Geochemistry Commons^™

The Vinylguaiacol/Indole Or Vgi ("Veggie") Ratio: A Novel Molecular Parameter To Evaluate The Relative Contributions Of Terrestrial And Aquatic Organic Matter To Sediments., Michael A. Kruge, Kevin K. Olsen, Jaroslaw W. Slusarczyk, Elaine Gomez

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The organic matter (OM) fraction of estuarine sediments is often distinctive and thus diagnostically useful in determinations of sedimentary provenance. Among the most fundamental distinctions to be made is that between terrestrial and aquatic OM. To supplement the parameters commonly used for this purpose (e.g., C/N and stable isotope ratios), we proposed the Vinylguaiacol/Indole or VGI ("Veggie") ratio, defined as [vinylguaiacol / (indole + vinylguaiacol)] using data produced by analytical pyrolysis-gas chromatography/mass spectrometry of dried, homogenized sediment samples. The ratio employs the peak areas of these two compounds on the mass chromatograms of their molecular ions (m/z 150 and 117). …

Geochemical Investigation Of An Offshore Sewage Sludge Deposit, Barcelona, Catalonia, Spain, Michael A. Kruge, Albert Permanyer, Jordi Serra, Danlin Yu

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

For 20 years ending in the 1990’s the city of Barcelona discharged the products from a large primary sewage treatment plant directly into the Mediterranean Sea via underwater conduits. About ca. 3 million m³ of relict sewage sludge, rich in organic matter and heavy metals, has spread over an elongated area offshore, due to successive ruptures of the conduits. The use of the discharge pipes ceased, but he sludge deposit remains in place for the time being.

To understand the history and present state of the sludge deposit in advance of future remediation, a program of geophysical mapping, sampling, …

Export Of Terrestrial Dissolved Organic Matter Along A River To Ocean Transect Of The Lower Chesapeake Bay Investigated By Advanced Analytical Techniques, Rachel Leigh Sleighter

Chemistry & Biochemistry Theses & Dissertations

Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) has proved essential for the complete separation of the thousands of peaks present in natural organic matter (NOM), a complex assemblage of organic molecules present in water, soils, and sediments. An improved understanding of its composition is crucial to understand how pollutants interact with NOM and how NOM cycles through global carbon cycles.

Optimizing the acquisition and handling of the FTICR mass spectra is the first step to obtaining high quality data. A simple method to internally calibrate the peaks in the complex spectra, using naturally present fatty …

Organic Geochemical Investigation Of A Highly Contaminated Urban Waterway: The Gowanus Canal, Brooklyn, New York, Usa, Michael A. Kruge, Kevin K. Olsen, Eric A. Stern

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The Gowanus Canal is an industrial waterway constructed in the mid-19^th century by widening and deepening a natural tidal channel. It is ca. 3 km in length and empties into Gowanus Bay, an arm of New York Harbor. Its banks, reinforced by bulkheads and piers, became the site of intensive industrial activity, including oil refining, coal gasification, soap making and tanning. Even though much of the industrial activity along the canal has ceased, its sediments remain highly enriched in organic and inorganic contaminants, with combined sewer outfalls continuing to transport pollutants into the canal. The canal area remains densely …

Significance Of Polycyclic Aromatic Hydrocarbons (Pahs) And Petroleum Biomarker Compounds In Contaminated Passaic River Sediments, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The lower Passaic River (northeastern New Jersey) flows through one of the most densely populated regions of the United States. The area’s long history of industrial activity is reflected in the complex and variable hydrocarbon composition of the river sediments. Sediments from river bottom grab samples at Newark and a 30 cm deep core at Kearny were subjected to thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). This technique offers a practical alternative for rapid, inexpensive analysis, simply employing milligram quantities of dry, disaggregated sediment, avoiding the use of hazardous organic solvents. For each sample, a total of 181 hydrocarbons and organosulfur compounds …

Application Of Pyrolysis-Gc/Ms For Rapid Assessment Of Organic Contamination In Sediments From Barcelona Harbor, Michael A. Kruge, Albert Permanyer

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Pyrolysis-GC/MS is advantageous as a tool for rapid sediment contamination assessment because of the small sample size required, minimal sample preparation, and its ability to detect a wide variety of organic pollutants as well as naturally-occurring biological materials. Py-GC/MS was applied, together with determination of organic carbon, and major and minor element concentrations, to evaluate potentially contaminated sediments in the port of Barcelona (Spain) and the adjacent Llobregat River delta. Detected contaminant markers, most evident in the Old Port (Port Vell) area, included hopanes and alkylated PAHs (petroleum), sterenes (sewage), C₁₆-C₁₉ phenylalkanes (detergents) and parent …

Support For The Nye County Early Warning Drilling Program, Irene Farnham, Klaus J. Stetzenbach, Amy J. Smiecinski

Publications (YM)

This final report details the activities completed for Task 8 of the University and Community College System of Nevada (UCCSN) Cooperative Agreement with the US Department of Energy (DOE). Task 8, titled "Support for the Nye County Early Warning Drilling Program" provided for a variety of hydrochemical analyses. The requirements of the University and Community College System of Nevada (UCCSN) Quality Assurance (QA) Program were followed for all work performed on this task. The primary activity performed by the Harry Reid Center for Environmental Studies (HRC) for Task 8 was to provide hydrochemical analyses of the groundwater samples collected from …

Preliminary Geochemical Evaluation Of Groundwaters From Wells Of The Nye County Early Warning Drilling Program, Irene Farnham, Klaus J. Stetzenbach, Amy J. Smiecinski

Publications (YM)

As part of the Yucca Mountain Oversight program, the Nye County Nuclear Waste Repository Project Office (NWRPO) has established a groundwater monitoring program to protect groundwater resources for the residents of Nye County in Amargosa and Pahrump Valleys. This groundwater monitoring program, referred to as the Nye County Early Warning Drilling Program (NCEWDP), involves drilling a series of wells down-gradient from Yucca Mountain for long term groundwater monitoring and also to provide much needed geologic and hydrologic information in this area. A comprehensive database of aquifer parameters in the alluvial, volcanic, and carbonate aquifers down-gradient hydrogeologically of Yucca Mountain is …

Organic Geochemical Analysis Of Late-Glacial And Early-Holocene Ecosystem Changes: A Case Study From Northern New England Lakes, Michael A. Kruge, Andrea Lini

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The lacustrine sedimentary archive of organic remains provides important evidence for the reconstruction of the environmental histories of lakes and their watersheds, recording the response of the Earth's biota to changes on scales varying from the local to the global. The last Glacial-Interglacial transition presents an opportunity to investigate how, and at what rates, watershed and lake ecosystems were established on once glaciated, carbon and nutrient-poor landscapes. The small lakes of northern Vermont (USA) provide an appropriate setting in which to investigate such changes.

As part of a multidisciplinary study of three Vermont lake sediment cores, samples ranging in age …

Biogeochemistry And Contaminant Geochemistry Of Marine And Estuarine Sediments, New Haven, Connecticut (Usa), Michael A. Kruge, Gaboury Benoit

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The urbanized shore areas of Long Island Sound in the vicinity of New Haven, Connecticut (USA) have a long history of exposure to point and non-point sources of pollution, New Haven having been one of the birthplaces of the industrial revolution. As an unintended consequence of such activities, the region's sedimentary systems have incorporated a complex mixture of organic and inorganic contaminants. With its long and varied pollution history and the multiplicity of sedimentary environments (fluvial, estuarine, intertidal, marsh, etc.) present in a compact geographical area, the region is ideal natural laboratory for field testing new contamination assessment techniques. The …

Determination Of Thermal Maturity And Organic Matter Type By Principal Components Analysis Of The Distributions Of Polycyclic Aromatic Compounds, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The thermal maturity and organofacies sensitivity of polycyclic aromatic compound (PAC) distributions was explored by examination of the aromatic fractions of solvent extracts from a diverse set of 53 shales, coals and kerogen macerals which have undergone either natural or artificial maturation and which represent all three principal sedimentary organic matter (OM) types. Systematic changes with maturation were observed in the following groups of isomers: tri- and tetramethylnaphthalenes, methyl- and dimethylphenanthrenes, methyl- and dimethyldibenzothiophenes, methylpyrenes, and methylchrysenes. The maturity differences were quantified by mathematical ratios of the relative concentrations of the more thermally stable isomers to the less stable, on …

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 …

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 …

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 …

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 …

An Analysis Of Dissolved Organic Compounds And Their Contribution To Iron Complexation In The Shallow Leachate Plume Of The West Kl Landfill Kalamazoo, Michigan, Eric Fahle

Masters Theses

High concentrations of dissolved iron are present in downgradient groundwater samples adjacent to the western border of the West KL Landfill. Analysis by Rudder (1988) of groundwater samples indicates oversaturation of selected iron oxides, iron sulfides and siderite in monitoring wells TW-4 and M3.

Previous research suggests that pyrogallol, gallic acid, tannic acid and similar organic compounds may retard the oxidation of ferrous iron in the shallow leachate plume of the West KL landfill (Rudder, 1988). Present research utilizing solid phase extraction, reverse phase high performance chromatography, Fourier transform IR spectrophotometry, UV/Visible spectrophotometry, and gas chromatography/mass spectroscopy indicate that pyrogallol, …

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 …