Thermal alteration of Cretaceous black shale by diabase intrusions in the eastern Atlantic. II - Effects on bitumen and kerogen
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Fifty-eight rock chips from fifteen samples of sedimentary rocks from the Ramah Group (approximately 1.9 Ga) in northeastern Labrador, Canada, were analyzed for major and minor elements, including C and S, to elucidate weathering processes on the Earth's surface about 1.9 Ga ago. The samples come from the Rowsell Harbour, Reddick Bight, and Nullataktok Formations. Two rock series, graywackes-gray shales of the Rowsell Harbour, Reddick Bight and Nullataktok Formations, and black shales of the Nullataktok Formation, are distinguishable on the basis of lithology, mineralogy, and major and trace element chemistry. The black shales show lower concentrations than the graywackes-gray shales in TiO2 (0.3-0.7 wt% vs. 0.7-1.8 wt%), Al2O3 (9.5-20.1 wt% vs. 13.0-25.0 wt%), and sigma Fe (<1 wt% vs. 3.8-13.9 wt% as FeO). Contents of Zr, Th, U, Nb, Ce, Y, Rb, Y, Co, and Ni are also lower in the black shales. The source rocks for the Ramah Group sediments were probably Archean gneisses with compositions similar to those in Labrador and western Greenland. The major element chemistry of source rocks for the Ramah Group sedimentary rocks was estimated from the Al2O3/TiO2 ratios of the sedimentary rocks and the relationship between the major element contents (e.g., SiO2 wt%) and Al2O3/TiO2 ratios of the Archean gneisses. This approach is justified, because the Al/Ti ratios of shales generally retain their source rock values; however, the Zr/Al, Zr/Ti, and Cr/Ni ratios fractionate during the transport of sediments. The measured SiO2 contents of shales in the Ramah Group are generally higher than the estimated SiO2 contents of source rocks by approximately 5 wt%. This correction may also have to be applied when estimating average crustal compositions from shales. Two provenances were recognized for the Ramah Group sediments. Provenance I was comprised mostly of rocks of bimodal compositions, one with SiO2 contents approximately 45 wt% and the other approximately 65 wt%, and was the source for most sedimentary rocks of the Ramah Group, except for black shales of the Nullataktok Formation. The black shales were apparently derived from Provenance II that was comprised mostly of felsic rocks with SiO2 contents approximately 65 wt%. Comparing the compositions of the Ramah Group sedimentary rocks and their source rocks, we have recognized that several major elements, especially Ca and Mg, were lost almost entirely from the source rocks during weathering and sedimentation. Sodium and potassium were also leached almost entirely during the weathering of the source rocks. However, significant amounts of Na were added to the black shales and K to all the rock types during diagenesis and/or regional metamorphism. The intensity of weathering of source rocks for the Ramah Group sediments was much higher than that of typical Phanerozoic sediments, possibly because of a higher PCO2 in the Proterozoic atmosphere. Compared to the source rock values, the Fe3+/Ti ratios of many of the graywackes and gray shales of the Ramah Group are higher, the Fe2+/Ti ratios are lower, and the sigma Fe/Ti ratios are the same. Such characteristics of the Fe geochemistry indicate that these sedimentary rocks are comprised of soils formed by weathering of source rocks under an oxygen-rich atmosphere. The atmosphere about 1.9 Ga was, therefore, oxygen rich. Typical black shales of Phanerozoic age exhibit positive correlations between the organic C contents and the concentrations of S, U, and Mo, because these elements are enriched in oxygenated seawater and are removed from seawater by organic matter in sediments. However, such correlations are not found in the Ramah Group sediments. Black shales of the Ramah Group contain 1.7-2.8 wt% organic C, but are extremely depleted in sigma Fe (<1 wt% as FeO), S (<0.3 wt%), U (approximately l ppm), Mo (<5 ppm), Ni (<2 ppm), and Co (approximately 0 ppm). This lack of correlation, however, does not imply that the approximately 1.9 Ga atmosphere-ocean system was anoxic. Depletion of these elements from the Ramah Group sediments may have occurred during diagenesis.
A regional pattern of three closely spaced erosional events at and above the K/T boundary was determined from six Cretaceous/Tertiary boundary sections in the Negev of Israel. The sections were collected from locations throughout the central and northern Negev. All sections are lithologically similar. The Maastrichtian consists of a sequence of limestone beds intercalated with thin marly beds. In some sections, the last limestone bed is followed by 1 to 2 m of calcareous marls grading upwards into several meters of grey shale. In other sections the limestone bed is followed directly by grey shale with the contact containing particles of limestone and marl. A 5 to 20 cm thick dark grey organic-rich clay layer is present about 1.5 to 2.5 m above the base of the grey shale. The grey shale grades upwards into increasingly carbonate rich marls. No unconformities are apparent in field outcrops. During field collection the dark grey clay layer was believed to represent the K/T boundary clay. Microfossil analysis however identified the boundary at the base of the grey shale. The black shale represents a low productivity anoxic event similar to, but younger than, the K/T boundary clay in other K/T boundary sections. High resolution planktic foraminiferal and carbonate analysis of these sections (at 5 to 10 cm intervals) yield surprising results. The K/T boundary is marked by an erosional event which removed part or all of the uppermost Maastrichtian marls above the last limestone bed. Percent carbonate data for four Negev sections are illustrated and show the regional similarities in carbonate sedimentation. Faunal and carbonate data from the Negev sections thus show three closely spaced short erosional events at the K/T boundary and within the first 50,000 to 100,000 years of the Danian. These K/T boundary erosional events may represent global climatic or paleoceanographic events.
The upper part of the New Albany Shale is divided into three members. In ascending order, these are (1) the Morgan Trail Member, a laminated brownish-black shale; (2) the Camp Run Member, an interbedded brownish-black and greenish-gray shale; and (3) the Clegg Creek Member, also a laminated brownish-black shale. The Morgan Trail and Camp Run Members contain 5% to 6% total organic carbon (TOC) and 2% sulfide sulfur. Isotopic composition of sulfide in these members ranges from -5.0% to -20.0%. C/S plots indicate linear relationships between abundances of these elements, with a zero intercept characteristic of sediments deposited in a non-euxinic marine environment. Formation of diagenetic pyrite was carbon limited in these members. The Clegg Creek Member contains 10% to 15% TOC and 2% to 6% sulfide sulfur. Isotopic compositions of sulfide range from -5.0% to -40%. The most negative values occur in the uppermost Clegg Creek Member and are characteristic of syngenetic pyrite, formed within an anoxic water column. Abundances of carbon and sulfur are greater and uncorrelated in this member, consistent with deposition in as euxinic environment. In addition, DOP (degree of pyritization) values suggest that formation of pyrite was generally iron limited throughout Clegg Creek deposition, but sulfur isotopes indicate that syngenetic (water-column) pyrite becomes an important component in the sediment only in the upper part of the member. At the top of the Clegg Creek Member, a zone of phosphate nodules and trace-metal enrichment coincides with maximal TOC values. During euxinic deposition, phosphate and trace metals accumulated below the chemocline because of limited vertical circulation in the water column. Increased productivity would have resulted in an increased flux of particulate organic matter to the sediment, providing an effective sink for trace metals in the water column. Phosphate and trace metals released from organic matter during early diagenesis resulted in precipitation of metal-rich phosphate nodules.
The nature of the sph eroidal unicellular fossils 10 to 62 micrometers in diameter that are abundant in black shales referred to the Stoer Formation of lower Torridonian age at Stoer Bay, in northwest Scotland, is examined. It is shown that their biological affinities are obscure; it is, however, not unlikely that many or most of them are independent unicellular members of the marine phytoplankton.
Magnetic microspherules were identified in over 20 K/T boundary sites, and in numerous Deep Sea Drilling Project (DSDP) cores from the Caribbean and Pacific, synchronous with the extinction of several radiolarian species near the end of the Eocene. The K/T magnetic spherules are of particular interest as carriers of Ir and other siderophiles generally found in abundance in K/T boundary clay. Furthermore the textures and unusual chemistry of their component magnetic phases indicate an origin at high temperature, possibly related to (an) unusual event(s) marking the end of the Cretaceous and Eocene periods. Their origin, along with the non-magnetic (sanidine) spheules, is generally ascribed directly to megaimpact events hypothesized to have periodically disrupted life on Earth. A survey of microspherical forms associated with known meteorite and impact derived materials reveals fundamental differences from the extinction related spherules. Low temperature magnetic experiments on the K/T and Upper Eocene spheroids indicate that, unlike tektites, extremely small superparamagnetic carriers are not present in abundance. The extensive subaerial exposure of Cretaceous combustible black shale during sea level regression in the latest Cretaceous represents a potential source for the magnetic spheroids found in certain K/T boundary clays. The recent discovery of high Ir abundances distributed above and below the K/T boundary within shallow water sediments in Israel, which also contain the most extensive known zones of combustion metamorphism, the so called Mottled Zone, adds a further dramatic footnote to the proposed association between the magnetic spheroids and combustion of organic shales. Interestingly, the Mottled Zone also contains the rare mineral magnesioferrite, which was identified both within the K/T magnetic spheroids and as discrete crystals in boundary clay from marine and continental sites.
Records of major geologic events of the past about 260 Myr including: biologic extinction events, ocean-anoxic and black-shale events, major changes in sea level, major evaporite (salt) deposits, continental flood-basalt eruptions, first-order discontinuities in sea-floor spreading, and major mountain building events, have been aggregated and analyzed with moving-window and spectral techniques that facilitate recognition of clustering and possible cyclicity. Significant clustering of events suggests a model in which changes in rates and directions of sea-floor spreading ('ridge jumps') are associated with episodic rifting, volcanism, mountain building, global sea level and changes in the composition of the earth's atmosphere via the carbon cycle. The geologic data formally show a statistically significant underlying periodicity of 26.6 Myr for the Mesozoic and Cenozoic. Phase information suggests that the most recent maximum of the cycle occurred with the last 9 Myr, and may be close to the present time.
The study of the fossilization processes of modern cyanobacteria provides insights needed to recognize bacterial microfossils. The fossilization of cyanobacteria is discussed and images of recent and fossil bacteria and cyanobacteria from the Early Proterozoic to Neogene carbonaceous rocks (kerites, shungites, and black shales) and phosphorites are provided. These are compared with biomorphic microstructures and possible microfossils encountered in-situ in carbonaceous meteorites.
Superplumes offer a new approach for understanding global C cycles. Isotopes help to discern the impacts of geological, environmental and biological processes ujpun the evolution of these cycles. For example, C-13/C-12 values of coeval sedimentary organics and carbonates give global estimates of the fraction of C buried as organics (Forg), which today lies near 0.2. Before Oxygenic photosynthesis arose, our biosphere obtained reducing power for biosynthesis solely from thermal volatiles and rock alteration. Thus Forg was dominated by the mantle redox state, which has remained remarkably constant for greater than Gy. Recent data confirm that the long-term change in Forg had been small, indicating that the mantle redox buffer remains important even today. Oxygenic photosynthesis enabled life to obtain additional reducing power by splitting the water molecule. Accordingly, biological organic production rose above the level constrained by the mantle-derived flux of reduced species. For example, today, chemoautotrophs harvesting energy from hydrothermal emanations can synthesize at most between 0.2 x 10(exp 12) and 2x 10(exp 12) mol C yr-1 of organic C globally. In contrast, global photosynthetic productivity is estimated at 9000 x 10(exp 12) mol C yr-1. Occasionally photosynthetic productivity did contribute to dramatically -elevated Forg values (to 0.4 or more) as evidenced by very high carbonate C-13/C-12. The interplay between biological, tectonic and other environmental factors is illustrated by the mid-Archean to mid-Proterozoic isotopic record. The relatively constant C-13/C-12 values of Archean carbonates support the view that photosynthetically-driven Forg increases were not yet possible. In contrast, major excursions in C-13/C-12, and thus also in Forg, during the early Proterozoic confirmed the global importance of oxygenic photosynthesis by that time. Remarkably, the superplume event at 1.9 Ga did not trigger another major Forg increase, despite the favorable conditions for organic burial that were evidenced by elevated sea levels and higher black shale abundances. Perhaps those superplume-rated processes that favored enhanced organic burial were offset by the ability of mantle-derived redox buffering, which was enhanced during the superplume event, to limit excursions in Forg.
In an effort to locate sources of natural gas in Ohio, the fractures and lineaments in Black Devonian shale were measured by: (1) field mapping of joints, swarms, and fractures; (2) stereophotointerpretation of geomorphic lineaments with precise photoquads; and (3) by interpreting the linear features on LANDSAT images. All results were compiled and graphically represented on 1:250,000 scale maps. The geologic setting of Lawrence County was defined and a field fracture map was generated and plotted as rose patterns at the exposure site. All maps were compared, contrasted, and correlated by superimposing each over the other as a transparency. The LANDSAT lineaments had significant correlation with the limits of oil and gas producing fields. These limits included termination of field production as well as extensions to other fields. The lineaments represent real rock fractures with zones of increased permeability in the near surface bedrock.
One intriguing and important issue of the Sudbury Structure concerns the source of the relatively large amount of C in the Onaping Formation Black member. This dilemma was recently addressed, and the conclusion was reached that an impactor could not have delivered all of the requisite C. Becker et al. have suggested that much of the C came from the impactor and reported the presence of interstellar He "caged" inside some fullerenes that may have survived the impact. So, conceivably, the C inventory in the Sudbury Structure comes from both target and impactor materials, although the known target rocks have little C. We discuss here the possibility of two terrestrial sources for at least some of the C: (1) impact evaporation/dissociation of C from carbonate target rocks and (2) the presence of heretofore-unrecognized C-rich (up to 26 wt%) siliceous "shale," fragments, which are found in the upper, reworked Black member. Experimental: Hypervelocity impact of a 0.635-diameter Al projectile into dolomite at 5.03 km/s (performed at the Ames Research Center vertical gun range) produced a thin, black layer (= 0.05 mm thick) that partially lined the crater and coated impactor remnants. Scanning electronic microscope (SEM) imagery shows this layer to be spongelike on a submicron scale and Auger spectroscopic analyses yield: 33% C, 22% Mg, 19% 0, and 9% Al (from the projectile). Elemental mapping shows that all of the available 0 is combined with Ca and Mg, Al is not oxidized, and C is in elemental form. Dissociation efficiency of C from CO2 is estimated to be <10% of crater volume. Raman spectroscopy indicates that the C is highly disorganized graphite. Another impact experiment [4] also produced highly disordered graphite from a limestone target (reducing collector), in addition to small amounts of diamond/lonsdaleite/chaoite (oxidizing collector). These experiments confirm the reduction of C from carbonates in impact vapor plumes. Observational: SEM observations and microprobe analyses of small, black shalelike inclusions in the upper Black Onaping indicate high C contents (7-26 wt% avg. = 16%). They contain mostly quartz and carbonaceous matter with small amounts of altered K-feldspar, clays, Fe oxide, and a sulfide. No evidence of shock is seen in quartz, and overall characteristics indicate a natural, lightly metamorphosed carbonaceous shale or mudstone that probably existed as a preimpact rock in the target region and distal fragments washed in during early crater filling. Fragments range in size from tens of microns to cm and increase in abundance in the upper Black toward the Onwatin contact, although their distribution is highly irregular. This increase corresponds to an increase in "organic" C with increasingly negative delta-13 C values and S, together with a decrease in fullerene abundance. In addition, we have found soot in acid-demineralized residues of the Onwatin but not in the Onaping samples. These data could be consistent with impact plume and atmospheric chemical processes, with possible diageneric ovedays. We are analyzing carbonaceous fractions of the Onaping and Onwatin to determine diagnostic C isotopic signatures Analyses by Whitehead et al. on bulk samples revealed no definitive source or processes, although delta-13 C values for "organic" C overlapped those for some meteorites. Discussion: If impact evaporation of Sudbury target carbonates did occur, then where are the carbonates? Distal carbonate (limestone/dolostone) exposures of the Espanola Formation (Huronian Supergroup) are generally thin-bedded, although remnants that partially encompass the Sudbury Crater are variable in thickness and may locally reach 250 m . If a carbonate thickness of 100-200 in existed at the target site, then copious amounts of C could have been reduced by impact processing of carbonates and also C-shale, depending on the efficiency of the processing and the amount of postimpact oxidation. Conclusion: The Sudbury crater offers a unique opportunity to study preserved characteristics of immediate carbonaceous fallback matter and particles of short-term residency in the impact plume as well as dust/aerosols from postimpact atmospheric processing.
Forest canopies over different sedimentary lithologies of valleys and ridges are composed of different dominant species and have significantly different reflectance and emittance. In a botanical survey of eighty-seven forest sites, sedimentary lithologies were found to differ in the species which dominate the forest canopy. Sandstone sites had abundant chestnut oak (Quercus prinus), black oak (Q. velutina), and northern red oak (Q. rubra). On shale sites chestnut oak, white oak (Q. alba), northern red oak and red pine (Pinus resinosa) were dominant. Limestone sites had a variable species composition with the most common species, northern red oak, white oak, and black locust (Robinia pseudocacia) accounting for only 30 percent of the total trees. Thematic Mapper Simulator (TMS) data obtained during the growing season were analyzed to determine if sandstones, shales, and limestones could be distinguished on the basis of forest-canopy reflectance. The observations compared in the analysis were means of the eight TMS bands for 10 x 10-pixel test sites selected from areas with complete canopy closure. In August imagery the three lithologies were separable based on differences in TMS band 3 (630-690 nm) and band 8 (10.4-12.5 microns).
Remote sensing was included in a comprehensive investigation of the use of geophysical techniques to aid in underground mine placement. The primary objective was to detect faults and slumping, features which, due to structural weakness and excess water, cause construction difficulties and safety hazards in mine construction. Preliminary geologic reconnaissance was performed on a potential site for an underground oil shale mine in the Piceance Creek Basin of Colorado. LANDSAT data, black and white aerial photography and 3 cm radar imagery were obtained. LANDSAT data were primarily used in optical imagery and digital tape forms, both of which were analyzed and enhanced by computer techniques. The aerial photography and radar data offered supplemental information. Surface linears in the test area were located and mapped principally from LANDSAT data. A specific, relatively wide, linear pointed directly toward the test site, but did not extend into it. Density slicing, ratioing, and edge enhancement of the LANDSAT data all indicated the existence of this linear. Radar imagery marginally confirmed the linear, while aerial photography did not confirm it.
The Black Sea is the world's largest anoxic basin; it is also a contemporary analogue of the environment in which carbonaceous shales and petroleum source beds formed. Recently, Repeta et al. reported that anoxygenic photosynthesis may be an important component of carbon cycling in the present Black Sea, owing to a shoaling of the chemocline and consequent penetration of the photic zone by anaerobic waters in the past few decades. It has been suggested that this was due to an anthropogenic decrease in freshwater input to the Black Sea, although natural causes were not ruled out. Here we report the distributions of sequestered photosynthetic pigments in eight core samples of sediments from the Black Sea ranging in age from zero to 6,200 years before the present. Our results show that photosynthetic green sulphur bacteria (Chlorobiaceae [correction of Clorobiaceae]) have been active in the Black Sea for substantial periods of time in the past. This finding indicates that the penetration of the photic zone by anaerobic waters is not a recent phenomenon, and suggests that natural causes for shoaling of the chemocline are more likely than anthropogenic ones.
The 0.3-2.6 micrometers spectral reflectance properties of carbon polymorphs (graphite, carbon black, diamond), carbides (silicon carbide, cementite), and macromolecular organic-bearing materials (coal, coal tar extract, oil sand, oil shale) are found to vary from sample to sample and among groups. The carbon polymorphs are readily distinguishable on the basis of their visible-near infrared spectral slopes and shapes. The spectra of macromolecular organic-bearing materials show increases in reflectance toward longer wavelengths, exceeding the reflectance rise of more carbon-rich materials. Reflectance spectra of carbonaceous materials are affected by the crystal structure, composition, and degree of order/disorder of the samples. The characteristic spectral properties can potentially be exploited to identify individual carbonaceous grains in meteorites (as separates or in situ) or to conduct remote sensing geothermometry and identification of carbonaceous phases on asteroids.
The distributions of hydroxyacids in a variety of recent and ancient sediments have been determined by gas chromatography-mass spectrometry. A lacustrine sediment (Rostherne Mere, U.K.) and two marine situations (Cariaco Trench, Black Sea) were analyzed as examples of recent depositional environments. Beta-hydroxyacids occurred in all of the recent sediments, consistent with their presumed microbial origin, whereas di- and trihydroxyacids were present in the sediments with a significant higher plant input (Black Sea and Rostherne Mere sediments). The two ancient (Eocene) sediments examined, viz, the Greene River (U.S.) and Messel (Germany) oil shales, contained only trace amounts of hydroxyacids. These results provide evidence that hydroxyacids are in general not well preserved over geological time.
Monitoring changes in greenhouse gas (GHG) emission is critical for assessing climate mitigation efforts towards the Paris Agreement goal. A crucial aspect of science-based GHG monitoring is to provide objective information for quality assurance and uncertainty assessment of the reported emissions. Emission estimates from combustion events (gas flaring and biomass burning) are often calculated based on activity data (AD) from satellite observations, such as those detected from the visible infrared imaging radiometer suite (VIIRS) onboard the Suomi-NPP and NOAA-20 satellites. These estimates are often incorporated into carbon models for calculating emissions and removals. Consequently, errors and uncertainties associated with AD propagate into these models and impact emission estimates. Deriving uncertainty of AD is therefore crucial for transparency of emission estimates but remains a challenge due to the lack of evaluation data or alternate estimates. This work proposes a new approach using machine learning (ML) for combustion detection from NASA's Black Marble product suite and explores the assessment of potential uncertainties through comparison with existing detections. We jointly characterize combustion using thermal and light emission signals, with the latter improving detection of probable weaker combustion with less distinct thermal signatures. Being methodologically independent, the differences in ML-derived estimates with existing approaches can indicate the potential uncertainties in detection. The approach was applied to detect gas flares over the Eagle Ford Shale, Texas. We analyzed the spatio-temporal variations in detections and found that approximately 79.04% and 72.14% of the light emission-based detections are missed by ML-derived detections from VIIRS thermal bands and existing datasets, respectively. This improvement in combustion detection and scope for uncertainty assessment is essential for comprehensive monitoring of resulting emissions and we discuss the steps for extending this globally.
Cyclic diterpenoid compounds have been found by various investigators in the geosphere (e.g., fossil resins, coals, soil, shale, and deep-sea sediments). These compounds occur in significant amounts only in higher plants and are therefore potential markers of terrigenous plant lipids. Diterpenoids with the abietane skeleton (mainly dehydroabietic acid) have been identified in the lipids of sediment samples from the northeast Pacific Ocean, Black Sea, and North Atlantic Ocean. The presence of these resin-derived compounds was correlated with the terrigenous clay components and with the presence of pollen. The presence of polycyclic diterpenoids was also correlated with the distribution patterns and inferred sources of other sediment lipid constituents. Potamic transport, followed by turbidite redistribution, is the probable input mechanism of these resin-derived compounds to the deep-sea sediments. These diterpenoids appear to be excellent biological markers of resinous higher plants.