA. They occurred in the patch reef phase of a small carbonate mudmound-patchreef. The three modern specimens (collected and identified by F. Collier) are the crustose algae Lithothamnion, Clathromorphum and Phymatolithon …

Chemistry Of Maceral And Groundmass Density Fractions Of Torbanite And Cannel Coal, Zhiwen Han, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Microscopically, torbanite and cannel coal are composed of coarser macerals set in a fine-grained to amorphous groundmass. It is often assumed that the amorphous groundmass is genetically related to the distinct macerals. The separation of macerals and groundmass from 14 late Paleozoic torbanite, cannel, and humic coals permits the analysis of individual constituents using elemental analysis and flash pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Cluster and principal component analyses of the Py-GC/MS data further reveal the chemical similarities and differences between the various constituents. Pyrolyzates of Botryococcus-related alginites are characterized by an abundance of normal alkadienes, alkenes, and alkanes. Even their …

Classification Of Torbanite And Cannel Coal. Ii. Insights From Organic Geochemical And Multivariate Statistical Analysis, Zhiwen Han, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Petrographic and megascopic criteria have traditionally been used as the basis for the classification of torbanite and cannel coal. For this study, it was hypothesized that modern analytical organic geochemical and multivariate statistical techniques could provide an alternative approach. Towards this end, the demineralized residues of 14 torbanite (rich in Botryococcus-related alginite) and cannel (essentially, rich in organic groundmass and/or sporinite) coal samples were analyzed by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Cluster analysis performed on the Py-GC/MS data clearly distinguished the torbanite from the cannel coal, demonstrating a consistency between the chemical properties and the petrographic composition. All the torbanite …

Molecular Organic Geochemistry Of New York Bight Sediments. Sources Of Biogenic Organic Matter And Polycyclic Aromatic Hydrocarbons, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

As part of a multidisciplinary evaluation of the environmental impact of waste disposal in the New York Bight, a preliminary effort was undertaken to assess the molecular geochemistry of its sedimentary organic matter (OM). For this initial phase of the study, samples were taken from two New York Bight cores collected outside the area of known dumping [in Sandy Hook Bay, NJ], to establish the environmental context for future work on sediments from within dumpsite zones. The method employed was flash pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), which is an organic microanalysis technique suitable for solid samples, in this case dried, raw …

Environmental And Botanical Controls On Peatification - A Comparative Study Of Two New Zealand Restiad Bogs Using Py-Gc/Ms, Petrography And Fungal Analysis, Tomasz K. Kuder, Michael A. Kruge, J C. Shearer, S L. Miller

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

This study shows that chemical properties of two restiad species, Empodisma minus and Sporadanthus traversii, may contribute to their success as peat-formers in a climate of the North Island of New Zealand which is not conducive to raised mire development. Unlike Sphagnum, the equivalent northern hemisphere peat-former, restiads possess lignin in their tissues. In addition, the presence of non-lignin polyphenols (including tannins and phenolic acids) in restiads may be an important factor in peat formation due to the allelopathic decay retardation. Patterns of degradation of plant biopolymers have been examined and the pathway of degradation of monocotyledons (loss …

A Molecular Evaluation Of Contaminants And Natural Organic Matter In Surface Sediments From Western Lake Ontario, Michael A. Kruge, Prasanta K. Mukhopadhyay, C.F. Michael Lewis

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) analysis of bottom sediment from Lake Ontario was shown to be effective in assessing organic contaminants, especially attractive as it is a rapid technique requiring little sample preparation. Pyrolyzates of samples richer in organic matter (OM) were relatively enriched in aliphatic hydrocarbons and pyrrolic nitrogen compounds, while leaner samples were more aromatic and pyridinic. Alkylbenzene and alkylphenol distributions in the pyrolyzates were most compatible with derivation from aquatic (algal, bacterial) OM. The organonitrogen compounds indicated the presence of degraded proteinaceous material from aquatic sources and/or sewage. Normal and polycyclic aromatic hydrocarbon distributions indicate, at least in …

Petrographic And Chemical Properties Of Carboniferous Resinite From The Herrin No. 6 Coal Seam, John C. Crelling, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Resinite is a naturally occurring substance found in coal and derived from original plant resins. It is ubiquitous in North American coals and comprises 1 to 4% by volume of most Illinois coals. It has been commercially exploited in the western USA for use in adhesives, varnishes and thermal-setting inks. The major objectives of this study were: (1) to separate resinite macerals from the Herrin No. 6 coal seam and to carefully verify, by petrographic and fluorescence microspectrophotometric methods, that the separated material was indeed resinite; (2) to characterize the chemical composition of the separated resinite by Py–GC–MS techniques; and …

Application Of Environmental Organic Petrology And Geochemistry To Fingerprint Organic Pollutants In The Recent Sediments Of Lake Ontario, Prasanta K. Mukhopadhyay, Michael A. Kruge, C.F. Michael Lewis

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Selected surface sediment samples (sediment depth 0-10 cm) collected in the Niagara basin (western Lake Ontario) were chosen for organic matter characterization using organic petrological and geochemical techniques normally reserved for the study of coal, petroleum source rock and crude oil. The study was performed to assess the effectiveness of these techniques in discriminating between natural and anthropogenic organic matter and to determine the extent of organic pollution of the lake sediments. The organic carbon contents of the samples vary from 1.5 to 3.5%, with upper layer (0-5 cm) samples have higher TOC values than those from the lower layer …

Comparison Of Source Rock Geochemistry Of Selected Rocks From The Schei Point Group And Ringnes Formation, Sverdrup Basin, Arctic Canada, P. K. Mukhopadhyay, F. Goodarzi, Michael A. Kruge, M. H. Alimi

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Organic-rich from the Schei Point group (middle to late Triassic in age) and the Ringnes formation (late Jurassic) from the Sverdrup basin of the Canadian arctic archipelago have been geochemically evaluated for source rock characterization. Most samples from the Schei Point group are organic-rich (> 2% TOC) and are considered as immature to mature oil-prone source rocks [kerogen types I, I-II (IIA) and II (IIA)]. These kerogen types contain abundant AOM1, AOM2 and alginite (Tasmanales, Nostocopsis, Leiosphaeridia, acritarch and dinoflagellate) with variable amounts of vitrinite, inertinite and exinite. Samples from the Ringnes formation contain dominant vitrinite and inertinite …

Separation And Artificial Maturation Of Macerals From Type Ii Kerogen, Michael A. Kruge, Patrick Landais, David F. Bensley, B Artur Stankiewicz, Marcel Elie, Olivier Ruau

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Immature Type II kerogen (HI= 660 mg/g) from the Lower Toarcian of the Paris Basin was separated into an alginite concentrate (HI = 952 mg/g) and an amorphous organic matter (AOM) concentrate (HI = 573 mg/g) by density centrifugation. The flash pyrolyzate of the alginite is characterized by high relative concentrations of several series of n-alkanones and n-alkenones (including mid-chain alkyl ketones), in addition to n-alkanes, n-alk-1-enes and n-alkadienes. To our knowledge, this Toarcian alginite is the oldest example of marine organic matter whose pyrolyzate contains mid-chain alkanones in such high relative concentrations. In sharp …

Artificial Maturation Of Alginite And Organic Groundmass Separated From Torbanites, Michael A. Kruge, Patrick Landais, David F. Bensley

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The two principal organic constituents — Botryococcus-related alginite and organic groundmass — were isolated by density separation from two torbanite samples (from the Stellarton Fm., Nova Scotia, Canada and the King Cannel, Utah, USA). The groundmass consisted of degraded algal, bacterial and terrestrial plant debris. Aliquots of alginite and groundmass were separately heated in gold tubes for 24 hr. with 70 MPa confining pressure, at fixed temperatures ranging between 250 and 375°C. The 250, 300 and 325°C experiments run on the alginite produced very low yields of CHCl3-extractable organic matter (EOM), indicating that very little of the generation potential …

Organic Geochemistry And Petrology Of Oil Source Rocks, Carpathian Overthrust Region, Southeastern Poland — Implications For Petroleum Generation, Michael A. Kruge, Maria Mastalerz, Andrzej Solecki, B Artur Stankiewicz

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The organic matter 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, 18α(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 …

Flash Pyrolysis Of Anthropogenic And Natural Organic Matter In Polluted Sediments, Sami T. Abdel Bagi, Michael A. Kruge, Gary L. Salmon

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

INTRODUCTION - Combustion products along with spilled petroleum and industrial chemicals contribute to environmental degradation by contaminating soils and sediments. Such anthropogenic organic matter (OM), if preserved in sediments, can serve an archival function, documenting the local, history of industrial pollution. Christensen and Zhang (1993) determined the sources of polycyclic aromatic hydrocarbons (P AH) to Lake Michigan from sedimentary records, finding that coal combustion was a major source for PAHs in these sediments. Bodzek and Luks-Betlej (1993) reported that atmospheric deposition is the main source of PAH in soils of the heavily industrialized Upper Silesia region of Poland. Smith and …

Organic Facies And Maturation Of Jurassic/Cretaceous Rocks, And Possible Oil-Source Rock Correlation Based On Pyrolysis Of Asphaltenes, Scotian Basin, Canada, Prasanta K. Mukhopadhyay, John A. Wade, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

This paper establishes source rock characterization and oil-oil and oil-source rock correlations of selected organic-rich shale source rocks and selected light oils and condensates from Jurassic and Cretaceous formations of the Scotian Basin. Multiple source rocks of Kerogen Types IIA (oil-prone), IIA-IIB (oil- and condensate-prone), IIB (condensate and gas prone), III (gas-prone), and IV (nonsource) are identified in various stratigraphic horizons. Vitrinite reflectance and T_max data indicate variable maturation histories, in different parts of the basin, which are related to differences in lithology-related heat conductivity and the presence of older sediments closer to areas of rifting. Multiple linear regression …

Speciation Of Heteroatoms In Coal By Sulfur- And Nitrogen-Selective Techniquestrogen-Selective Techniques, Stephen R. Palmer, Michael A. Kruge, Edwin J. Hippo, John C. Crelling

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The peroxyacetic acid oxidation products from a series of coals of organic sulfur content 0.5-9.8 wt% were examined. The distributions of organic S and N compounds were determined by gas chromatography with sulfur-selective flame photometric and nitrogen-selective thermionic specific detection respectively. A selected sample was also examined in greater detail using low-voltage high-resolution mass spectrometry. The distribution of organic sulfur compounds in the oxidation products was remarkably similar for all the coals. The number of sulfur compounds detected was small compared with that of organic nitrogen compounds detected. This suggests that the sulfur chemistry of coal is considerably simpler than …

Fossil Charcoal In Cretaceous-Tertiary Boundary Strata: Evidence For Catastrophic Firestorm And Megawave, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Organic matter separated from calcareous sandstone from the upper portion of a deep-water tsunami deposit at Arroyo el Mimbral, Taumalipas (Mexico), which marks the biostratigraphically-defined Cretaceous-Tertiary boundary, consists primarily of fossil charcoal, including semifusinite and pyrofusinite. Analytical pyrolysis-gas chromatography-mass spectrometry revealed the highly aromatic and polyaromatic character of the organic matter assemblage, typical of the products of partial combustion. The organic matter probably originated as terrestrial vegetation that was caught in a firestorm and subsequently transported far offshore in the backwash of a megawave. These data are consistent with the hypothesis of combustion of large masses of vegetation triggered by …

Flash Pyrolysis-Gas Chromatography/Mass Spectrometry Of Lower Kittanning Vitrinites: Changes In The Distributions Of Polyaromatic Hydrocarbons As A Function Of Coal Rank, Michael A. Kruge, David F. Bensley

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Chemical analyses restricted to a single coal maceral permit a focus on rank effects without concern for variations in organic matter type. Vitrinite concentrates of high purity were isolated from coal samples of the Lower Kittanning seam by multi-step density gradient centrifugation, with reflectances ranging from 0.66 to 1.39% Rmax. In addition to the previously recognized losses of phenolic compounds, the vitrinite pyrolyzates exhibit marked increases in relative concentrations of tri- and tetraaromatic hydrocarbons (especially benzo[a]fluorene, methyl-phenanthrenes, methylfluorenes and methylchrysenes) above 0.9% Rmax, i.e., beyond the "second coalification jump" of Teichmüller. Thus, petrographically-recognizable physical transformations are shown …

Organic Geochemistry Of Permian Organic-Rich Sediments From The Sudetes Area, Sw Poland, Shareen R. Yawanarajah, Michael A. Kruge, Maria Mastalerz, Wojciech Sliwinski

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Lacustrine and marine sediments from the Permian rift-basins of southwestern Poland were analysed using GC-MS and petrographic techniques. High Pr/Ph ratios, gamma- and beta-carotanes and gammacerane in the lacustrine sediments indicate deposition under elevated water salinities. The primary organic matter is represented by bacterial and algal lipids with variable terrestrial input. Marine algal lipids with minor bacterial and cyanobacterial lipids are the primary source of organic matter in the marine sediments. Extended hopanes, n-alkanes with even-odd predominance and low Ts/Tm ratios are consistent with deposition in a closed, evaporitic basin with substantial carbonate sedimentation.

Organic Geochemistry And Petrography Of Spanish Oil Shales, Michael A. Kruge, Isabel Suarez-Ruiz

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Four of the principal oil shale units of Spain were examined by organic geochemical and petrographic methods. The samples included three lacustrine shales (Carboniferous from Puertollano, Cretaceous from Llames and Miocene from Rubielos de Mora) and one marine shale (Lower Jurassic from Punta del Cuerno ). The petrographic observations show a dominance of liptodetrinite associated with bitumen-stained mineral matter and alginite, as well as a paucity of structured terrestrial organic matter. Geochemical work shows that the soluble organic matter is a mixture of terrestrially derived and aquatic, with the lacustrine samples having the strongest land plant signatures. Low values of …

Aspects Of Sporinite Chemistry, Michael A. Kruge, John C. Crelling, Edwin J. Hippo, Stephen R. Palmer

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

With the recent advent of the ability to separate coal into maceral concentrates of high purity, the individual constituents of coal can now be analyzed separately, without their mutual interference, giving a much better understanding of the macromolecular structure of coal. The sporinites from two Pennsylvanian age coal samples (Illinois Basin, U.S.A.) were studied, one from a vitrinite-rich high-volatile bituminous coal, the other from a liptinite-rich high-volatile bituminous coal of slightly higher rank. Sporinites were isolated from each coal by density gradient centrifugation. The sporinite of the vitrinite-rich coal was compared chemically and petrographically with the parent coal and with …

Biological Markers In Lower Jurassic Synrift Lacustrine Black Shales, Hartford Basin, Connecticut, U.S.A., Michael A. Kruge, John F. Hubert, Jay F. Akes, Paul E. Meriney

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The East Berlin Formation (Lower Jurassic, Hartford basin, Connecticut, U.S.A.) is distinctive for its six cyclic units of lacustrine black shale and gray mudstone. separated by playa and fluvial redbeds. The black shales arc each about a meter thick and were deposited in subtropical, thermally stratified, oligomictic lakes, the youngest of which (lakes 3 through 6) were large enough to flood most of the basin and attained depths of several tens of meters.

The saturate fractions of solvent extracts of organic-rich black shales from each of the six lakes, collected at fresh roadcuts near East Berlin, arc dominated by extended …

Characterization Of Organic Sulfur Compounds In Coals And Coal Macerals, Stephen R. Palmer, Edwin J. Hippo, Michael A. Kruge, John C. Crelling

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Peroxyacetic acid oxidation has been used to investigate the type and distribution of organic sulfur species in samples of vitrinite, sporinite and inertinite, separated from the Herrin No.6 and an Indiana No.5 coal seam. It was established that organic sulfur species were selectively preserved during oxidation and their analysis led to some of the first sulfur-33 NMR spectra obtained for coal. The effects of maceral separation processes on model compounds were also studied. Results from our studies support the following conclusions: 1). Different macerals have different distributions and types of organic sulfur species. 2). Organic sulfur compounds in coal occur …

Organic Geochemistry Of A Lower Jurassic Synrift Lacustrine Sequence, Hartford Basin, Connecticut, U.S.A., Michael A. Kruge, John F. Hubert, David F. Bensley, John C. Crelling, R Jay Akes, Paul E. Meriney

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Synrift terrestrial strata of the Lower Jurassic East Berlin Formation (Hartford basin, Connecticut, U.S.A.) record cyclical expansion and contraction of major lakes, six of which were deep enough to develop anoxic bottom waters. We have studied one representative lacustrine sequence in detail, sampling a new roadcut near the village of East Berlin. The section examined is 4 m thick, with a gray siltstone at the base, deposited in shallow water, overlain by an organic-rich black shale (deep water), succeeded in turn by another gray siltstone, deposited as the lake waters gradually receded. The upper gray siltstone is chemically distinct from …

Biomarker Geochemistry Of The Miocene Monterey Formation, West San Joaquin Basin, California: Implications For Petroleum Generation, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Much of the Miocene Monterey Formation of California is rich in biogenic sediment, especially organic matter and silica. Because of the geologic structure, the Monterey in the subsurface near Lost Hills in the San Joaquin Basin forms a natural laboratory for the study of the diagenetic responses of these materials. Rocks of similar age and lithology are buried to depths ranging between 500 and 3500 m, and are thus exposed to a temperature range of 45–130°C. The diagenetic progression of silica from opal-A to opal-CT to microquartz is well-documented in Monterey burial history studies. However, diagenetic indicators need to be …

Diagenesis Of Miocene Biogenic Sediments In Lost Hills Oil Field, San Joaquin Basin, California, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Major portions of the Miocene Monterey formation of California were deposited under low oxygen conditions, with restricted clastic influx, beneath waters with high phytoplankton productivity. The resulting diatomaceous and organic-rich sediments underwent diagenetic modification as they were buried.

A suite of core samples was collected from eight wells in the Lost Hills oil field ranging in present depth of burial between 535 and 2285 meters. In one well, the entire Monterey section was sampled. Cores taken from the remaining wells sampled the Reef Ridge and Antelope Members of the Monterey Formation at various burial depths.

Silica mineralogy was studied using …