Depositional and diagenetic variability within the Cambrian Mount Simon Sandstone: Implications for carbon dioxide sequestration

USGS Publications Warehouse

Bowen, B.B.; Ochoa, R.I.; Wilkens, N.D.; Brophy, J.; Lovell, T.R.; Fischietto, N.; Medina, C.R.; Rupp, J.A.

2011-01-01

The Cambrian Mount Simon Sandstone is the major target reservoir for ongoing geologic carbon dioxide (CO2) sequestration demonstrations throughout the midwest United States. The potential CO2 reservoir capacity, reactivity, and ultimate fate of injected CO2 depend on textural and compositional properties determined by depositional and diagenetic histories that vary vertically and laterally across the formation. Effective and efficient prediction and use of the available pore space requires detailed knowledge of the depositional and diagenetic textures and mineralogy, how these variables control the petrophysical character of the reservoir, and how they vary spatially. Here, we summarize the reservoir characteristics of the Mount Simon Sandstone based on examination of geophysical logs, cores, cuttings, and analysis of more than 150 thin sections. These samples represent different parts of the formation and depth ranges of more than 9000 ft (>2743 m) across the Illinois Basin and surrounding areas. This work demonstrates that overall reservoir quality and, specifically, porosity do not exhibit a simple relationship with depth, but vary both laterally and with depth because of changes in the primary depositional facies, framework composition (i.e., feldspar concentration), and diverse diagenetic modifications. Diagenetic processes that have been significant in modifying the reservoir include formation of iron oxide grain coatings, chemical compaction, feldspar precipitation and dissolution, multiple generations of quartz overgrowth cementation, clay mineral precipitation, and iron oxide cementation. These variables provide important inputs for calculating CO2 capacity potential, modeling reactivity, and are also an important baseline for comparisons after CO2 injection. Copyright ??2011. The American Association of Petroleum Geologists/Division of Environmental Geosciences. All rights reserved.

Early Triassic fluctuations of the global carbon cycle: New evidence from paired carbon isotopes in the western USA basin

NASA Astrophysics Data System (ADS)

Caravaca, Gwénaël; Thomazo, Christophe; Vennin, Emmanuelle; Olivier, Nicolas; Cocquerez, Théophile; Escarguel, Gilles; Fara, Emmanuel; Jenks, James F.; Bylund, Kevin G.; Stephen, Daniel A.; Brayard, Arnaud

2017-07-01

In the aftermath of the catastrophic end-Permian mass extinction, the Early Triassic records recurrent perturbations in the carbon isotope signal, most notably during the Smithian and through the Smithian/Spathian Boundary (SSB; 1.5 myr after the Permian/Triassic boundary), which show some of the largest excursions of the Phanerozoic. The late Smithian also corresponds to major biotic turnovers and environmental changes, such as temperature fluctuations, that deeply impacted the recovery after the end-Permian mass extinction. Here we document the paired carbon isotope signal along with an analysis of the trace and major elements at the long-known Hot Springs section (southeastern Idaho, USA). This section records Early Triassic sediments from the Griesbachian-Dienerian up to the lower Spathian. We show that the organic and carbonate δ13C variations mirror the signals identified at a global scale. Particularly, the middle Smithian-SSB event represented by a negative-positive isotopic couplet is well identified and is not of diagenetic origin. We also document a positive excursion potentially corresponding to the Dienerian/Smithian Boundary. Observed Smithian-Spathian excursions are recorded similarly in both the organic and carbonate reservoirs, but the organic matter signal systematically shows unexpectedly dampened variations compared to its carbonate counterpart. Additionally, we show that variations in the net isotopic effect (i.e., Δ13C) probably resulted from a complex set of forcing parameters including either a mixing between terrestrial and marine organic matter depending on the evolution of the depositional setting, or variations in the biological fractionation. We establish that the Δ13C signal cannot be directly related to CO2-driven temperature variations at Hot Springs. Even though the carbon isotope signal mirrors the Early Triassic variations known at the global scale, the Hot Springs signal probably also reflects local influences on the carbon

Morphological recognition of Globigerinoides ruber morphotypes and their susceptibility to diagenetic alteration in the eastern Mediterranean Sea

NASA Astrophysics Data System (ADS)

Kontakiotis, G.; Antonarakou, A.; Mortyn, P. G.; Drinia, H.; Anastasakis, G.; Zarkogiannis, S.; Möbius, J.

2017-10-01

Planktonic foraminiferal geochemistry presents a valuable archive for paleoceanographic reconstructions. However in high salinity and carbonate super-saturated settings, precipitation of inorganic calcite onto foraminiferal tests can potentially alter the primary geochemical signal, biasing Mg/Ca ratios and ensuing paleoceanographic reconstructions. Here we utilize test biometrics (specifically related to the compression and elongation of the last chambers) to identify four distinct morphotypes (labelled A-D) of the paleoceanographically important planktonic foraminifer species Globigerinoides ruber, and further evaluate their susceptibility to diagenetic alteration from a suite of surface sediments in the eastern Mediterranean Sea. The three distinguished morphotypes (A-C) correspond to previously recognized morphotypes ("Normal", "Platys", "Elongate" respectively) in the Mediterranean Sea, while the remaining (D or "Twin") was designated for the first time. We also compare Scanning Electron Microscopy (SEM) observations performed on four distinguished morphotypes, indicative of potential diagenetic alteration influence. We identified 3 different overgrowth stages (OGA1-OGA3), as a function of geography in the study area. The early diagenesis degrees (involving all the morphotypes) are only geographically distinct along the eastern Mediterranean (increasing to the south), since the morphology does not play a role in the likelihood of diagenetic alteration. Particularly, in the north Aegean Sea, SEM analyses reveal the absence or limited presence of an overgrowth imprint in all recognized morphotypes, while in the central-south Aegean and Levantine Seas they show higher amplitudes of diagenetic overprint supporting the general trend to advanced diagenetic alteration. The semi-enclosed oligotrophic nature and high salinity of this setting, in combination with the different degree of carbonate precipitation and calcite super-saturation between the sub-basins, could

Diagenetic Crystal Growth in the Murray Formation, Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Kah, L. C.; Kronyak, R. E.; Ming, D. W.; Grotzinger, J. P.; Schieber, J.; Sumner, D. Y.; Edgett, K. S.

2015-01-01

The Pahrump region (Gale Crater, Mars) marks a critical transition between sedimentary environments dominated by alluvial-to-fluvial materials associated with the Gale crater rim, and depositional environments fundamentally linked to the crater's central mound, Mount Sharp. At Pahrump, the Murray formation consists of an approximately 14-meter thick succession dominated by massive to finely laminated mudstone with occasional interbeds of cross-bedded sandstone, and is best interpreted as a dominantly lacustrine environment containing tongues of prograding fluvial material. Murray formation mudstones contain abundant evidence for early diagenetic mineral precipitation and its subsequent removal by later diagenetic processes. Lenticular mineral growth is particularly common within lacustrine mudstone deposits at the Pahrump locality. High-resolution MAHLI images taken by the Curiosity rover permit detailed morphological and spatial analysis of these features. Millimeter-scale lenticular features occur in massive to well-laminated mudstone lithologies and are interpreted as pseudomorphs after calcium sulfate. The distribution and orientation of lenticular features suggests deposition at or near the sediment-water (or sediment-air) interface. Retention of chemical signals similar to host rock suggests that original precipitation was likely poikilotopic, incorporating substantial amounts of the primary matrix. Although poikilotopic crystal growth is common in burial environments, it also occurs during early diagenetic crystal growth within unlithified sediment where high rates of crystal growth are common. Loss of original calcium sulfate mineralogy suggests dissolution by mildly acidic, later-diagenetic fluids. As with lenticular voids observed at Meridiani by the Opportunity Rover, these features indicate that calcium sulfate deposition may have been widespread on early Mars; dissolution of depositional and early diagenetic minerals is a likely source for both calcium

Diagenetic Carbonates Related to Hydrocarbon-rich Fluid Seepage in the Nile Deep Sea Fan (East Mediterranean Sea)

NASA Astrophysics Data System (ADS)

Pierre, C.; Gontharet, S.; Blanc-Valleron, M. M.; Bayon, G.; Dupré, S.; Mascle, J.

2017-12-01

During the NAUTINIL (September-October 2003), MIMES (July 2004), BIONIL (October 2006) and MEDECO2 (November 2007) cruises, coring and submersible dives were realized in the Nile Deep Sea Fan (NDSF) area. Active fluid venting sites were identified by the presence of living benthic organisms and by methane plumes in the bottom waters above the seeping structures. At all sites, hard carbonate crusts cover irregularly the sea floor. The sediments from the venting areas are organic-rich, contain sometimes carbonate concretions and have a strong H2S smell indicative of active sulfate reduction. The mineralogy of carbonate crusts is dominated by aragonite and Mg-calcite; the mineralogy of concretions is more complex, with mixtures of Mg-calcite, dolomite and ankerite. The oxygen and carbon isotopic compositions of the carbonate from crusts and concretions exhibit large variations (-2.8< δ18O ‰ VPDB <+9.5; -42.6< δ13C ‰ VPDB <+22.4). The wide range of δ18O values reflects variable sources of fluids. Most of the authigenic carbonates from the NDSF were precipitated in isotopic equilibrium with the Mediterranean bottom water. The carbonate crusts and concretions from the brine seeps of the north-western NDSF are enriched in 18O indicating that a source of 18O-rich fluids originated from depth. Differently, a few crusts and concretions from the eastern NDSF exhibit relatively low δ18O values, which are due to precipitation at warm temperatures. The very low δ13C values of the diagenetic carbonates indicate that methane and possibly other heavier hydrocarbons were the major source of carbon that was oxidized as bicarbonate mostly through bacterial sulfate reduction coupled with anaerobic methane oxidation within the anoxic sediment. The very positive δ13C values of the diagenetic carbonates from many carbonate concretions are related to the production of 13C-rich CO2 during methanogenesis within the sub-seafloor sediments.

Petrology and diagenetic history of the upper shale member of the Late Devonian-Early Mississippian Bakken Formation, Williston Basin, North Dakota

USGS Publications Warehouse

Neil S. Fishman,; Sven O. Egenhoff,; Boehlke, Adam; Lowers, Heather A.

2015-01-01

The organic-rich upper shale member of the upper Devonian–lower Mississippian Bakken Formation (Williston Basin, North Dakota, USA) has undergone significant diagenetic alteration, irrespective of catagenesis related to hydrocarbon generation. Alteration includes precipitation of numerous cements, replacement of both detrital and authigenic minerals, multiple episodes of fracturing, and compaction. Quartz authigenesis occurred throughout much of the member, and is represented by multiple generations of microcrystalline quartz. Chalcedonic quartz fills radiolarian microfossils and is present in the matrix. Sulfide minerals include pyrite and sphalerite. Carbonate diagenesis is volumetrically minor and includes thin dolomite overgrowths and calcite cement. At least two generations of fractures are observed. Based on the authigenic minerals and their relative timing of formation, the evolution of pore waters can be postulated. Dolomite and calcite resulted from early postdepositional aerobic oxidation of some of the abundant organic material in the formation. Following aerobic oxidation, conditions became anoxic and sulfide minerals precipitated. Transformation of the originally opaline tests of radiolaria resulted in precipitation of quartz, and quartz authigenesis is most common in more distal parts of the depositional basin where radiolaria were abundant. Because quartz authigenesis is related to the distribution of radiolaria, there is a link between diagenesis and depositional environment. Furthermore, much of the diagenesis in the upper shale member preceded hydrocarbon generation, so early postdepositional processes were responsible for occlusion of significant original porosity in the member. Thus, diagenetic mineral precipitation was at least partly responsible for the limited ability of these mudstones to provide porosity for storage of hydrocarbons.

Diagenetic patterns and pore space distribution along a platform to outer-shelf transect (Urgonian limestone, Barremian-Aptian, SE France)

NASA Astrophysics Data System (ADS)

Léonide, Philippe; Fournier, François; Reijmer, John J. G.; Vonhof, Hubert; Borgomano, Jean; Dijk, Jurrien; Rosenthal, Maelle; van Goethem, Manon; Cochard, Jean; Meulenaars, Karlien

2014-06-01

The Urgonian limestones of Late Barremian/Early Aptian from Provence (SE, France) are characterized by the occurrence of microporous limestones at regional scale alternating with tight carbonates. This study, based on petrographical (sediment texture, facies) and diagenetical analyses (cement stratigraphy, porosity and isotope geochemistry) of more than 800 limestone samples provides insight into the parameters controlling the genesis, preservation or occlusion of microporosity along an inner platform to outer shelf transect. The tight and microporous Urgonian limestones from Provence can be grouped into 5 rock-types based on textures, associated depositional environments, porosity and pore-type, being: (1) tight inner-platform: TIP; (2) porous inner platform: PIP; (3) tight outer platform: TOP; (4) porous outer platform: POP and (5) tight outer shelf: TOS. In tight (TIP, TOP and TOS types) limestones intergranular and intragranular pore spaces were entirely occluded by early marine and/or early meteoric cementation, whereas in microporous (PIP, POP) limestones a significant fraction of the intergranular macroporosity was preserved during early and shallow burial diagenesis. Micrite neomorphism (hybrid Ostwald ripening process) occurred during meteoric shallow burial diagenesis in PIP and POP limestones during the regional Durancian Uplift event (Albian-Lower Cenomanian). This process resulted in microporosity enhancement and preservation. Circulation of meteoric fluids during exhumation produces intercrystalline microporosity enhancement and moldic porosity development. The present study documents the important role that both early diagenetic and depositional cycles and long-term tectonic processes have on pore space evolution and distribution in Mesozoic platform carbonates.

Diagenetic gypsum related to sulfur deposits in evaporites (Libros Gypsum, Miocene, NE Spain)

NASA Astrophysics Data System (ADS)

Ortí, Federico; Rosell, Laura; Anadón, Pere

2010-07-01

The Libros Gypsum is the thickest evaporite unit of the Miocene infill of the Teruel Basin in NE Spain. During the deposition of this unit, intense bacterial sulfate-reducing (BSR) activity in the lake depocenter generated a native sulfur deposit. Diagenetic gypsum resulted from subsequent sulfur oxidation. The different processes involved in these transformations were first investigated by Anadón et al. (1992). The present paper is concerned with this diagenetic gypsum from the stratigraphic, petrographic, isotopic and genetic points of view. Diagenetic gypsum occurs mainly as continuous or discontinuous layers, individual levels or lenses, irregular masses, nodules and micronodules, and veins. Its main textures are coarse-crystalline anhedral and fine-grained (alabastrine), both of which can replace any former lithology (carbonate, gypsum, and sulfur). The following sequence of processes and mineral/textural transformations is deduced: primary gypsum deposition — BSR and biodiagenetic carbonate/H 2S production — growth of native sulfur — growth of diagenetic gypsum — partial recrystallization of the diagenetic gypsum textures. The gypsification of the native sulfur generated two types of banded structures in the diagenetic gypsum: (1) concentric structures of centripetal growth, and (2) expansive, roughly concentric structures. In the first type, the gypsification operated from the outer boundaries towards the inner parts. In the second type, part of the carbonate hosting the sulfur was also gypsified (replaced/cemented). In the diagenetic gypsum, the δ34S values are in agreement with a native sulfur and H 2S provenance. The δ18O sulfate values, however, enable us to differentiate two main groups of values: one with positive values and the other with negative values. In the group of positive values, interstitial (evaporated) solutions participated in the sulfur oxidation; this process presumably occurred in a first oxidation stage during shallow

Early diagenesis driven by widespread meteoric infiltration of a Central European carbonate ramp: A reinterpretation of the Upper Muschelkalk

NASA Astrophysics Data System (ADS)

Adams, Arthur; Diamond, Larryn W.

2017-12-01

Meteoric diagenesis of carbonate ramps is often difficult to interpret and can commonly be confused with other coinciding diagenetic processes. The Middle Triassic Upper Muschelkalk of Switzerland provides an insightful case in which the effects of several overprinting diagenetic environments, including matrix dolomitization, can be clearly unravelled. Previous studies suggested that diagenesis took place in connate marine waters, with later meteoric waters being invoked to explain recrystallization of dolomite. In this study, diagenetic analyses (C-O stable isotope ratios, thin-section point counting, cathodoluminescence and UV-fluorescence microscopy) of calcitic bioclastic samples have revealed that early diagenesis (pre-stylolitization) and the accompanying porosity evolution did not occur exclusively in the presence of marine fluids. Five sequential stages of diagenesis have been identified: marine, shallow burial, mixing-zone, meteoric and dolomitization. Marine diagenesis induced precipitation of bladed and inclusion-rich syntaxial cements that fluoresce strongly under UV-light. Both cements account for a mean 7.5 vol% reduction in the porosity of bioclastic beds. Shallow burial diagenesis likely induced mouldic porosity and associated fluorescent dog-tooth cementation. Based on light oxygen isotope and elevated strontium isotope ratios, matrix aragonite-calcite neomorphism is interpreted to have occurred in a mixture of marine and meteoric fluids. The combination of shallow burial and mixing-zone processes reduced porosity on average by 4.8 vol%. Evidence for subsequent meteoric diagenesis is found in abundant dog-tooth and blocky calcite cements that have mean δ18OVPDB of - 9.36‰ and no signs of recrystallization. These meteoric cements reduced porosity by a further 13.4 vol%. Percolation of meteoric water through the ramp was driven by hydraulic gradients on an adjacent basement high, which was exposed by a cycle of early Ladinian regressions

Cyclic, Early Diagenetic Dolomite Formation in Alkaline Lake Van

NASA Astrophysics Data System (ADS)

McCormack, J.; Bontognali, T. R. R.; Immenhauser, A.; Kwiecien, O.

2017-12-01

rapid Northern Hemisphere temperature oscillation (i.e. Greenland Interstadials). Lake Vańs dolomite record thus provides compelling arguments suggesting that early diagenetic dolomite formation within an alkaline environment can be highly sensitive to hydrological changes even on centennial timescales.

Diagenesis in coastal carbonates related to Pleistocene sea level, Bermuda Platform

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vollbrecht, R.; Meischner, D.

1996-01-01

Pleistocene glacioeustatic sea-level oscillation on the stable Bermuda Platform is expressed in a succession of shallow-water carbonates interrupted by lowstand unconformities. In Bermuda, the maximum highstands of the last 400,000 yr ranged within 10 m around the present level. Coastal carbonates of various highstands are exposed along the present shoreline. These carbonates were penetrated by meteoric and marine pore waters during lowstands and highstands following on deposition. Two representative Pleistocene shoreline sections were studied to see whether early diagenesis has recorded these pore-water changes. The sediments of both sections show multiple generations of cement. Optical and scanning electron microscopy, cathodoluminescencemore » microscopy, X-ray diffraction, microprobe studies and stable-isotope analyses were used to determine the diagenetic environments involved. Regardless of the degree of substrate cementation, freshwater alteration was mainly vadose whereas marine cementation was either phreatic or vadose or both. Early diagenetic oscillation is easier recorded in coastal successions than in lagoonal sediments, mainly because marine cementation is more active nearshore.Because the coastal environment is prone to wave destruction, the potential for preserving these diagenetic features is usually low. Data published on tectonically unstable areas suggest that early diagenetic oscillation may characterize stable coastlines.« less

Diagenetic contrast of sandstones in hydrocarbon prospective Mesozoic rift basins (Ethiopia, UK, USA)

NASA Astrophysics Data System (ADS)

Wolela, A.

2014-11-01

Diagenetic studied in hydrocarbon-prospective Mesozoic rift basins were carried out in the Blue Nile Basin (Ethiopia), Ulster Basin (United Kingdom) and Hartford Basin (United States of America). Alluvial fan, single and amalgamated multistorey meandering and braided river, deep and shallow perennial lake, shallow ephemeral lake, aeolian and playa mud-flat are the prominent depositional environments. The studied sandstones exhibit red bed diagenesis. Source area geology, depositional environments, pore-water chemistry and circulation, tectonic setting and burial history controlled the diagenetic evolution. The diagenetic minerals include: facies-related minerals (calcrete and dolocrete), grain-coating clay minerals and/or hematite, quartz and feldspar overgrowths, carbonate cements, hematite, kaolinite, illite-smectite, smectite, illite, chlorite, actinolite, laumontite, pyrite and apatite. Diversity of diagenetic minerals and sequence of diagenetic alteration can be directly related to depositional environment and burial history of the basins. Variation in infiltrated clays, carbonate cements and clay minerals observed in the studied sandstones. The alluvial fan and fluviatile sandstones are dominated by kaolinite, illite calcite and ferroan calcite, whereas the playa and lacustrine sandstones are dominated by illite-smectite, smectite-chlorite, smectite, chlorite, dolomite ferroan dolomite and ankerite. Albite, pyrite and apatite are predominantly precipitated in lacustrine sandstones. Basaltic eruption in the basins modified mechanically infiltrated clays to authigenic clays. In all the studied sandstones, secondary porosity predominates over primary porosity. The oil emplacement inhabited clay authigenesis and generation of secondary porosity, whereas authigenesis of quartz, pyrite and apatite continued after oil emplacement.

PEaCH4 v.2.0: A modelling platform to predict early diagenetic processes in marine sediments with a focus on biogenic methane - Case study: Offshore Namibia

NASA Astrophysics Data System (ADS)

Arning, Esther T.; Häußler, Steffen; van Berk, Wolfgang; Schulz, Hans-Martin

2016-07-01

The modelling of early diagenetic processes in marine sediments is of interest in marine science, and in the oil and gas industry, here, especially with respect to methane occurrence and gas hydrate formation as resources. Early diagenesis in marine sediments evolves from a complex web of intertwining (bio)geochemical reactions. It comprises microbially catalysed reactions and inorganic mineral-water-gas interactions. A model that will describe and consider all of these reactions has to be complex. However, it should be user-friendly, as well as to be applicable for a broad community and not only for experts in the field of marine chemistry. The presented modelling platform PeaCH4 v.2.0 combines both aspects, and is Microsoft Excel©-based. The modelling tool is PHREEQC (version 2), a computer programme for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations. The conceptual PEaCH4 model is based on the conversion of sediment-bound degradable organic matter. PEaCH4 v.2.0 was developed to quantify and predict early diagenetic processes in marine sediments with the focus on biogenic methane formation and its phase behaviour, and allows carbon mass balancing. In regard to the irreversible degradation of organic matter, it comprises a "reaction model" and a "kinetic model" to predict methane formation. Both approaches differ in their calculations and outputs as the "kinetic model" considers the modelling time to integrate temperature dependent biogenic methane formation in its calculations, whereas the "reaction model" simply relies on default organic matter degradation. With regard to the inorganic mineral-water-gas interactions, which are triggered by irreversible degradation of organic matter, PEaCH4 v.2.0 is based on chemical equilibrium thermodynamics, appropriate mass-action laws, and their temperature dependent equilibrium constants. The programme is exemplarily presented with the example of upwelling sediments off Namibia

Compositional controls on early diagenetic pathways in fine-grained sedimentary rocks: Implications for predicting unconventional reservoir attributes of mudstones

USGS Publications Warehouse

Keller, Margaret A.; Macquaker, Joe H.S.; Taylor, Kevin G.; Polya, David

2014-01-01

Diagenesis significantly impacts mudstone lithofacies. Processes operating to control diagenetic pathways in mudstones are poorly known compared to analogous processes occurring in other sedimentary rocks. Selected organic-carbon-rich mudstones, from the Kimmeridge Clay and Monterey Formations, have been investigated to determine how varying starting compositions influence diagenesis.The sampled Kimmeridge Clay Formation mudstones are organized into thin homogenous beds, composed mainly of siliciclastic detritus, with some constituents derived from water-column production (e.g., coccoliths, S-depleted type-II kerogen, as much as 52.6% total organic carbon [TOC]) and others from diagenesis (e.g., pyrite, carbonate, and kaolinite). The sampled Monterey Formation mudstones are organized into thin beds that exhibit pelleted wavy lamination, and are predominantly composed of production-derived components including diatoms, coccoliths, and foraminifera, in addition to type-IIS kerogen (as much as 16.5% TOC), and apatite and silica cements.During early burial of the studied Kimmeridge Clay Formation mudstones, the availability of detrital Fe(III) and reactive clay minerals caused carbonate- and silicate-buffering reactions to operate effectively and the pore waters to be Fe(II) rich. These conditions led to pyrite, iron-poor carbonates, and kaolinite cements precipitating, preserved organic carbon being S-depleted, and sweet hydrocarbons being generated. In contrast, during the diagenesis of the sampled Monterey Formation mudstones, sulfide oxidation, coupled with opal dissolution and the reduced availability of both Fe(III) and reactive siliciclastic detritus, meant that the pore waters were poorly buffered and locally acidic. These conditions resulted in local carbonate dissolution, apatite and silica cements precipitation, natural kerogen sulfurization, and sour hydrocarbons generation.Differences in mud composition at deposition significantly influence subsequent

Insights into the diagenetic environment of fossil marine vertebrates of the Pisco Formation (late Miocene, Peru) from mineralogical and Sr-isotope data

NASA Astrophysics Data System (ADS)

Gioncada, A.; Petrini, R.; Bosio, G.; Gariboldi, K.; Collareta, A.; Malinverno, E.; Bonaccorsi, E.; Di Celma, C.; Pasero, M.; Urbina, M.; Bianucci, G.

2018-01-01

The late Miocene Pisco Formation of Peru is an outstanding example of richness and high-quality preservation of fossil marine vertebrates. In order to reconstruct the fossilization path, we present new textural, mineralogical and Sr-isotope data of diagenetic minerals formed in correspondence of fossil specimens such as marine vertebrates and mollusks. These fossil specimens were found at Cerro los Quesos, in the Ica Desert, within the diatomaceous strata of the Pisco Formation. Dolomite, gypsum, anhydrite and Mn minerals are the main phases found, while the calcium carbonate originally forming the mollusk valves is replaced by gypsum. An early formation of dolomite and of Mn minerals, triggered by the modifications of the geochemical environment due to organic matter degradation, is suggested by the textural relationships and is confirmed by the Sr isotopic ratio of dolomite, which agrees with that of seawater at the time of sedimentation. Instead, gypsum Sr isotopic ratios indicate a pre-Miocene seawater-derived brine circulating within the sedimentary sequence as a source for Sr. Oxidation of diagenetic sulfide causing a lowering of the pH of porewater is proposed as an explanation for Ca-carbonate dissolution. The diagenetic chemical environment was, nevertheless, favorable to bone preservation.

Diagenetic variation at the lamina scale in lacustrine organic-rich shales: Implications for hydrocarbon migration and accumulation

NASA Astrophysics Data System (ADS)

Liang, Chao; Cao, Yingchang; Liu, Keyu; Jiang, Zaixing; Wu, Jing; Hao, Fang

2018-05-01

Lacustrine carbonate-rich shales are well developed within the Mesozoic-Cenozoic strata of the Bohai Bay Basin (BBB) of eastern China and across southeast Asia. Developing an understanding of the diagenesis of these shales is essential to research on mass balance, diagenetic fluid transport and exchange, and organic-inorganic interactions in black shales. This study investigates the origin and distribution of authigenic minerals and their diagenetic characteristics, processes, and pathways at the scale of lacustrine laminae within the Es4s-Es3x shale sequence of the BBB. The research presented in this study is based on thin sections, field emission scanning electron microscope (FESEM) and SEM-catholuminescence (CL) observations of well core samples combined with the use of X-ray diffraction (XRD), energy dispersive spectroscopy, electron microprobe analysis, and carbon and oxygen isotope analyses performed using a laser microprobe mass spectrometer. The dominant lithofacies within the Es4s-Es3x sequence are a laminated calcareous shale (LCS-1) and a laminated clay shale (LCS-2). The results of this study show that calcite recrystallization1 is the overarching diagenetic process affecting the LCS-1, related to acid generation from organic matter (OM) thermal evolution. This evolutionary transition is the key factor driving the diagenesis of this lithofacies, while the transformation of clay minerals is the main diagenetic attribute of the LCS-2. Diagenetic differences occur within different laminae and at variable locations within the same lamina level, controlled by variations in mineral composition and the properties of laminae interfaces. The diagenetic fluid migration scale is vertical and responses (dissolution and replacement) are limited to individual laminae, between zero and 100 μm in width. In contrast, the dominant migration pathway for diagenetic fluid is lateral, along the abrupt interfaces between laminae boundaries, which leads to the vertical

Constraints on Early Triassic carbon cycle dynamics from paired organic and inorganic carbon isotope records

NASA Astrophysics Data System (ADS)

Meyer, K. M.; Yu, M.; Lehrmann, D.; van de Schootbrugge, B.; Payne, J. L.

2013-01-01

Large δ13C excursions, anomalous carbonate precipitates, low diversity assemblages of small fossils, and evidence for marine euxinia in uppermost Permian and Lower Triassic strata bear more similarity to Neoproterozoic carbonates than to the remainders of the Permian and Triassic systems. Middle Triassic diversification of marine ecosystems coincided with the waning of anoxia and stabilization of the global carbon cycle, suggesting that environment-ecosystem linkages were important to biological recovery. However, the Earth system behavior responsible for these large δ13C excursions remains poorly constrained. Here we present a continuous Early Triassic δ13Corg record from south China and use it to test the extent to which Early Triassic excursions in δ13Ccarb record changes in the δ13C of marine dissolved inorganic carbon (DIC). Regression analysis demonstrates a significant positive correlation between δ13Corg and δ13Ccarb across multiple sections that span a paleoenvironmental gradient. Such a correlation is incompatible with diagenetic alteration because no likely mechanism will alter both δ13Corg and δ13Ccarb records in parallel and therefore strongly indicates a primary depositional origin. A simple explanation for this correlation is that a substantial portion of the preserved Corg was derived from the contemporaneous DIC pool, implying that the observed excursions reflect variation in the δ13C of the exogenic carbon reservoir (ocean, atmosphere, biomass). These findings support existing evidence that large δ13C excursions are primary and therefore strengthen the case that large-scale changes to the carbon cycle were mechanistically linked to the low diversity and small size of Early Triassic fossils. Associated sedimentary and biogeochemical phenomena further suggest that similar associations in Neoproterozoic and Cambrian strata may reflect the same underlying controls.

Diagenetic history of the Surma Group sandstones (Miocene) in the Surma Basin, Bangladesh

NASA Astrophysics Data System (ADS)

Rahman, M. Julleh Jalalur; McCann, Tom

2012-02-01

This study examines the various diagenetic controls of the Miocene Surma Group sandstones encountered in petroleum exploration wells from the Surma Basin, which is situated in the northeastern part of the Bengal Basin, Bangladesh. The principal diagenetic minerals/cements in the Surma Group sandstones are Fe-carbonates (with Fe-calcite dominating), quartz overgrowths and authigenic clays (predominantly chlorite, illite-smectite and minor kaolin). The isotopic composition of the carbonate cement revealed a narrow range of δ 18O values (-10.3‰ to -12.4‰) and a wide range of δ 13C value (+1.4‰ to -23.1‰). The δ 13C VPDB and δ 18O VPDB values of the carbonate cements reveal that carbon was most likely derived from the thermal maturation of organic matter during burial, as well as from the dissolution of isolated carbonate clasts and precipitated from mixed marine-meteoric pore waters. The relationship between the intergranular volume (IGV) versus cement volume indicates that compaction played a more significant role than cementation in destroying the primary porosity. However, cementation also played a major role in drastically reducing porosity and permeability in sandstones with poikilotopic, pore-filling blocky cements formed in early to intermediate and deep burial areas. In addition to Fe-carbonate cements, various clay minerals including illite-smectite and chlorite occur as pore-filling and pore-lining authigenic phases. Significant secondary porosity has been generated at depths from 2500 m to 4728 m. The best reservoir rocks found at depths of 2500-3300 m are well sorted, relatively coarse grained; more loosely packed and better rounded sandstones having good porosities (20-30%) and high permeabilities (12-6000 mD). These good quality reservoir rocks are, however, not uniformly distributed and can be considered to be compartmentalized as a result of interbedding with sandstone layers of low to moderate porosities, low permeabilities owing to poor

Temperature and composition of carbonate cements record early structural control on cementation in a nascent deformation band fault zone: Moab Fault, Utah, USA

NASA Astrophysics Data System (ADS)

Hodson, Keith R.; Crider, Juliet G.; Huntington, Katharine W.

2016-10-01

Fluid-driven cementation and diagenesis within fault zones can influence host rock permeability and rheology, affecting subsequent fluid migration and rock strength. However, there are few constraints on the feedbacks between diagenetic conditions and structural deformation. We investigate the cementation history of a fault-intersection zone on the Moab Fault, a well-studied fault system within the exhumed reservoir rocks of the Paradox Basin, Utah, USA. The fault zone hosts brittle structures recording different stages of deformation, including joints and two types of deformation bands. Using stable isotopes of carbon and oxygen, clumped isotope thermometry, and cathodoluminescence, we identify distinct source fluid compositions for the carbonate cements within the fault damage zone. Each source fluid is associated with different carbonate precipitation temperatures, luminescence characteristics, and styles of structural deformation. Luminescent carbonates appear to be derived from meteoric waters mixing with an organic-rich or magmatic carbon source. These cements have warm precipitation temperatures and are closely associated with jointing, capitalizing on increases in permeability associated with fracturing during faulting and subsequent exhumation. Earlier-formed non-luminescent carbonates have source fluid compositions similar to marine waters, low precipitation temperatures, and are closely associated with deformation bands. The deformation bands formed at shallow depths very early in the burial history, preconditioning the rock for fracturing and associated increases in permeability. Carbonate clumped isotope temperatures allow us to associate structural and diagenetic features with burial history, revealing that structural controls on fluid distribution are established early in the evolution of the host rock and fault zone, before the onset of major displacement.

Giant calcite concretions in aeolian dune sandstones; sedimentological and architectural controls on diagenetic heterogeneity, mid-Cretaceous Iberian Desert System, Spain

NASA Astrophysics Data System (ADS)

Arribas, Maria Eugenia; Rodríguez-López, Juan Pedro; Meléndez, Nieves; Soria, Ana Rosa; de Boer, Poppe L.

2012-01-01

Aeolian dune sandstones of the Iberian erg system (Cretaceous, Spain) host giant calcite concretions that constitute heterogeneities of diagenetic origin within a potential aeolian reservoir. The giant calcite concretions developed in large-scale aeolian dune foresets, at the transition between aeolian dune toeset and damp interdune elements, and in medium-scale superimposed aeolian dune sets. The chemical composition of the giant concretions is very homogeneous. They formed during early burial by low Mg-calcite precipitation from meteoric pore waters. Carbonate components with yellow/orange luminescence form the nuclei of the poikilotopic calcite cement. These cements postdate earlier diagenetic features, characterized by early mechanical compaction, Fe-oxide cements and clay rims around windblown quartz grains resulting from the redistribution of aeolian dust over the grain surfaces. The intergranular volume (IGV) in friable aeolian sandstone ranges from 7.3 to 15.3%, whereas in cemented aeolian sandstone it is 18.6 to 25.3%. The giant-calcite concretions developed during early diagenesis under the influence of meteoric waters associated with the groundwater flow of the desert basin, although local (e.g. activity of fluid flow through extensional faults) and/or other regional controls (e.g. variations of the phreatic level associated with a variable water influx to the erg system and varying sea level) could have favoured the local development of giant-calcite concretions. The spatial distribution pattern of carbonate grains and the main bounding surfaces determined the spatial distribution of the concretions. In particular, the geometry of the giant calcite concretions is closely associated with main bounding aeolian surfaces. Thus, interdune, superimposition and reactivation surfaces exerted a control on the concretion geometries ranging from flat and tabular ones (e.g. bounded by interdunes) to wedge-shaped concretions at the dune foresets (e.g. bounded by

Integrated diagenetic and sequence stratigraphy of a late Oligocene-early Miocene, mixed-sediment platform (Austral Basin, southern Patagonia): Resolving base-level and paleoceanographic changes, and paleoaquifer characteristics

NASA Astrophysics Data System (ADS)

Dix, George R.; Parras, Ana

2014-06-01

A condensed (~ 20-m-thick) marine transgressive-highstand succession comprises the upper San Julián Formation (upper Oligocene-lower Miocene) of the northern retroarc Austral Basin, southern Patagonia. Mixed-sediment facies identify a shelf-interior setting, part of an overall warm-temperate regional platform of moderate energy. Giant oyster-dominated skeletal-hiatal accumulations along the maximum flooding surface and forming high-energy event beds in the highstand succession preserve relict micrite in protected shelter porosity, and identify periods of reduced sediment accumulation. The stratigraphic distribution of marine-derived glaucony and diagenetic carbonates is spatially related to sequence development. Depositional siderite coincides with prominent marine transgression, defining transient mixing of marine and meteoric waters across coastal-plain deposits. Chemically evolved autochthonous glaucony coincides with periods of extended seafloor exposure and transgressions that bracket the marine succession, and within the oyster-dominated skeletal accumulations. Seafloor cement, likely once magnesian calcite, formed in association with an encrusting/boring biota along the maximum flooding surface in concert with incursion of cool (11-13 °C) water. The cement is present locally in skeletal event beds in the highstand succession suggesting a possible association with high-order base-level change and cooler water. As the highstand succession coincides with elevated global sea level in the late Oligocene-early Miocene, the locally marine-cemented glauconitic skeletal event beds in the highstand succession may identify higher order glacio-eustatic control. Local stratal condensation, however, is best explained by regional differences in basement subsidence. In the burial realm, carbonate diagenesis produced layers of phreatic calcrete coincident with skeletal-rich deposits. Zeolite (clinoptilolite-K) cement is restricted to the lowermost marine transgressive

A biodetrital coral mound complex: Key to early diagenetic processes in the mississippian bangor limestone

USGS Publications Warehouse

Haywick, D.W.; Kopaska-Merkel, D. C.; Bersch, M.G.

2009-01-01

The Bangor Limestone is a Mississippian (Chesterian) shallow marine carbonate formation exposed over a large portion of the Interior Low Plateaus province of northern Alabama. It is dominated by oolitic grainstone and skeletal wackestone and packstone, but in one outcrop near Moulton, Alabama, the Bangor contains a five m thick, 25 m wide, oolitebiodetrital moundtidal flat succession. This sequence is interpreted as a 4th order sea level cycle. Four petrofacies (oolite, mound, skeletal and mudstone/dolomicrite) and four diagenetic phases (iron oxide, fibrous calcite cement, calcite spar cement and dolomite) are distinguished at the study site. Iron oxide, a minor component, stained and/or coated some ooids, intraclasts and skeletal components in the oolite petrofacies. Many of the allochems were stained prior to secondary cortical growth suggesting a short period of subaerial exposure during oolite sedimentation. The oolite petrofacies also contains minor amounts of fibrous calcite cement, a first generation marine cement, and rare infiltrated micrite that might represent a second phase of marine cement, or a first phase of meteoric cement (i.e., "vadose silt") (Dunham 1969). Intergranular pore space in all four petrofacies is filled with up to three phases of meteoric calcite spar cement. The most complete record of meteoric cementation is preserved within coralline void spaces in the mound petrofacies and indicates precipitation in the following order: (1) non-ferroan scalenohedral spar, (2) ferroan drusy spar (0.1-0.4 wt% Fe2+) and (3) non-ferroan drusy spar. The first scalenohedral phase of meteoric cement is distributed throughout the oolite and mound petrofacies. The ferroan phase of meteoric calcite is a void-filling cement that is abundant in the mound petrofacies and less common in the skeletal and mudstone/dolomicrite petrofacies. Non-ferroan drusy calcite is pervasive throughout the Bangor Limestone at the Moulton study site. Growth of the fourth

The origin of decoupled carbonate and organic carbon isotope signatures in the early Cambrian (ca. 542-520 Ma) Yangtze platform

NASA Astrophysics Data System (ADS)

Jiang, Ganqing; Wang, Xinqiang; Shi, Xiaoying; Xiao, Shuhai; Zhang, Shihong; Dong, Jin

2012-02-01

The early Cambrian (ca. 542-520 Ma) strata in South China record two prominent negative carbonate carbon isotope (δ13Ccarb) excursions of early Nemakit-Daldynian (N-D) and early Tommotian ages. Across each of these excursions, carbonate and organic carbon isotopes (δ13Ccarb and δ13Corg) are strongly decoupled. Regional correlation across a shelf-to-basin transect shows lateral heterogeneity of δ13Corg during the early-middle N-D but more homogenized δ13Corg values across the basin during the late N-D and Tommotian. The temporal and lateral variations in δ13Corg suggest that decoupled δ13Ccarb and δ13Corg across the N-D δ13Ccarb excursion were possibly caused by diagenetic alteration of organic matter and/or amplification of detrital organic carbon isotope signature in low-TOC carbonates. In contrast, decoupled δ13Ccarb and δ13Corg of the upper N-D and Tommotian were likely resulted from chemoautotrophic-methanotrophic biomass contribution to TOC in organic-rich black shale and carbonates. The decoupled δ13Ccarb-δ13Corg pattern from the lower N-D strata (ca. 542 Ma) shows striking similarities with those from the basal (ca. 635 Ma) and upper (ca. 551 Ma) Doushantuo Formation. In all three cases, decoupled δ13Ccarb-δ13Corg are seen in organic-poor carbonates (TOC ≤ 0.1‰) and coupled δ13Ccarb-δ13Corg occur in organic-rich black shale and carbonates at the end of the negative δ13Ccarb excursion. These similarities suggest that the shift from decoupled to coupled δ13Ccarb-δ13Corg has no causal link with the terminal oxidation of a large oceanic DOC reservoir. Given the pervasive anoxia/euxinia in Ediacaran-early Cambrian oceans, local DOC-rich environments may have been common, but a large oceanic DOC reservoir capable of buffering the δ13C of marine organic matter requires independent evidence.

Carbonate petrography, kerogen distribution, and carbon and oxygen isotope variations in an early Proterozoic transition from limestone to iron-formation deposition, Transvaal Supergroup, South Africa

NASA Technical Reports Server (NTRS)

Beukes, N. J.; Klein, C.; Kaufman, A. J.; Hayes, J. M.

1990-01-01

The transition zone comprises Campbellrand microbialaminated (replacing "cryptalgalaminate") limestone and shale, with minor dolomite, conformably overlain by the Kuruman Iron Formation of which the basal part is characterized by siderite-rich microbanded iron-formation with minor magnetite and some hematite-containing units. The iron-formation contains subordinate intraclastic and microbialaminated siderite mesobands and was deposited in deeper water than the limestones. The sequence is virtually unaltered with diagenetic mineral assemblages reflecting a temperature interval of about 110 degrees to 170 degrees C and pressures of 2 kbars. Carbonate minerals in the different rock types are represented by primary micritic precipitates (now recrystallized to microsparite), early precompactional sparry cements and concretions, deep burial limpid euhedral sparites, and spar cements precipitated from metamorphic fluids in close contact with diabase sills. Paragenetic pathways of the carbonate minerals are broadly similar in all lithofacies with kerogen intimately associated with them. Kerogen occurs as pigmentation in carbonate crystals, as reworked organic detritus in clastic-textured carbonate units, and as segregations of kerogen pigment around late diagenetic carbonate crystals. Locally kerogen may also be replaced by carbonate spar. Carbon isotope compositions of the carbonate minerals and kerogen are dependent on their mode of occurrence and on the composition of the dominant carbonate species in a specific lithofacies. Integration of sedimentary, petrographic, geochemical, and isotopic results makes it possible to distinguish between depositional, early diagenetic, deep burial, and metamorphic effects on the isotopic compositions of the carbonate minerals and the kerogen in the sequence. Major conclusions are that deep burial thermal decarboxylation led to 13C depletion in euhedral ferroan sparites and 13C enrichment in kerogen (organic carbon). Metamorphic

Petrography and geochemistry of the Permian-Triassic boundary interval, Yangou section, South China: Implications for early Griesbachian seawater δ13CDIC gradient with depth

NASA Astrophysics Data System (ADS)

Li, Rong

2017-04-01

The carbon isotopic composition (δ13Ccarb) recorded in shelf carbonates has been widely used as a proxy for the isotopic composition (δ13CDIC) of surface ocean water to establish paleocean chemistry and circulation patterns. However, δ13Ccarb values do not necessarily preserve the δ13CDIC, due to post-depositional diagenetic alteration. In order to examine the early Griesbachian surface-to-deep δ13CDIC gradient with depth, the diagenetic features of the Permian-Triassic boundary interval (beds 18 to 35) from Yangou section, located in the Yangtze carbonate platform interior, South China, are delineated to compare with those of the slope GSSP Meishan section. The petrographic and geochemical observations show that the early Griesbachian carbonates in the Yangou section underwent pervasive dolomitization in its early diagenetic history. Three types of early replacement dolomites and one type of dolomite cement are present. The dolomite crystals display internal zonation, with high-Ca calcian dolomite (HCD) core being encased successively by calcite and an outermost Fe-rich HCD cortex. The initial dolomitization took place in anoxic seawater, and underwent subsequent diagenetic system involved with meteoric water. The two most negative δ13C values in claystones of Beds 21-3 and 35 are probably related to meteoric diagenesis. Above and/or below the meteorically influenced beds, the dolomite and calcite have uniformly positive δ13C values. The primary carbon isotopic compositions are probably preserved in the early Griesbachian carbonate from the platform Yangou section, which could probably be related to the poor formation of the outermost Fe-rich HCD cortex. Compared to the slope carbonate from the Meishan section, the platform carbonate from the Yangou section has lower primary δ13Ccarb values. It is estimated that the δ13CDIC gradient with depth between Yangou and Meishan is less than the previously suggested. The results highlight the need for evaluation

Overview of the diagenetic features analyzed by ChemCam onboard Curiosity

NASA Astrophysics Data System (ADS)

Mangold, N.; Forni, O.; Nachon, M.; Blaney, D. L.; Wiens, R. C.; Kah, L. C.; Kronyak, R. E.; Clegg, S. M.; Cousin, A.; Fisk, M. R.; Gasnault, O.; Grotzinger, J. P.; Lanza, N.; Lasue, J.; Le Deit, L.; Le Mouelic, S.; Maurice, S.; Meslin, P. Y.; Rapin, W.; Newsom, H. E.; Sumner, D. Y.

2015-12-01

The Curiosity rover has encountered a variety of sedimentary rocks with significant variations in both texture and composition. Most of the sandstones and mudstones are interpreted as having been deposited in a fluvio-lacustrine environment, as analyzed in details in the waypoints named Yellowknife Bay, Kimberley and Pahrump. All of these sediments have been crossed by diagenetic features of different composition. Light-toned Ca-sulfate veins observed initially at Yellowknife Bay were observed along the traverse, and in high density at the Pahrump location. As they appear in all sediments and show straight fractures, they correspond to late-stage diagenetic features, due to fluid circulation, with fractures probably due to hydraulic stress at depth. In contrast to light-toned veins, earlier-stage diagenetic features have shown variable composition in the three areas. At Yellowknife Bay, raised ridges display enriched Mg proportion, probably linked to Mg-clay whereas outcrops at Kimberley display fracture fills enriched in Mn and Zn. Pahrump displays a large variety of diagenetic features distinct from these previous examples. Mg-enriched concretions contain S and abundant Ni. Mg enrichments have also been observed in resistant zones along fractures and in resistant layers. Locally concretions also display high Fe, S-bearing material interpreted as Fe-sulfate, probably jarosite. A special location named Garden City at the top of the Parhump sequence displays a complex area with light-toned veins surrounded by darker veins. The latter display strong Ca signatures correlated with F, interpreted as fluorite. No C or S emissions were observed that could alternatively explain the high Ca abundance by carbonates or sulfates. The dark tone of the F-bearing minerals may be due to the presence of Fe. These specific dark veins could derive from the leaching of F-apatite, a mineral that has been observed both in the sandstones and in some of the igneous clasts analyzed by Chem

Origin of the diagenetic carbonate crusts and concretions from the mud volcanoes of the Nile deep-sea fan

NASA Astrophysics Data System (ADS)

Gontharet, S.; Pierre, C.; Blanc Valleron, M.; Rouchy, J.; Fouquet, Y.; Bayon, G.

2004-12-01

sources of diagenetic fluids. Typically, the very low \\delta13C values of the authigenic carbonates indicate that CH4 was the major source of carbon which was oxidized as CO2, either through bacterial sulfate reduction within the sediment, or via bacterial aerobic oxidation at the sea floor. Similar isotopic values were previously measured in the diagenetic carbonate crusts from the mud volcanoes of the Mediterranean Ridge area (Aloisi et al., 2000) as well as in other areas of cold seeps outside the Mediterranean sea (for instance Gulf of Mexico, Cascadia margin, Barbados prism). References: Aloisi G., Pierre C., Rouchy J.M., Foucher J.P., Woodside J. and the Medinaut Scientific Party, 2000. E.P.S.L., 184, 321-338. Loncke L., Gaullier V., Bellaiche G., and Mascle J., 2004. A.A.P.G. Bull

Diagenetic overprinting of the sphaerosiderite palaeoclimate proxy: are records of pedogenic groundwater δ18O values preserved?

USGS Publications Warehouse

Ufnar, David F.; Gonzalez, Luis A.; Ludvigson, Greg A.; Brenner, Richard L.; Witzkes, Brian J.

2004-01-01

Meteoric sphaerosiderite lines (MSLs), defined by invariant ??18O and variable ??13C values, are obtained from ancient wetland palaeosol sphaerosiderites (millimetre-scale FeCO3 nodules), and are a stable isotope proxy record of terrestrial meteoric isotopic compositions. The palaeoclimatic utility of sphaerosiderite has been well tested; however, diagenetically altered horizons that do not yield simple MSLs have been encountered. Well-preserved sphaerosiderites typically exhibit smooth exteriors, spherulitic crystalline microstructures and relatively pure (> 95 mol% FeCO3) compositions. Diagenetically altered sphaerosiderites typically exhibit corroded margins, replacement textures and increased crystal lattice substitution of Ca2+, Mg2+ and Mn2+ for Fe2+. Examples of diagenetically altered Cretaceous sphaerosiderite-bearing palaeosols from the Dakota Formation (Kansas), the Swan River Formation (Saskatchewan) and the Success S2 Formation (Saskatchewan) were examined in this study to determine the extent to which original, early diagenetic ??18O and ??13C values are preserved. All three units contain poikilotopic calcite cements with significantly different ??18O and ??13C values from the co-occurring sphaerosiderites. The complete isolation of all carbonate phases is necessary to ensure that inadvertent physical mixing does not affect the isotopic analyses. The Dakota and Swan River samples ultimately yield distinct MSLs for the sphaerosiderites, and MCLs (meteoric calcite lines) for the calcite cements. The Success S2 sample yields a covariant ??18O vs. ??13C trend resulting from precipitation in pore fluids that were mixtures between meteoric and modified marine phreatic waters. The calcite cements in the Success S2 Formation yield meteoric ??18O and ??13C values. A stable isotope mass balance model was used to produce hyperbolic fluid mixing trends between meteoric and modified marine end-member compositions. Modelled hyperbolic fluid mixing curves for the

Cement Distribution and Diagenetic Pathway of the Miocene Sediments on Kardiva Platform, Maldives.

NASA Astrophysics Data System (ADS)

Laya, J. C.; Prince, K.; Betzler, C.; Eberli, G. P.; Blättler, C. L.; Swart, P. K.; Reolid, J.; Alvarez Zarikian, C. A.; Reijmer, J.

2017-12-01

The Maldives archipelago is an ideal example for understanding the dynamics of isolated carbonate platforms. While previous sedimentological studies have focused on oceanographic and climatic controls on deposition, there have been limited studies on the diagenetic evolution of the Maldives archipelago. This project seeks to establish a relationship between the facies, cement distribution, and diagenetic evolution of the Kardiva Platform and associated diagenetic fluids. Samples from cores of IODP Expedition 359 at Sites U1645, U1469, and U1470 were analyzed for stable isotope geochemistry and detailed petrography including SEM, confocal and CL microscopy to investigate variations in facies, cements, porosity and diagenetic products. The facies analyzed consist mainly of planktonic and benthic foraminifers, red coralline algae, echinoderm, coral and skeletal fragments. The main facies include foraminifera grain/packstone, red algae rich grain/packstone, algal floatstone and coral floatstone. Those facies present a cyclic and general shallowing upwards trend. These facies are interpreted as shallow platform deposits on proximal areas to the margin associated with the oligophotic zone. Cement volume varies between 5% and 48%, and they have been classified as isopachous, bladed to fibrous (dog tooth), drusy and equant. Equant and drusy show recognizable growth bands with CL and confocal. Evidence of intense dissolution is shown by extensive moldic porosity within phreatic and limited vadose zones. In addition, dolomite appears as a replacement phase associated with red-algae-rich horizons and as cement on pore walls and voids. These deposits experienced a variety of diagenetic processes driven by the evolution of diagenetic fluid chemistry and by the nature of the skeletal components. Those processes can be tied to external controls such as climate (monsoonal effects), sea-level and currents.

Fluid expulsion sites on the Cascadia accretionary prism: mapping diagenetic deposits with processed GLORIA imagery

USGS Publications Warehouse

Carson, Bobb; Seke, Erol; Paskevich, Valerie F.; Holmes, Mark L.

1994-01-01

Point-discharge fluid expulsion on accretionary prisms is commonly indicated by diagenetic deposition of calcium carbonate cements and gas hydrates in near-surface (<10 m below seafloor; mbsf) hemipelagic sediment. The contrasting clastic and diagenetic lithologies should be apparent in side scan images. However, sonar also responds to variations in bottom slope, so unprocessed images mix topographic and lithologic information. We have processed GLORIA imagery from the Oregon continental margin to remove topographic effects. A synthetic side scan image was created initially from Sea Beam bathymetric data and then was subtracted iteratively from the original GLORIA data until topographic features disappeared. The residual image contains high-amplitude backscattering that we attribute to diagenetic deposits associated with fluid discharge, based on submersible mapping, Ocean Drilling Program drilling, and collected samples. Diagenetic deposits are concentrated (1) near an out-of-sequence thrust fault on the second ridge landward of the base of the continental slope, (2) along zones characterized by deep-seated strikeslip faults that cut transversely across the margin, and (3) in undeformed Cascadia Basin deposits which overlie incipient thrust faults seaward of the toe of the prism. There is no evidence of diagenetic deposition associated with the frontal thrust that rises from the dècollement. If the dècollement is an important aquifer, apparently the fluids are passed either to the strike-slip faults which intersect the dècollement or to the incipient faults in Cascadia Basin for expulsion. Diagenetic deposits seaward of the prism toe probably consist dominantly of gas hydrates.

Hg concentrations from Late Triassic and Early Jurassic sedimentary rocks: first order similarities and second order depositional and diagenetic controls

NASA Astrophysics Data System (ADS)

Yager, J. A.; West, A. J.; Bergquist, B. A.; Thibodeau, A. M.; Corsetti, F. A.; Berelson, W.; Bottjer, D. J.; Rosas, S.

2016-12-01

Mercury concentrations in sediments have recently gained prominence as a potential tool for identifying large igneous province (LIP) volcanism in sedimentary records. LIP volcanism coincides with several mass extinctions during the Phanerozoic, but it is often difficult to directly tie LIP activity with the record of extinction in marine successions. Here, we build on mercury concentration data reported by Thibodeau et al. (Nature Communications, 7:11147, 2016) from the Late Triassic and Early Jurassic of New York Canyon, Nevada, USA. Increases in Hg concentrations in that record were attributed to Central Atlantic Magmatic Province (CAMP) activity in association with the end-Triassic mass extinction. We expand the measured section from New York Canyon and report new mercury concentrations from Levanto, Peru, where dated ash beds provide a discrete chronology, as well as St. Audrie's Bay, UK, a well-studied succession. We correlate these records using carbon isotopes and ammonites and find similarities in the onset of elevated Hg concentrations and Hg/TOC in association with changes in C isotopes. We also find second order patterns that differ between sections and may have depositional and diagenetic controls. We will discuss these changes within a sedimentological framework to further understand the controls on Hg concentrations in sedimentary records and their implications for past volcanism.

Diagenetic evaluation of Pannonian lacustrine deposits in the Makó Trough, southeastern Hungary

NASA Astrophysics Data System (ADS)

Szőcs, Emese; Milovský, Rastislav; Gier, Susanne; Hips, Kinga; Sztanó, Orsolya

2017-04-01

The Makó Trough is the deepest sub-basin of the Pannonian Basin. As a possible shale gas and tight gas accumulation the area was explored by several hydrocarbon companies. In this study, we present the preliminary results on the diagenetic history and the porosity evolution of sandstones and shales. Petrographic (optical microscopy, CL, blue light microscopy) and geochemical methods (SEM-EDX, WDX, O and C stable isotopes) were applied on core samples of Makó-7 well (3408- 5479 m). Processes which influenced the porosity evolution of the sandstones were compaction, cementation, mineral replacement and dissolution. The most common diagenetic minerals are carbonates (non-ferroan and Fe-bearing calcite, dolomite and ankerite), clay minerals (kaolinite, mixed layer illite-smectite and chlorite) and other silicates (quartz and feldspar). Initial clay mineral and ductile grain content also influences reservoir quality. The volumetrically most significant diagenetic minerals are calcite and clay minerals. The petrography of calcite is variable (bright orange to dull red luminescence color, pore-filling cement, replacive phases which are occasionally scattered in the matrix). The δ13 C-PDB values of calcite range from 1.7 ‰ to -5.5 ‰, while δ18 O-PDB values range from 0.5 ‰ to -9.1 ‰, no depth related trend was observed. These data suggest that calcite occurs in more generations, i.e. eogenetic pre-compactional and mesogenetic post-compactional. Kaolinite is present in mottles in size similar to detrital grains, where remnants of feldspars can be seen. This indicates feldspar alteration via influx of water rich in organic derived carbon dioxide. Secondary porosity can be observed in carbonates and feldspars at some levels, causing the improvement of the reservoir quality.

The influence of seawater carbonate chemistry, mineralogy, and diagenesis on calcium isotope variations in Lower-Middle Triassic carbonate rocks

DOE PAGES

Lau, Kimberly V.; Maher, Kate; Brown, Shaun T.; ...

2017-11-01

various geological ages. By using a model of early marine diagenetic water-rock interaction, we illustrate that this general correlation can be explained by the chemical evolution of bulk carbonate sediment samples with different initial mineralogical compositions that subsequently underwent recrystallization. Although early diagenetic resetting and carbonate mineralogy strongly influence the carbonate δ 44/40 Ca values, the relationship between [Sr] and δ 44/40 Ca holds potential for reconstructing first-order secular changes in seawater δ 44/40 Ca composition.« less

The influence of seawater carbonate chemistry, mineralogy, and diagenesis on calcium isotope variations in Lower-Middle Triassic carbonate rocks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lau, Kimberly V.; Maher, Kate; Brown, Shaun T.

various geological ages. By using a model of early marine diagenetic water-rock interaction, we illustrate that this general correlation can be explained by the chemical evolution of bulk carbonate sediment samples with different initial mineralogical compositions that subsequently underwent recrystallization. Although early diagenetic resetting and carbonate mineralogy strongly influence the carbonate δ 44/40 Ca values, the relationship between [Sr] and δ 44/40 Ca holds potential for reconstructing first-order secular changes in seawater δ 44/40 Ca composition.« less

Diagenetic Iron Cycling in Ancient Alkaline Saline Lacustrine Sedimentary Rocks: A Case Study on the Jurassic Brushy Basin Member of the Morrison Formation, Colorado Plateau, USA

NASA Astrophysics Data System (ADS)

Potter-McIntyre, S. L.; Chan, M. A.; McPherson, B. J. O. L.

2014-12-01

The upper part of the Brushy Basin Member in the Four Corners region of the U.S. was deposited in an ephemeral alkaline saline lake system with copious input of volcanic ash. The variegated shale formation provides a setting for the study of early diagenetic iron cycling that records the action of alkaline saline fluid chemistries reacting with volcaniclastic sediments in the presence of microbes. A bull's-eye pattern of authigenic minerals with increasing alteration towards the basinal center similar to modern alkaline saline lakes provides evidence for an extreme paleoenvironmental interpretation. The purpose of this research is to document specific factors, such as reactive sediments, microbial influences, and grain size that affect concretion formation and iron cycling in an ancient extreme environment. Three broad diagenetic facies are interpreted by color and associated bioturbation features: red, green and intermediate. Diagenetic facies reflect meter-scale paleotopography: red facies represent shallow water to subaerial, oxidizing conditions; green facies reflect saturated conditions and reducing pore water chemistry shortly after deposition, and intermediate facies represent a combination of the previous two conditions. Evidence of biotic influence is abundant and trace fossils exhibit patterns associated with the diagenetic facies. Red diagenetic facies typically contain burrows and root traces and green diagenetic facies exhibit restricted biotic diversity typically limited to algal molds (vugs). Microbial fossils are well-preserved and are in close proximity to specific iron mineral textures suggesting biotic influence on the crystal morphology. Three categories of concretions are characterized based on mineralogy: carbonate, iron (oxyhydr)oxide and phosphate concretions. Concretion mineralogy and size vary within an outcrop and even within a stratigraphic horizon such that more than one main category is typically present in an outcrop. Variation in

Repeated occurrences of methanogenic zones, diagenetic dolomite formation and linked silicate alteration in southern Bering Sea sediments (Bowers Ridge, IODP Exp. 323 Site U1341)

NASA Astrophysics Data System (ADS)

Wehrmann, L. M.; Ockert, C.; Mix, A. C.; Gussone, N.; Teichert, B. M. A.; Meister, P.

2016-03-01

Diagenetic precipitates, such as dolomite, and the chemistry of residual deeply buried porewater often represent the only traces of past biogeochemical activity in marine sediments. A 600 m thick sedimentary section, recently drilled at Integrated Ocean Drilling Program (IODP) Site U1341 on Bowers Ridge (southern Bering Sea), provides insight into such a 4.3 Ma old paleo-diagenetic archive. Hard-lithified calcite-dolomite layers, and laminae of disseminated carbonate, were recovered in diatom-rich sediments over a depth range of 400 m. Carbon isotope values of the diagenetic carbonates between -16.6 and -14.4‰ (VPDB) and strontium isotope ratios of dolomites close to past seawater values suggest carbonate precipitation induced by the production of dissolved inorganic carbon (DIC) during elevated rates of organic carbon mineralization, primarily via sulfate reduction, at shallow sediment depth below the paleo-seafloor. Diagenetic carbonates at 280-440 m below seafloor were likely also produced by the intermittent onset of sulfate reduction coupled to the anaerobic oxidation of methane (AOM) at sulfate-methane transition zones (SMTZ). These microbially mediated processes do not occur in the sediment at this site at present but were likely connected to the presence of a methanogenic zone at 2.58-2.51 Ma. A minimum in sulfate concentrations in modern porewaters and low sedimentary Ba/Al ratios resulting from former sulfate depletion are reminiscent of the presence of this large methanogenic zone. The minimum in sulfate concentrations is reflected in a minimum in magnesium concentrations, less radiogenic strontium and isotopically light calcium in the porewater. It is proposed that magnesium was removed from the porewater during carbonate precipitation and volcanic ash alteration which occurred in the former methanogenic zone and also released strontium with a less radiogenic isotope ratio and isotopically light calcium into the porewater. The isotopic composition of

Dynamic depositional and early diagenetic processes in a deep-water shelf setting, upper cretaceous Austin Chalk, North Texas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hovorka, S.D.; Nance, H.S.

1994-12-31

The Austin Chalk of north Texas was deposited on a deep-water shelf north of the Sea Marcos Platform during a worldwide Coniacian and Santonian sea-level highstand. Transgressive (lowermost lower Austin Chalk), highstand (uppermost lower Austin Chalk), and regressive (middle and upper Austin Chalk) phases of cyclic chalk and marl sedimentation are recognized in excavations and tunnels created in Ellis County for the Superconducting Super Collider provide new evidence of sediment transport during Austin Chalk deposition. During transgression, bottom currents syndepositionally reworked nannoplankton oozes, incising channels as much as 120 ft across and 8 ft deep. Weakly burrowed channel fills havingmore » preservation of fine lamination document rapid infilling. Channel fills are composed of pyritized and carbonized wood and Inoceramus lag deposits, pellets, echinoderm fragments, and globigerinid grainstones, and coccolith ooze. During maximum highstand, bottom reworking was suppressed. Detrital content of highstand marls is low (>20 percent); organic content is high (1.4 to 3.5 percent). Coccolith preservation is excellent because of minimal diagenetic alteration. Regression is marked by resumed channel cutting and storm-bed winnowing in the middle and upper Austin Chalk. Suppressed resistivity log response and recessive weathering characteristics of the middle Austin Chalk are not primarily related to depositional environment but rather to increased input of volcanic ash during the accumulation of this interval. Early stabilization of ash produced clay-coated microfabrics in sediments that are otherwise similar to the transgressive deposits.« less

Raman hyperspectral imaging as an effective and highly informative tool to study the diagenetic alteration of fossil bones.

PubMed

Dal Sasso, Gregorio; Angelini, Ivana; Maritan, Lara; Artioli, Gilberto

2018-03-01

Retrieving the pristine chemical or isotopic composition of archaeological bones is of great interest for many studies aiming to reconstruct the past life of ancient populations (i.e. diet, mobility, palaeoenvironment, age). However, from the death of the individual onwards, bones undergo several taphonomic and diagenetic processes that cause the alteration of their microstructure and composition. A detailed study on bone diagenesis has the double purpose to assess the preservation state of archaeological bones and to understand the alteration pathways, thus providing evidence that may contribute to evaluate the reliability of the retrieved information. On these bases, this research aims to explore the effectiveness of Raman hyperspectral imaging to detect types, extent and spatial distribution of diagenetic alteration at the micro-scale level. An early-Holocene bone sample from the Al Khiday cemetery (Khartoum, Sudan) was here analysed. Parameters related to the collagen content, bioapatite crystallinity and structural carbonate content, and to the occurrence of secondary mineral phases were calculated from Raman spectra. The acquired data provided spatially-resolved information on both the preservation state of bone constituents and the diagenetic processes occurring during burial. Given the minimal sample preparation, the easy and fast data acquisition and the improvement of system configurations, micro-Raman spectroscopy can be extensively applied as a screening method on a large set of samples in order to characterise the preservation state of archaeological bones. This technique can be effectively applied to identify suitable and well preserved portions of the analysed sample on which perform further analyses. Copyright © 2017 Elsevier B.V. All rights reserved.

Photochemical dissolution of organic matter from resuspended sediments: Impact of source and diagenetic state on photorelease

NASA Astrophysics Data System (ADS)

Helms, J. R.; Glinski, D. A.; Mead, R. N.; Southwell, M.; Avery, G. B., Jr.; Kieber, R. J.; Skrabal, S. A.

2015-12-01

Resuspended sediments exposed to simulated solar radiation release dissolved organic carbon (DOC). However, it is unclear how the provenance of sedimentary organic matter (OM) impacts this photorelease. In the first geographically extensive study of this phenomenon, twenty three size fractionated, fine grained sediments (< ca. 10-20 μm) from a variety of drainage basins were resuspended (at suspended solid loading of 29- 255 mg/l) and exhibited a net photochemical DOC release ranging from 2 to 178 μmol/g/h. There was a logarithmic increase in photoreleased DOC vs. the proportion of sedimentary OC (%), most likely due to photon limitation at high sedimentary OC loading (i.e. high mass-specific absorption limiting light penetration). Sediment source and quality - determined using lipid biomarkers - had a significant effect on DOC photorelease. The fatty acid terrestrial aquatic ratio (TARFA) indicated that terrestrially derived sediments exhibited relatively greater DOC photorelease. The long chain carbon preference index (CPI24-34) indicated that diagenetically unaltered terrestrial OM photoreleased more DOC than diagenetically altered terrestrial OM. The short chain carbon preference index (CPI14-22) demonstrated that sediments containing diagenetically altered planktonic or algal derived OM had a greater photorelease rate of DOC than fresh algal OM. This suggests that humic substances (humus and/or adsorbed humic and fulvic acids) play an important role in the photochemical dissolution of OC regardless of whether or not they are imported from upstream (i.e. terrestrial humics) or generated within the depositional or sedimentary environment (i.e. humification of algal dissolved OM).

Microfacies and diagenesis of the Middle Jurassic Dhruma carbonates, southwest Riyadh, Saudi Arabia

NASA Astrophysics Data System (ADS)

El-Sorogy, Abdelbaset S.; Galmed, Mahmoud A.; Al-Kahtany, Khaled; Al-Zahrani, Ali

2017-06-01

In order to document the microfacies analysis and diagenetic alterations of the Middle Jurassic Dhruma Formation at southwest Riyadh City of central Saudi Arabia, a stratigraphic section was studied in detail at Khashm adh Dhi'bi area. Mudstones, wackstones, packstones, grainstones and boundstones are the main microfacies types in the studied area. These microfacies types with field investigations and fossil content indicated an environment ranging from deep shelf to organic buildup on platform margins for the studied carbonates. Cementation and recrystallization, dissolution, fragmentation and compaction, silicification, dolomitization, and bioerosion were the main diagenetic alterations affected the carbonate rocks of the Dhruma Formation. Cementation and recrystallization are represented by equant calcite crystals, Dog-tooth fringes of thin isopachous calcites and blocky low Mg-calcites. Gastrochaenolites, Trypanites and Meandropolydora spp. were the most bioeroders in coral heads and large bivalves and hardgrounds. These bioeroders indicated a long post-mortem period during the early diagenetic stage.

Evaporite geometries and diagenetic traps, lower San Andres, Northwest shelf, New Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keller, D.R.

An east-west-trending belt of lower San Andres oil fields extends 80 mi across southeastern New Mexico from the Pecos River near Roswell to the Texas-New Mexico border. These fields are along a porosity pinch-out zone where porous carbonates grade laterally into bedded anhydrite and halite. The lower San Andres traps are associated with pre-Tertiary structural or stratigraphic traps. Oil and water production relationships from these fields are not consistent with present-day structure. These fields have been commonly interpreted to be hydrodynamic traps created by the eastern flow of fresh surface water that enters the lower San Andres outcrops west ofmore » Pecos River. There is no evidence, however, that surface water has moved through the lower San Andres in this area. This conclusion is supported by the fact that formation-water resistivities are uniform throughout the producing trend, no significant dissolution of carbonates or evaporites has occurred, and there has been no increase in biogradation of oils adjacent to the lower San Andres outcrops. These fields actually are diagenetic traps created by porosity occlusion in the water column beneath the oil accumulations. Hydrocarbons originally were trapped in pre-Tertiary structural and structural-stratigraphic traps. Bedded evaporites were effective barriers to vertical and lateral hydrocarbon migration. Eastward tilting of the Northwest shelf during the Tertiary opened these traps, but the oil remained in these structurally unfavorable positions because of the diagenetic sealing. The gas-solution drive in these reservoirs is a result of this sealing. The sequence of events leading to diagenetic entrapment include (1) Triassic and Jurassic migration of hydrocarbons into broad, low-relief post-San Andres structural and structural-stratigraphic traps; (2) rapid occlusion of porosity in the water column beneath oil reservoirs, and (3) Tertiary tilt-out traps.« less

Assessment of diagenetic alteration of dinosaur eggshells through petrography and geochemical analysis

NASA Astrophysics Data System (ADS)

Enriquez, M. V.; Eagle, R.; Eiler, J. M.; Tripati, A. K.; Ramirez, P. C.; Loyd, S. J.; Chiappe, L.; Montanari, S.; Norell, M.; Tuetken, T.

2012-12-01

Carbonate clumped isotope analysis of fossil eggshells has the potential to constrain both the physiology of extinct animals and, potentially, paleoenvironmental conditions, especially when coupled with isotopic measurements of co-occurring soil carbonates. Eggshell samples from both modern vertebrates and Cretaceous Hadrosaurid, Oviraptorid, Titanosaur, Hypselosaurus, Faveoolithus, dinosaur fossils have been collected from Auca Mahuevo, Argentina and Rousett, France, amongst other locations, for geochemical analysis to determine if isotopic signatures could be used to indicate warm- or cold-bloodedness. In some locations soil carbonates were also analyzed to constrain environmental temperatures. In order to test the validity of the geochemical results, an extensive study was undertaken to establish degree of diagenetic alteration. Petrographic and cathodoluminescence characterization of the eggshells were used to assess diagenetic alteration. An empirical 1-5 point scale was used to assign each sample an alteration level, and the observations were then compared with the geochemical results. Specimens displayed a wide range of alteration states. Some of which were well preserved and others highly altered. Another group seemed to be structural intact and only under cathodoluminescence was alteration clearly observed. In the majority of samples, alteration level was found to be predictably related to geochemical results. From specimens with little evidence for diagenesis, carbonate clumped isotope signatures support high (37-40°C) body temperature for Titanosaurid dinosaurs, but potentially lower body temperatures for other taxa. If these data do, in fact, represent original eggshell growth temperatures, these results support variability in body temperature amongst Cretaceous dinosaurs and potentially are consistent with variations between adult body temperature and size — a characteristic of 'gigantothermy'.

Does burial diagenesis reset pristine isotopic compositions in paleosol carbonates?

NASA Astrophysics Data System (ADS)

Bera, M. K.; Sarkar, A.; Tandon, S. K.; Samanta, A.; Sanyal, P.

2010-11-01

Sedimentological study of early Oligocene continental carbonates from the fluvial Dagshai Formation of the Himalayan foreland basin, India resulted in the recognition of four different types namely, soil, palustrine, pedogenically modified palustrine and groundwater carbonates. Stable oxygen and carbon isotopic ( δ18O and δ13C) analyses of fabric selective carbonate microsamples show that although the pristine isotopic compositions are largely altered during deep-burial diagenesis, complete isotopic homogenization does not occur. δ18O and δ13C analyses of ~ 200 calcrete and palustrine carbonates from different stratigraphic horizons and comparison with δ18O of more robust bioapatite (fossil vertebrate tooth) phase show that dense micrites (~ > 70% carbonate) invariably preserve the pristine δ18O value (mean) of ~ - 9.8‰, while altered carbonates show much lower δ18O value ~ - 13.8‰. Such inhomogeneity causes large intra-sample and intra-soil profile variability as high as > 5‰, suggesting that soils behave like a closed system where diagenetic overprinting occurs in local domains. A simple fluid-rock interaction model suggests active participation of clay minerals to enhance the effect of fluid-rock ratio in local domains during diagenesis. This places an upper limit of 70% micrite concentration above which the effect of diagenetic alteration is minimal. Careful sampling of dense micritic part of the soil carbonate nodules, therefore, does provide pristine isotopic composition and it is inappropriate, as proposed recently, to reject the paleoclimatic potential of all paleosol carbonates affected by burial diagenesis. Based on pristine δ13C value of - 8.8 ± 0.2‰ in soil carbonates an atmospheric CO 2 concentration between ~ 764 and ~ 306 ppmv is estimated for the early Oligocene (~ 31 Ma) Dagshai time. These data show excellent agreement between two independent proxy records (viz. soil carbonate and marine alkenone) and support early Oligocene

Diagenetic Features in Yellowknife Bay, Gale Crater, Mars: Implications for Substrate Rheology and Potential Gas Release

NASA Technical Reports Server (NTRS)

Kah, L. C.; Stack, K; Siebach, K.; Grotzinger, J.; Summer, D.; Farien, A.; Oehler, D.; Schieber, J.; Leville, R.; Edgar, L;

Early diagenetic high-magnesium calcite and dolomite indicate that coal balls formed in marine or brackish water: Stratigraphic and paleoclimatic implications

NASA Astrophysics Data System (ADS)

Raymond, Anne

2016-04-01

Coal balls are carbonate and pyrite permineralizations of peat that contain three-dimensional plant fossils preserved at the cellular level. Coal balls, which occur in Pennsylvanian and earliest Permian equatorial coals, provide a detailed record of terrestrial ecology and tropical climate during the Late Paleozoic Ice Age; yet their depositional environment remains controversial. The exquisite preservation of some coal-ball fossils, e.g. pollen with pollen tubes and leaves with mesophyll, indicates rapid formation. The presence of abundant, cement-filled, void spaces within and between the plant debris in most coal balls indicates that they formed in uncompacted peat, near the surface of the mire. Botanical, taphonomic and isotopic evidence point to a freshwater origin for coal balls. The nearest living relatives of coal ball plants (modern lycopsids, sphenopsids, marratialean ferns and conifers) grow in fresh water. Coal-ball peat contains a high percentage of aerial debris, similar to modern freshwater peat. The stable oxygen isotopes of coal-ball carbonate (δ18O = 16 to 3 per mil) suggest a freshwater origin. However, the widespread occurrence of marine invertebrates and early diagenetic framboidal pyrite in coal balls suggests that many formed in close proximity to marine water. Indeed, carbonate petrology points to a marine or brackish water origin for the first-formed carbonate cements in coal balls. Petrographic and geochemical (microprobe) analysis of coal-ball carbonates in Pennsylvanian coals from the midcontinent of North America (Western Interior Basin, West Pangaea) and the Ruhr and Donets Basins (East Pangaea) indicate that the first formed carbonate is either radaxial, nonstochiometric dolomite or high magnesium calcite (9 - 17 mol % MgCO3, indicating precipitation in marine or brackish water. Although both primary dolomite and high magnesium calcite can form in lacustrine settings, the lakes in which these minerals form occur in carbonate terranes

Diagenetic effects of compaction on reservoir properties: The case of early callovian ``Dalle Nacrée'' formation (Paris basin, France)

NASA Astrophysics Data System (ADS)

Nader, Fadi H.; Champenois, France; Barbier, Mickaël; Adelinet, Mathilde; Rosenberg, Elisabeth; Houel, Pascal; Delmas, Jocelyne; Swennen, Rudy

2016-11-01

The impact of compaction diagenesis on reservoir properties is addressed by means of observations made on five boreholes with different burial histories of the Early Callovian ;Dalle Nacrée; Formation in the Paris Basin. Petrographic analyses were carried out in order to investigate the rock-texture, pore space type and volume, micro-fabrics, and cement phases. Based on the acquired data, a chronologically ordered sequence of diagenetic events (paragenesis) for each borehole was reconstructed taking the burial history into account. Point counting and a segmentation algorithm (Matlab) were used to quantify porosity, as well as the amounts of grain constituents and cement phases on scanned images of studied thin sections. In addition, four key samples were analyzed by 3D imaging using microfocus X-ray computer tomography. Basin margin grainstones display a different burial diagenesis when compared to basin centre grainstones and wackestones. The former have been affected by considerable cementation (especially by blocky calcite) prior to effective burial, in contrast to the basin centre lithologies where burial and compaction prevailed with relatively less cementation. Fracturing and bed-parallel stylolitization, observed especially in basinal wackestone facies also invoke higher levels of mechanical and chemical compaction than observed in basin marginal equivalents. Compaction fluids may have migrated at the time of burial from the basin centre towards its margins, affecting hence the reservoir properties of similar rock textures and facies and resulting in cross-basin spatial diagenetic heterogeneities.

Sedimentary Carbon, Sulfur, and Iron Relationships in Modern and Ancient Diagenetic Environments of the Eel River Basin (U.S.A.)

USGS Publications Warehouse

Sommerfield, C.K.; Aller, R.C.; Nittrouer, C.A.

2001-01-01

Depositional and diagenetic controls on the distributions of carbon, sulfur, and iron (C-S-Fe) in modern sediments and upper Pleistocene mudrocks of the Eel River Basin (ERB), northern California continental margin, were investigated using a combination of geochemical, radioisotopic, and sedimentological methods. A mass balance based on down-core profiles of porewater and solid-phase constituents and diagenetic modeling suggests that only 12-30% of the pyrite-S produced via SO4-2 reduction during burial is retained in modern shelf and upper slope deposits of the ERB. Bioturbational reoxidation of initially reduced S is inferred to be the major control on S preservation, on the basis of an observed inverse relationship between pyrite-S retention and biological mixing intensity, estimated from profiles of excess 234Th. Importantly, these findings argue that massive depositional episodes on the shelf following floods of the Eel River have a negligible long-term impact on bioturbating macrofauna and the potential to affect geochemical properties of the sediments. Down-core profiles of reactive Fe3+and Py-Fe(II) for the modern deposits suggest that highly reactive Fe phases are sulfidized well within ∼ 500-2000 years of burial, thereby limiting later pyritization, which could occur through sulfidation of less reactive phases. This result explains the low (≤ 0.4) degree of pyritization (DOP) values exhibited by both modern and ancient deposits of the ERB and lends support to the notion that pyritization in aerobic continental-margin sediments is largely associated with highly reactive detrital Fe oxides. Comparable mean C/S weight ratios for modern sediments (5.4 ± 3.3, 1σ) and mudrocks (6.9 ± 4.5) of the ERB suggest that the upper Pleistocene strata reflect a geochemical environment analogous to that of the modern margin. Specifically, the C-S-Fe signatures shared by the modern and ancient deposits are a consequence of similar detrital Fe mineralogies, initial

Iodine-to-calcium ratios in carbonates suggest a primary origin for the Precambrian Lomagundi and Shuram carbon isotope excursions

NASA Astrophysics Data System (ADS)

Hardisty, D. S.; Lu, Z.; Planavsky, N. J.; Osburn, M. R.; Bekker, A.; Lyons, T. W.

2013-12-01

the Archean, suggest very early dolomitization in an oxidizing surface ocean promoting aerobic iodine cycling. This interpretation is consistent with earlier suggestions relating a >+10 ‰ δ13Ccarb shift to substantial organic carbon burial and associated oxygen production. Extremely negative δ13Ccarb (down to <-10 ‰) observed during the Shuram event have been linked to both diagenetic and primary mechanisms. We propose, however, that a marked increase in I/Ca ratios associated with the negative δ13Ccarb excursion in the Khufai Formation of Oman provides evidence for a primary origin for the Shuram. Such an increase could be interpreted as enhanced delivery of IO3- or total iodine from the deep ocean, perhaps driven by deep ocean ventilation and/or oxidation of a large pool of marine-derived organic matter. Overall, regardless of the individual primary controls driving increases in carbonate I/Ca during the Lomagundi and Shuram events, authigenic/diagenetic controls allowing for increased I/Ca are unlikely, suggesting a primary origin for the two largest δ13Ccarb excursions in Earth history.

Dehydroxylation and diagenetic variations in diatom oxygen isotope values

NASA Astrophysics Data System (ADS)

Dodd, Justin P.; Wiedenheft, Wilson; Schwartz, Joshua M.

2017-02-01

Numerous studies have documented changes in the dissolution and reactivity of biogenic silica as it is transferred from the water column to sediment archives; here we present the first experimental data that demonstrate a physical mechanism by which the oxygen isotope (δ18Osil) values of biogenic silica (diatoms) are altered during early diagenesis. The δ18Osil value of diatom silica cultured at 19.3 °C was +31.9‰ ± 0.2‰ (n = 6); the same silica experimentally aged in an artificial seawater media at near silica saturation at 85 °C had an average δ18Osil value of +27.1‰ ± 0.6‰ (n = 20). The most significant change in the δ18Osil value was coincident with an initial reduction in the total silanol abundance, indicating that the timing of dehydroxylation reactions in natural sedimentary environments is associated with diagenetic changes in the recorded δ18Osil values. The rate of change in the experimental aging environment at 85 °C was rapid, with significant changes in both silanol abundance and δ18Osil values. Additionally, the silica-water fractionation relationship recorded by the experimentally-aged samples approaches the equilibrium quartz-water fractionation factor. The linear rate law was used to estimate the timing of these changes in low temperature environments; the initial and most significant change in silica reactivity and δ18Osil values is likely to occur on the order of 10's of years at 4 °C. Published silica-water fractionation factors for sedimentary diatoms most likely represent a combination of growth and diagenetic environments, and the δ18O value of diagenetic water needs to be addressed when using δ18Osil values to reconstruct paleoceanographic and paleoenvironmental conditions.

Hydrothermal and Diagenetic Mineralization on Mars

NASA Astrophysics Data System (ADS)

Ehlmann, B. L.; Quinn, D. P.

2015-12-01

Predicted by geophysical modeling, the mineraolgic record of early Mars groundwater has only recently been discovered. First, rover exploration in sedimentary basins reveals diagenesis. At Meridiani, sandstone porosity is occluded by precipitation of secondary sulfates, hematite, and silica. Multiple alteration episodes are indicated by crystal vugs, disruption of preexisting textures by hematite concretions, and grain coatings (e.g. McLennan et al., 2005). At Gale crater, raised ridges in mudstones, interpreted to be early diagenetic features, are crossed by later-emplaced hydrated calcium sulfate veins (e.g. Grotzinger et al., 2014). Waters in Gale were likely circumneutral while jarosite mineralogy at Meridiani implies acidic waters. Second, systems of raised ridges at 100-m scale are observed from orbit in multiple Martian sedimentary rock units. An outstanding example is sulfate-bearing sediments exhumed at the northern margin of the Syrtis Major lavas (e.g. Quinn & Ehlmann, 2015). Polygonal and with no clearly preferred orientation, the ridges rise 5-30 m above the surrounding terrain. Parallel light-toned grooves with dark interiors (indicative of isopachous fills) and jarosite in ridge mineralogy point to mineralization by acidic waters. Third, some mineral assemblages observed from orbit represent the products of subsurface aqueous alteration at elevated temperatures (Ehlmann et al., 2011). These are globally distributed, exposed in scarps and by impact cratering. Mineral assemblages variously include (a) serpentine and carbonate; (b) prehnite and chlorite, and (c) zeolites. Collectively, these datasets indicate that groundwaters were spatially widespread on ancient Mars, contributing to the sustenance of lakes and to the alteration of bedrock to >1 km depths. While the Martian surface may have always been relatively inhospitable, a warmer, wetter subsurface provided a long-term potentially habitable environment. Key outstanding questions remaining include

Quantifying the impact of early calcite cementation on the reservoir quality of carbonate rocks: A 3D process-based model

NASA Astrophysics Data System (ADS)

Hosa, Aleksandra; Wood, Rachel

2017-06-01

The reservoir properties of carbonate rocks are controlled by both deposition and diagenesis. The latter includes the early precipitation of calcite cements, which can exert a strong control on the evolution of subsequent diagenetic pathways. We quantify the impact of early marine cement growth in grainstones on evolving pore space by examining trends in the relationship between cementation and permeability using a 3D process-based model (Calcite3D). The model assumes varying proportions of polycrystalline and monocrystalline grain types, upon which we grow isopachous and syntaxial calcite cement types, respectively. We model two syntaxial cement shapes, compact and elongated, that approximate the geometries of typical rhombohedral calcite forms. Results demonstrate the effect of cement competition: an increasing proportion of monocrystalline grains creates stronger competition and a reduction in the impact of individual grains on final calcite cement volume and porosity. Isopachous cement is effective in closing pore throats and limiting permeability. We also show that the impact of syntaxial cement on porosity occlusion and therefore flow is highly dependent on monocrystalline grain location and the orientation of crystal axes. This demonstrates the importance of diagenetic overprint in controlling the evolution of rock properties, but also that this process can be essentially random. We also show that diagenesis alone can create notable heterogeneity in the permeability of carbonates. While Calcite3D is successful in modelling realistic changes in cement volumes and pore space morphology, modelled permeabilities (0.01 -30D) are above the range reported in reservoir grainstones due to the very high permeability of the initial synthetic sediment deposit (58.9D). Poroperm data generated by Calcite3D, however, exhibits a linear relationship between the logarithms of porosity and permeability with a high coefficient of determination, as observed in natural media.

Paleo-fluid flow in folded, poorly lithified Quaternary sediments revealed by diagenetic concretions developed during the growth of Quattro Castella Anticline (Northern Apennines, Italy)

NASA Astrophysics Data System (ADS)

Pizzati, Mattia; Balsamo, Fabrizio; Iacumin, Paola; Swennen, Rudy; Storti, Fabrizio

2017-04-01

Diagenetic concretions and mineral masses may provide a useful tool to better understand paleo-fluid flows in transforming porous media. Moreover, the selective cementation responsible of diagenetic alterations formation, plays a key role in diminishing sediments porosity and permeability and hence reservoir quality. In compressive settings of a fold-and-thrust-belt, the presence of deep or blind thrusts could lead to the generation of folds which may influence syn-kinematic sedimentation, deep fluids migration and shallow fluid flow pattern. In this contribution we present a multidisciplinary field and laboratory study on carbonate concretions developed in Quaternary poorly lithified, shallow marine syn-kinematic sediments of the Quattro Castella Anticline in Northern Apennines (Italy). The study site is located along the Enza River, where shallow marine to continental sediments are exposed along the forelimb of the fold nucleated during Late Miocene and still active today. Field mapping was aimed to link bedding attitude of syn-kinematic sediments with the geometry, arrangement, shape and size of concretionary bodies. The studied concretions are both tabular (i.e. parallel to sediment bedding) and elongate single or coalescent concretionary bodies (i.e. plunging at different angle to bedding dip throughout the stratigraphic section). Concretions dimensions range from a few centimeters in single elongate concretions, up to a few meters in tabular and coalescent ones. In situ permeability measurements and laboratory grain size analyses were performed along the studied section to constrain the petrophysical properties of sediments hosting carbonate concretions. Carbon and oxygen stable isotopes analyses on carbonate concretions (performed both on hand specimens and also on thin sections), together with petrographic and cathodoluminescence observations, were used to better constrain the diagenetic environment in which calcite precipitation occurred. Our results

Geochemistry of Precambrian carbonates. IV - Early Paleoproterozoic (2.25 +/- 0.25 Ga) seawater

NASA Technical Reports Server (NTRS)

Veizer, Jan; Clayton, R. N.; Hinton, R. W.

1992-01-01

The mineralogy, chemistry, and isotopic composition of the Malmani Dolomite, Duck Creek Dolomite, and Bruce 'Limestone' Member of the Espanola Formation are studied in an effort to restrict the first- and second-order variations in isotopic composition of Early Paleoproterozoic seawater. The diagenetic rank is found to increase in the order Duck Creek less than Bruce less than Malmani. The interpolation of alteration trends to 'best' value yields an estimate of 0.70550 for Sr-87/Sr-86. For delta C-13, the measured range of 0 +/- 1.5 percent PDB is similar to that observed for Phanerozoic marine carbonates, while the 'best' delta O-18 value for dolostones is -5 percent PDB, depleted in O-18 relative to Phanerozoic counterparts but comparable to estimates obtained for Archean facies. The isotope geochemistry and mineralogy of Bruce 'Limestone' Member is consistent with the proposition that the sequence was deposited in a lacustrine environment.

A subtle diagenetic trap in the Cretaceous Glauconite Sandstone of Southwest Alberta

USGS Publications Warehouse

Meshri, I.D.; Comer, J.B.

1990-01-01

Despite the long history of research which documents many studies involving extensive diagenesis, there are a few examples of a fully documented diagenetic trap. In the context of this paper, a trap is a hydrocarbon-bearing reservoir with a seal; because a reservoir without a seal acts as a carrier bed. The difficulty in the proper documentation of diagenetic traps is often due to the lack of: (a) extensive field records on the perforation and production histories, which assist in providing the depth of separation between hydrocarbon production and non-hydrocarbon or water production; and (b) the simultaneous availability of core data from these intervals, which could be studied for the extent and nature of diagenesis. This paper provides documentation for the existence of a diagenetic trap, based on perforation depths, production histories and petrologic data from the cored intervals, in the context of the geologic and stratigraphic setting. Cores from 15 wells and SP logs from 45 wells were carefully correlated and the data on perforated intervals was also acquired. Extensive petrographic work on the collected cores led to the elucidation of a diagenetic trap that separates water overlying and updip from gas downdip. Amoco's Berrymore-Lobstick-Bigoray fields, located near the northeastern edge of the Alberta Basin, are prolific gas producers. The gas is produced from reservoir rock consisting of delta platform deposits formed by coalescing distributary mouth bars. The overlying rock unit is composed of younger distributary channels; although it has a good reservoir quality, it contains and produces water only. The total thickness of the upper, water-bearing and lower gas-bearing sandstone is about 40 ft. The diagenetic seal is composed of a zone 2 to 6 ft thick, located at the base of distributary channels. This zone is cemented with 20-30% ankerite cement, which formed the gas migration and is also relatively early compared to other cements formed in the water

Composition, diagenetic transformation and alkalinity potential of oil shale ash sediments.

PubMed

Mõtlep, Riho; Sild, Terje; Puura, Erik; Kirsimäe, Kalle

2010-12-15

Oil shale is a primary fuel in the Estonian energy sector. After combustion 45-48% of the oil shale is left over as ash, producing about 5-7 Mt of ash, which is deposited on ash plateaus annually almost without any reuse. This study focuses on oil shale ash plateau sediment mineralogy, its hydration and diagenetic transformations, a study that has not been addressed. Oil shale ash wastes are considered as the biggest pollution sources in Estonia and thus determining the composition and properties of oil shale ash sediment are important to assess its environmental implications and also its possible reusability. A study of fresh ash and drillcore samples from ash plateau sediment was conducted by X-ray diffractometry and scanning electron microscopy. The oil shale is highly calcareous, and the ash that remains after combustion is derived from the decomposition of carbonate minerals. It is rich in lime and anhydrite that are unstable phases under hydrous conditions. These processes and the diagenetic alteration of other phases determine the composition of the plateau sediment. Dominant phases in the ash are hydration and associated transformation products: calcite, ettringite, portlandite and hydrocalumite. The prevailing mineral phases (portlandite, ettringite) cause highly alkaline leachates, pH 12-13. Neutralization of these leachates under natural conditions, by rainwater leaching/neutralization and slow transformation (e.g. carbonation) of the aforementioned unstable phases into more stable forms, takes, at best, hundreds or even hundreds of thousands of years. Copyright © 2010 Elsevier B.V. All rights reserved.

Remote detection of fluid-related diagenetic mineralogical variations in the Wingate Sandstone at different spatial and spectral resolutions

NASA Astrophysics Data System (ADS)

Okyay, Unal; Khan, Shuhab D.

2016-02-01

Well-exposed eolian units of the Jurassic system on the Colorado Plateau including the Wingate Sandstone, show prominent color variations throughout southeastern Utah due to diagenetic changes that include precipitation and/or removal of iron oxide, clay, and carbonate cement. Spatially variable characteristic diagenetic changes suggest fluid-rock interactions through the sandstone. Distinctive spectral signatures of diagenetic minerals can be used to map diagenetic mineral variability and possibly fluid-flow pathways. The main objective of this work was to identify characteristic diagenetic minerals, and map their spatial variability from regional to outcrop scale in Wingate Sandstone exposures of Lisbon Valley, Utah. Laboratory reflectance spectroscopy analysis of the samples facilitated identification of diagnostic spectral characteristics of the common diagenetic minerals and their relative abundances between altered and unaltered Wingate Sandstone. Comparison of reflectance spectroscopy with satellite, airborne, and ground-based imaging spectroscopy data provided a method for mapping and evaluating spatial variations of diagenetic minerals. The Feature-oriented Principal Component Selection method was used on Advanced Spaceborne Thermal Emission and Reflection Radiometer data so as to map common mineral groups throughout the broader Wingate Sandstone exposure in the area. The Minimum Noise Fraction and Spectral Angle Mapper methods were applied on airborne HyMap and ground-based hyperspectral imaging data to identify and map mineralogical changes. The satellite and airborne data showed that out of 25.55 km2 total exposure of Wingate Sandstone in Lisbon Valley, unaltered sandstone cover 12.55 km2, and altered sandstone cover 8.90 km2 in the northwest flank and 5.09 km2 in the southern flank of the anticline. The ground-based hyperspectral data demonstrated the ability to identify and map mineral assemblages with two-dimensional lateral continuity on near

Fatty acids in sparry calcite fracture fills and microsparite cement of septarian diagenetic concretions

NASA Astrophysics Data System (ADS)

Pearson, M. J.; Hendry, J. P.; Taylor, C. W.; Russell, M. A.

2005-04-01

Sparry calcite fracture fills and concretion body cements in concretions from the Flodigarry Shale Member of the Staffin Shale Formation, Isle of Skye, Scotland, entrap and preserve mineral and organic materials of sedimentary and diagenetic origin. Fatty acids are a major component of the lipids recovered by decarbonation and comprise mainly n-alkanoic and α-ω dicarboxylic acids. Two generations of fracture-fill calcite (early brown and later yellow) and the concretion body microspar yield significantly different fatty acid profiles. Early brown calcites yield mainly medium-chain n-alkanoic acids with strong even predominance; later yellow calcites are dominated by α-ω dicarboxylic acids with no even predominance. Both fracture fills lack the long-chain n-alkanoic and α-ω dicarboxylic acids additionally recovered from the concretion bodies. The absence of longer chain acids in the calcite spar fracture fills is inferred to result from the transport of fatty acids by septarian mineralising fluids whereby low-aqueous solubility of longer chain acids or their salts accounts for their relative immobility. Comparative experiments have been carried out using conventional solvent extraction on the concretion body and associated shales, both decarbonated and untreated. Extracted lipid yields are higher, but the fatty acids probably derive from mixed locations in the rock including both kerogen- and carbonate-associated lipid pools. Only experiments involving decarbonation yielded α-ω dicarboxylic acids in molecular distributions probably controlled mainly by fluid transport. Alkane biomarker ratios indicate very low thermal maturity has been experienced by the concretions and their host sediments. Septarian cracks lined by brown calcite formed during early burial. Microbial CO 2 from sulphate-reducing bacteria was probably the main source of mineralising carbonate. Emplacement of the later septarian fills probably involved at least one episode of fluid invasion.

Making a black shale shine: the interaction of hydrothermal fluids and diagenetic processes

NASA Astrophysics Data System (ADS)

Gleeson, Sarah; Magnall, Joe; Reynolds, Merilie

2016-04-01

Hydrothermal fluids are important agents of mass and thermal transfer in the upper crust. This is exemplified by shale-hosted massive sulphide deposits (SHMS), which are anomalous accumulations of Zn and Pb sulphides (± barite) in sedimentary basins created by hydrothermal fluids. These deposits occur in passive margin settings and, typically, there is no direct evidence of magmatic input. Recent studies of Paleozoic deposits in the North American Cordillera (MacMillan Pass and Red Dog Districts) have shown that the deposits are formed in a sub-seafloor setting, where the potential for thermal and chemical gradients is high. Mineralization is characterized by the replacement and displacement of unconsolidated, partially lithified and lithified biosiliceous mudstones (± carbonates), and commonly the sulphide mineralization post-dates, and replaces, bedded barite units in the sediments. The Red Dog District (Alaska, USA) contain some of the largest Zn-Pb deposits ever discovered. The host-rocks are dominantly carbonaceous mudstones, with carbonate units and some radiolarites. The ore forms massive sulphide bodies that replace pyritized mudstones, barite and carbonate units. Lithological and textural relationships provide evidence that much of the ore formed in bioturbated, biosiliceous zones that may have had high primary porosity and/or permeability. Sediment permeability may have been further modified by aging of the silica rich sediments and the dissolution/replacement of carbonate and barite beds. At the Tom and Jason deposits (MacMillan Pass, Yukon) the fault-controlled hydrothermal upflow zone is uniquely preserved as an unequivocal vent complex. Here, the metal bearing fluids are hot (300°C), low salinity (6 wt% NaCl equiv.) and acidic (pH < 4.5). These fluids were initially in thermal and chemical disequilibrium with a partially lithified organic rich host-rock but cooled rapidly during fluid rock interaction and the input of diagenetic pore fluids

(S, C, O, Sr) isotopic constraints on the diagenetic evolution of the COX clay formations at the Bure URL site, Paris Basin)

NASA Astrophysics Data System (ADS)

Lerouge, C.; Gaucher, E. C.; Tournassat, C.; Agrinier, P.; Widory, D.; Guerrot, C.; Buschaert, S.

2009-04-01

The Underground Research Laboratory of Bure, located in the Eastern part of the Paris Basin, was selected by ANDRA (French Agency for Nuclear Management) in order to study the feasibility of a nuclear waste disposal in the Callovian-Oxfordian thick clayey formation at 400 meters depth. Since 1994's, numerous investigations have been initiated to understand and predict the behaviour of the clay formation in time and in space, by constraining its stability, the chemical evolution of the porewaters, and solution transfers between the clayey formation and its adjacent limestone sequences during geological times (ANDRA, 2005). In that way, this study presents combined new mineralogical and isotopic data of the diagenetic mineral sequence to constrain the porewater chemistry of the rock at different stages of the sedimentary then burial history of the clayey formation. The petrological study of Callovian-Oxfordian claystones provided evidence of the following diagenetic mineral sequence: 1) Framboïdal pyrite ± micritic calcite in replacement of carbonate bioclasts and in bioturbations, 2) Iron-rich euhedral carbonates (ankerite, sideroplesite), Glauconite, 3) Sparry dolomite, celestite in residual porosity, 4) Chalcedony 5) quartz/calcite. Pyrite in bioturbations shows a wide range of δ34S (-38 to +74 permil/CDT), providing evidence of bacterial sulphate reduction processes. The lowest negative values (-38 to -22 permil) indicate precipitation of pyrite in a marine environment with a permanent recharge in sulphate, whereas the higher pyrite δ34S values (-14 up to +74 permil) show that pyrite precipitated in a system that closed for sulphate. Consequently the variations of pyrite δ34S in bioturbations along the lithostratigraphic profil indicate a change of sedimentation conditions from a deep marine environment to an environment with alternative recharge of marine sulphates; that is consistent with the transgression/regression cycle observed in the middle sequence

Early diagenetic partial oxidation of organic matter and sulfides in the Middle Pennsylvanian (Desmoinesian) Excello Shale Member of the Fort Scott Limestone and equivalents, northern Midcontinent region, USA

USGS Publications Warehouse

Hatch, J.R.; Leventhal, M.S.

1997-01-01

A process of early diagenetic partial oxidation of organic matter and sulfides has altered the chemical composition of the Middle Pennsylvanian Excello Shale Member of the Fort Scott Limestone and equivalents in the northern Midcontinent region. This process was identified by comparison of organic carbon contents, Rock-Eval hydrogen indices, organic carbon ??13C and element compositions of core and surface mine samples of the Excello Shale Member with analyses of three other underlying and overlying organic-matter-rich marine shales (offshore shale lithofacies) from southern Iowa, northern Missouri, eastern Kansas and northeastern Oklahoma. The end product of the partial oxidation process is shale with relatively low contents of hydrogen-poor, C13-enriched organic matter, lower contents of sulfur and sulfide-forming elements, and relatively unchanged contents of phosphorus and many trace elements (e.g. Cr, Ni, and V). However, because of lower organic carbon contents, element/organic carbon ratios are greatly increased. The partial oxidation process apparently took place during subaerial exposure of the overlying marine carbonate member (Blackjack Creek Member of the Fort Scott Limestone) following a marine regression when meteoric waters percolated down to the level of the Excello muds allowing oxidation of organic matter and sulfides. This hypothesis is supported by earlier workers, who have identified meteoric carbonate cements within, and soil horizons at the top of the Blackjack Creek Member. The period of oxidation is constrained in that organic matter and sulfides in the Little Osage Shale Member of the Fort Scott Limestone and equivalents (immediately overlying the Blackjack Creek Member) appear unaltered. Similar alteration of other shales in the Middle and Upper Pennsylvanian sections may be local to regional in extent and would depend on the extent and duration of the marine regression and be influenced by local variations in permeability and topography

Effects of early sea-floor processes on the taphonomy of temperate shelf skeletal carbonate deposits

NASA Astrophysics Data System (ADS)

Smith, Abigail M.; Nelson, Campbell S.

2003-10-01

Cool-water shelf carbonates differ from tropical carbonates in their sources, modes, and rates of deposition, geochemistry, and diagenesis. Inorganic precipitation, marine cementation, and sediment accumulation rates are absent or slow in cool waters, so that temperate carbonates remain longer at or near the sea bed. Early sea-floor processes, occurring between biogenic calcification and ultimate deposition, thus take on an important role, and there is the potential for considerable taphonomic loss of skeletal information into the fossilised record of cool-water carbonate deposits. The physical breakdown processes of dissociation, breakage, and abrasion are mediated mainly by hydraulic regime, and are always destructive. Impact damage reduces the size of grains, removes structure and therefore information, and ultimately may transform skeletal material into anonymous particles. Abrasion is highly selective amongst and within taxa, their skeletal form and structure strongly influencing resistance to mechanical breakdown. Dissolution and precipitation are the end-members of a two-way chemical equilibrium operating in sea water. In cool waters, inorganic precipitation is rare. There is conflicting opinion about the importance of diagenetic dissolution of carbonate skeletons on the temperate sea floor, but test maceration and early loss of aragonite in particular are reported. Dissolution may relate to undersaturated acidic pore waters generated locally by a combination of microbial metabolisation of organic matter, strong bioturbation, and oxidation of solid phase sulphides immediately beneath the sea floor in otherwise very slowly accumulating skeletal deposits. Laboratory experiments demonstrate that surface-to-volume ratio and skeletal mineralogy are both important in determining skeletal resistance to dissolution. Biological processes on the sea floor include encrustation and bioerosion. Encrustation, a constructive process, may be periodic or seasonal, and can be

Origin and diagenetic transformations of C 25 and C 30 highly branched isoprenoid sulphur compounds: Further evidence for the formation of organically bound sulphur during early diagenesis

NASA Astrophysics Data System (ADS)

Kohnen, M. E. L.; Damsté, J. S. Slnninghe; Kock-van Dalen, A. C.; Haven, H. L. Ten; Rullkötter, J.; De Leeuw, J. W.

1990-11-01

A number of C 25 and C 30 highly branched isoprenoid (HBI) sulphur compounds (E.G., thiolanes, 1-oxo-thiolanes, thiophenes, and benzo[ b]thiophenes) with 2,6,10,14-tetramethyl-7-(3-methylpentyl)pentadecane and 2,6,10,14,18-pentamethyl-7-(3-methylpentyl)nonadecane carbon skeletons were identified in sediments, ranging from Holocene to Upper Cretaceous. These identifications are based on mass spectral characterisation, desulphurisation, and, in some cases, by comparison of mass spectral and relative retention time data with those of authentic standards. The presence of unsaturated C 25 and C 30 HBI thiolanes in a Recent sediment from the Black Sea (age 3-6 × 10 3 a) strongly supports their formation during early diagenesis. The co-occurrence of HBI polyenes (C 25 and C 30) and unsaturated HBI thiolanes (C 25 and C 30) possessing two double bonds less than the corresponding HBI polyenes, in this Recent sediment, testifies to the formation of unsaturated HBI thiolanes by a reaction of inorganic sulphur species with double bonds of the HBI polyenes. Furthermore, a diagenetic scheme for HBI sulphur compounds is proposed based on the identification of HBI sulphur compounds in sediment samples with different maturity levels.

Diagenetic Mineralogy at Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Vaniman, David; Blake, David; Bristow, Thomas F.; Chipera, Steve; Gellert, Ralf; Ming, Douglas; Morris, Richard; Rampe, E. B.; Rapin, William

2015-01-01

Three years into exploration of sediments in Gale crater on Mars, the Mars Science Laboratory rover Curiosity has provided data on several modes and episodes of diagenetic mineral formation. Curiosity determines mineralogy principally by X-ray diffraction (XRD), but with supporting data from thermal-release profiles of volatiles, bulk chemistry, passive spectroscopy, and laser-induced breakdown spectra of targeted spots. Mudstones at Yellowknife Bay, within the landing ellipse, contain approximately 20% phyllosilicate that we interpret as authigenic smectite formed by basalt weathering in relatively dilute water, with associated formation of authigenic magnetite as in experiments by Tosca and Hurowitz [Goldschmidt 2014]. Varied interlayer spacing of the smectite, collapsed at approximately 10 A or expanded at approximately 13.2 A, is evidence of localized diagenesis that may include partial intercalation of metal-hydroxyl groups in the approximately 13.2 A material. Subsequent sampling of stratigraphically higher Windjana sandstone revealed sediment with multiple sources, possible concentration of detrital magnetite, and minimal abundance of diagenetic minerals. Most recent sampling has been of lower strata at Mount Sharp, where diagenesis is widespread and varied. Here XRD shows that hematite first becomes abundant and products of diagenesis include jarosite and cristobalite. In addition, bulk chemistry identifies Mg-sulfate concretions that may be amorphous or crystalline. Throughout Curiosity's traverse, later diagenetic fractures (and rarer nodules) of mm to dm scale are common and surprisingly constant and simple in Ca-sulfate composition. Other sulfates (Mg,Fe) appear to be absent in this later diagenetic cycle, and circumneutral solutions are indicated. Equally surprising is the rarity of gypsum and common occurrence of bassanite and anhydrite. Bassanite, rare on Earth, plays a major role at this location on Mars. Dehydration of gypsum to bassanite in the

Diagenetic silica enrichment and late-stage groundwater activity in Gale crater, Mars

USGS Publications Warehouse

Frydenvang, Jens; Gasda, Patrick J.; Hurowitz, Joel A.; Grotzinger, John P.; Wiens, Roger C.; Newsom, Horton E.; Edgett, Ken S.; Watkins, Jessica; Bridges, John C.; Maurice, Sylvestre; Fisk, Martin R.; Johnson, Jeffrey R.; Rapin, William; Stein, Nathan; Clegg, Sam M.; Schwenzer, S. P.; Bedford, C.; Edwards, P.; Mangold, Nicolas; Cousin, Agnes; Anderson, Ryan; Payre, Valerie; Vaniman, David; Blake, David; Lanza, Nina L.; Gupta, Sanjeev; Van Beek, Jason; Sautter, Violaine; Meslin, Pierre-Yves; Rice, Melissa; Milliken, Ralf; Gellert, Ralf; Thompson, Lucy; Clark, Ben C.; Sumner, Dawn Y.; Fraeman, Abigail A.; Kinch, Kjartan M; Madsen, Morten B.; Mitofranov, Igor; Jun, Insoo; Calef, Fred J.; Vasavada, Ashwin R.

2017-01-01

Diagenetic silica enrichment in fracture-associated halos that crosscut lacustrine and unconformably overlying aeolian sedimentary bedrock is observed on the lower north slope of Aeolis Mons in Gale crater, Mars. The diagenetic silica enrichment is colocated with detrital silica enrichment observed in the lacustrine bedrock yet extends into a considerably younger, unconformably draping aeolian sandstone, implying that diagenetic silica enrichment postdates the detrital silica enrichment. A causal connection between the detrital and diagenetic silica enrichment implies that water was present in the subsurface of Gale crater long after deposition of the lacustrine sediments and that it mobilized detrital amorphous silica and precipitated it along fractures in the overlying bedrock. Although absolute timing is uncertain, the observed diagenesis likely represents some of the most recent groundwater activity in Gale crater and suggests that the timescale of potential habitability extended considerably beyond the time that the lacustrine sediments of Aeolis Mons were deposited.

Percolation of diagenetic fluids in the Archaean basement of the Franceville basin

NASA Astrophysics Data System (ADS)

Mouélé, Idalina Moubiya; Dudoignon, Patrick; Albani, Abderrazak El; Cuney, Michel; Boiron, Marie-Christine; Gauthier-Lafaye, François

2014-01-01

-rich formations; a low-salinity fluid likely of meteoric origin migrating through the granitic basement; mineralizing fluids resulting from the mixing of fluids 1 and 3; high-temperature fluids resulting from the natural nuclear reactor environment (Mathieu et al., 2000). The present paper attempts to characterize the succession of alteration events that have affected the top of the basement below the Palaeoproterozoic sediment unconformity. Are these alterations related to early post-magmatic to hydrothermal events, to palaeoweathering, or to late infiltration of diagenetic brines from the overlying basin? Our study, carried out on drill core samples from Kiéné, is supported by petrographic investigation, new fluid inclusion data and U-Pb geochronology on monazite.

Latent volcanic heat and further unique aspects of early diagenetic stratiform copper mineralization in the White Pine-Presque Isle District, northern Michigan

NASA Astrophysics Data System (ADS)

Brown, Alex C.

2018-06-01

The curious occurrence of copper-rich early diagenetic sediment-hosted stratiform copper mineralization in the finest-grained facies of Nonesuch greybeds in northern Michigan has been previously attributed to the warming of cupriferous brines in the footwall Copper Harbor Conglomerate by latent volcanic heat from the subjacent Porcupine Volcanics shield volcano. That anomalous footwall warming is employed here to explain other unique aspects of the White Pine-Presque Isle mineralization: the abrupt downward sulfide zoning from disseminated pyrite to chalcocite across the top of the cupriferous zone; the absence of bornite and chalcopyrite in the cupriferous zone proper; and the essential absence of pseudomorphs after pyrite euhedra and framboidal aggregates within the cupriferous zone proper, as well as the relatively coarse-grained character of disseminated chalcocite in the cupriferous zone.

Diagenetic Crystal Clusters and Dendrites, Lower Mount Sharp, Gale Crater

NASA Technical Reports Server (NTRS)

Kah, L. C.; Kronyak, R.; Van Beek, J.; Nachon, M.; Mangold, N.; Thompson, L.; Wiens, R.; Grotzinger, J.; Farmer, J.; Minitti, M.;

Diagenetic alteration of impact spherules in the Neoarchean Monteville layer, South Africa

USGS Publications Warehouse

Kohl, I.; Simonson, B.M.; Berke, M.

2006-01-01

Intercontinental correlation of distal Archean impact ejecta layers can be used to help create a global time-stratigraphic framework for early Earth events. For example, an impact spherule layer in the Neoarchean Monteville Formation (Griqualand West Basin, South Africa) may be correlated with layers in one or more formations in Western Australia. To help assess the degree to which diagenetic alteration would hinder such correlations, we performed a petrographic study of spherules in the Monteville layer. Most of the spherules in the Monteville layer have botryoidal rims composed of radial-fibrous K-feldspar, but compaction and replacement have greatly altered their appearance and mineralogy. Moreover, the Monteville spherule layer consists of three main subunits, and spherule compaction varies between subunits as well as across the Griqualand West region. Compaction is about three times greater in a medial spherulerich subunit as compared to a basal subunit rich in large intraclasts, resulting in better preservation of the shapes of melt particles in the latter. However, spherule rims have omparable numbers of fractures in both subunits, indicating the melt particles were fractured prior to compaction. Some spherules contain mica ribbons with a septarian geometry. Fracturing via rapid thermal quenching could help explain all of these features. f hot spherules possessing crystalline rims were thermally shocked when they hit the ocean, fractures would have the observed geometries and provide pathways for fluid infiltration and local replacement of glass by mica. Although heavily distorted, impact spherules in the Monteville layer are very similar to those in the Hesta occurrence of the Neoarchean Jeerinah spherule layer of the Hamersley Basin, even showing similar diagenetic histories. In this instance, diagenetic alteration may actually help rather than hinder intercontinental correlation of impact spherule layers. ??2006 Geological Society of America.

Authigenic carbonates from methane seeps of the Congo deep-sea fan

NASA Astrophysics Data System (ADS)

Pierre, Catherine; Fouquet, Yves

2007-06-01

Submersible investigations with the ROV Victor 6000 of some pockmark structures on the seafloor of the Congo deep-sea fan have shown that they are active venting sites of methane-rich fluids, associated with abundant fauna and carbonate crusts. Moreover, methane hydrates have been observed both outcropping and deep in the sediments in the centre of the “Regab” giant pockmark. Authigenic carbonates, mostly calcite sometimes mixed with aragonite, are cementing the sedimentary matrix components and fauna; diatoms are abundant but only as moulds, indicating that biogenic silica dissolution occurred in situ synchronous with carbonate precipitation. The occurrence of diagenetic barite and pyrite in some carbonate crusts demonstrates that they can be formed either within the sulphate/methane transition zone or deeper in sulphate-depleted sediments. The oxygen isotopic compositions of the diagenetic carbonates (3.17 6.01‰ V-PDB) indicate that precipitation occurred with bottom seawater mixed with a variable contribution of water from gas hydrate decomposition. The very low carbon isotopic compositions of the diagenetic carbonates (-57.1 to -27.75‰ V-PDB) demonstrate that carbon derives mostly from the microbial oxidation of methane.

A critical evaluation of carbon isotope stratigraphy and biostratigraphic implications for Late Cretaceous global correlation

NASA Astrophysics Data System (ADS)

Wendler, Ines

2013-11-01

carbonate, and in partitioning of carbon between organic carbon and carbonate sinks. These variations are mainly controlled by changes in climate and eustasy. Additionally, some globally synchronous shifts in the bulk δ13Ccarb records could result from parallel variation in the contribution of authigenic carbonate to the sediment. Formation of these cements through biologically mediated early diagenetic processes is related to availability of oxygen and organic material and, thus, can be globally synchronized by fluctuations in eustasy, atmospheric and oceanic oxygen levels or in large-scale oceanic circulation. Because the influence of early diagenetic cements on the bulk δ13Ccarb signal can, but need not be synchronized, chemostratigraphy should not be used as a stand-alone method for trans-continental correlation, and especially minor isotopic shifts have to be interpreted with utmost care. Nevertheless, the observed consistency of the δ13C correlations confirms global scale applicability of bulk sediment δ13C chemostratigraphy for the Late Cretaceous, including sediments that underwent lithification and burial diagenesis such as the sediments from the Himalayan and Alpine sections. Limitations arise from increased uncertainties (1) in sediments with very low carbonate content, (2) from larger δ13C variability in sediments from very shallow marine environments, (3) from unrecognized hiatuses or strong changes in sedimentation rates, and (4) in sections with short stratigraphic coverage or with few biostratigraphic marker horizons.

Dolomitization in Late Jurassic-Early Cretaceous Platform Carbonates (Berdiga Formation), Ayralaksa Yayla (Trabzon), NE Turkey

NASA Astrophysics Data System (ADS)

Yıldız, Merve; Ziya Kırmacı, Mehmet; Kandemir, Raif

2017-04-01

ABSTRACT Pontides constitute an E-W trending orogenic mountain belt that extends about 1100 km along the northern side of Turkey from the immediate east of Istanbul to the Georgian border at the east. Tectono-stratigraphically, the Pontides are divided into three different parts: Eastern, Central, and Western Pontides. The Eastern Pontides, including the studied area, comprise an area of 500 km in length and 100 km in width, extending along the southeast coast of the Black Sea from the Kizilirmak and Yesilirmak Rivers in the vicinity of Samsun to the Little Caucasus. This area is bordered by the Eastern Black Sea basin to the north and the Ankara-Erzincan Neotethyan suture zone to the south. The Late Jurassic-Early Cretaceous platform carbonates are widely exposed in E-W direction in the Eastern Pontides (NE Turkey). The Platform carbonates shows varying lithofacies changing from supratidal to platform margin reef laterally and vertically, and was buried until the end of Late Cretaceous. The studied Ayralaksa Yayla (Trabzon, NE Turkey) area comprises one of the best typical exposures of formation in northern zone of Eastern Pontides. In this area, the lower parts of the formation are pervasively dolomitized by fabric-destructive and fabric-preserving replacement dolomite which are Ca-rich and nonstoichiometric (Ca56-66Mg34-44). Replacement dolomites (Rd) are represented by D18O values of -19.0 to -4.2 (VPDB), D13C values of 4.4 to 2.1 \\permil (VPDB) and 87Sr/86Sr ratios of 0.70889 to 0.70636. Petrographic and geochemical data indicate that Rd dolomites are formed prior to compaction at shallow-moderate burial depths from Late Jurassic-Early Cretaceous seawater and/or partly modified seawater as a result of water/rock interaction and they were recrystallized at elevated temperatures during subsequent burial. In the subsequent diagenetic process during the Late Cretaceous when the region became a magmatic arc, as a result of interaction with Early Jurassic volcanic

Diagenetic alteration of biogenic silica oxygen isotope values: implications for use as a paleoenvironmental proxy

NASA Astrophysics Data System (ADS)

Dodd, J. P.; Abbott, T.; Scherer, R. P.

2016-12-01

formation in the early Pliocene Ross Sea may be driven by regional and global scale climate processes. Sedimentary diatoms most likely represent a combination of growth and diagenetic environments, and the δ18O value of diagenetic water needs to be addressed when reconstructing paleoceanographic and paleoenvironmental conditions.

Experimental evidence for an effect of early-diagenetic interaction between labile and refractory marine sedimentary organic matter on nitrogen dynamics

NASA Astrophysics Data System (ADS)

Turnewitsch, Robert; Domeyer, Bettina; Graf, Gerhard

2007-05-01

In most natural sedimentary systems labile and refractory organic material (OM) occur concomitantly. Little, however, is known on how different kinds of OM interact and how such interactions affect early diagenesis in sediments. In a simple sediment experiment, we investigated how interactions of OM substrates of different degradability affect benthic nitrogen (N) dynamics. Temporal evolution of a set of selected biogeochemical parameters was monitored in sandy sediment over 116 days in three experimental set-ups spiked with labile OM (tissue of Mytilus edulis), refractory OM (mostly aged Zostera marina and macroalgae), and a 1:1 mixture of labile and refractory OM. The initial amounts of particulate organic carbon (POC) were identical in the three set-ups. To check for non-linear interactions between labile and refractory OM, the evolution of the mixture system was compared with the evolution of the simple sum of the labile and refractory systems, divided by two. The sum system is the experimental control where labile and refractory OM are virtually combined but not allowed to interact. During the first 30 days there was evidence for net dissolved-inorganic-nitrogen (DIN) production followed by net DIN consumption. (Here 'DIN' is the sum of ammonium, nitrite and nitrate.) After ˜ 30 days a quasi steady state was reached. Non-linear interactions between the two types of OM were reflected by three main differences between the early-diagenetic evolutions of nitrogen dynamics of the mixture and sum (control) systems: (1) In the mixture system the phases of net DIN production and consumption commenced more rapidly and were more intense. (2) The mixture system was shifted towards a more oxidised state of DIN products [as indicated by increased (nitrite + nitrate)/(ammonium) ratios]. (3) There was some evidence that more OM, POC and particulate nitrogen were preserved in the mixture system. That is, in the mixture system more particulate OM was preserved while a higher

Chemistry of diagenetic features analyzed by ChemCam at Pahrump Hills, Gale crater, Mars

USGS Publications Warehouse

Nachon, Marion; Mangold, Nicolas; Forni, Olivier; Kah, Linda C.; Cousin, Agnes; Wiens, Roger C.; Anderson, Ryan; Blaney, Diana L.; Blank, Jen G.; Calef, Fred J.; Clegg, Samuel M.; Fabre, Cecile; Fisk, Martin R.; Gasnault, Olivier; Grotzinger, John P.; Kronyak, Rachel; Lanza, Nina L.; Lasue, Jeremie; Le Deit, Laetitia; Le Mouelic, Stephane; Maurice, Sylvestre; Meslin, Pierre-Yves; Oehler, D. Z.; Payre, Valerie; Rapin, William; Schroder, Susanne; Stack, Katherine M.; Sumner, Dawn

2017-01-01

The Curiosity rover's campaign at Pahrump Hills provides the first analyses of lower Mount Sharp strata. Here we report ChemCam elemental composition of a diverse assemblage of post-depositional features embedded in, or cross-cutting, the host rock. ChemCam results demonstrate their compositional diversity, especially compared to the surrounding host rock: (i) Dendritic aggregates and relief enhanced features, characterized by a magnesium enhancement and sulfur detection, and interpreted as Mg-sulfates; (ii) A localized observation that displays iron enrichment associated with sulfur, interpreted as Fe-sulfate; (iii) Dark raised ridges with varying Mg- and Ca-enriched compositions compared to host rock; (iv) Several dark-toned veins with calcium enhancement associated with fluorine detection, interpreted as fluorite veins. (v) Light-toned veins with enhanced calcium associated with sulfur detection, and interpreted as Ca-sulfates. The diversity of the Pahrump Hills diagenetic assemblage suggests a complex post-depositional history for fine-grained sediments for which the origin has been interpreted as fluvial and lacustrine. Assessment of the spatial and relative temporal distribution of these features shows that the Mg-sulfate features are predominant in the lower part of the section, suggesting local modification of the sediments by early diagenetic fluids. In contrast, light-toned Ca-sulfate veins occur in the whole section and cross-cut all other features. A relatively late stage shift in geochemical conditions could explain this observation. The Pahrump Hills diagenetic features have no equivalent compared to targets analyzed in other locations at Gale crater. Only the light-toned Ca-sulfate veins are present elsewhere, along Curiosity's path, suggesting they formed through a common late-stage process that occurred at over a broad area.

Cryogenic brines as diagenetic fluids: Reconstructing the diagenetic history of the Victoria Land Basin using clumped isotopes

NASA Astrophysics Data System (ADS)

Staudigel, Philip T.; Murray, Sean; Dunham, Daniel P.; Frank, Tracy D.; Fielding, Christopher R.; Swart, Peter K.

2018-03-01

The isotopic analyses (δ13C, δ18O, and Δ47) of carbonate phases recovered from a core in McMurdo Sound by ANtarctic geologic DRILLing (ANDRILL-2A) indicate that the majority of secondary carbonate mineral formation occurred at cooler temperatures than the modern burial temperature, and in the presence of fluids with δ18Owater values ranging between -11 and -6‰ VSMOW. These fluids are interpreted as being derived from a cryogenic brine formed during the freezing of seawater. The Δ47 values were converted to temperature using an in-house calibration presented in this paper. Measurements of the Δ47 values in the cements indicate increasingly warmer crystallization temperatures with depth and, while roughly parallel to the observed geothermal gradient, consistently translate to temperatures that are cooler than the current burial temperature. The difference in temperature suggests that cements formed when they were ∼260 ± 100 m shallower than at the present day. This depth range corresponds to a period of minimal sediment accumulation from 3 to 11 Myr; it is therefore interpreted that the majority of cements formed during this time. This behavior is also predicted by time-integrated modeling of cementation at this site. If this cementation had occurred in the presence of these fluids, then the cryogenic brines have been a longstanding feature in the Victoria Land Basin. Brines such as those found at this site have been described in numerous modern high-latitude settings, and analogous fluids could have played a role in the diagenetic history of other ice-proximal sediments and basins during glacial intervals throughout geologic history. The agreement between the calculated δ18Owater value and the measured values in the pore fluids shows how the Δ47 proxy can be used to identify the origin of negative δ18O values in carbonate rocks and that extremely negative values do not necessarily need to be a result of the influence of meteoric fluids or reaction at

Global Links to Local Carbon Cycling Perturbation

NASA Astrophysics Data System (ADS)

Chen, J.; Montanez, I. P.; Wang, X.; Qi, Y.

2016-12-01

Carbon cycle perturbations recorded by stable carbon isotope excursions (CIEs) play an important role in understanding climate, oceanography, and the biosphere through time. Recent studies, however, reveal the influence of regional processes on apparent global CIEs. Deconvolving local/regional from global processes imprinted in the carbon isotopic records of sedimentary successions requires integrated sedimentologic, stratigraphic, and geochemical study. Here we present coupled C and Sr isotopic records of diagenetically screened micrite and brachiopods from late Mississippian shallow-marine, carbonate platform and contemporaneous carbonate slope successions from the east Paleotethys Ocean region (South China). These records reveal distinctly different signatures of the depositional response to the onset of Carboniferous glaciation. C and Sr isotopic compositions of the platform carbonates exhibit systematic fluctuations in step with inferred sea-level changes captured by depositional cycles. CIEs in the platform succession can be correlated to the contemporaneous C isotope record from the Antler carbonate ramp (Idaho, USA). In contrast, slope carbonate and conodont isotopic records exhibit minimal variability interpreted to record the open-ocean seawater composition. The isotopic disparity between successions is interpreted to record the influence of local depositional, but not diagenetic, processes operating on the carbonate platform in response to glacioeustasy. Variability in the nature of coupled isotopic and inferred sea level fluctuations is interpreted to record stepwise onset of the late Paleozoic ice age in the late Mississippian. Initial large magnitude shifts in C and Sr isotopic compositions of late Visean to early Serpukhovian carbonates correspond to 1 to 2 myr-scale cycles driven by the buildup of continental glaciers. Subsequent decreased magnitude of isotopic shifts coincident with a shift to shorter duration and smaller magnitude sea

Chemistry of diagenetic features analyzed by ChemCam at Pahrump Hills, Gale crater, Mars

DOE PAGES

Nachon, M.; Mangold, N.; Forni, O.; ...

2017-09-01

The Curiosity rover's campaign at Pahrump Hills provides the first analyses of lower Mount Sharp strata. We report ChemCam elemental composition of a diverse assemblage of post-depositional features embedded in, or cross-cutting, the host rock. ChemCam results demonstrate their compositional diversity, especially compared to the surrounding host rock: (i) Dendritic aggregates and relief enhanced features, characterized by a magnesium enhancement and sulfur detection, and interpreted as Mg-sulfates; (ii) A localized observation that displays iron enrichment associated with sulfur, interpreted as Fe-sulfate; (iii) Dark raised ridges with varying Mg- and Ca-enriched compositions compared to host rock; (iv) Several dark-toned veins withmore » calcium enhancement associated with fluorine detection, interpreted as fluorite veins. (v) Light-toned veins with enhanced calcium associated with sulfur detection, and interpreted as Ca-sulfates. The diversity of the Pahrump Hills diagenetic assemblage suggests a complex post-depositional history for fine-grained sediments for which the origin has been interpreted as fluvial and lacustrine. Assessment of the spatial and relative temporal distribution of these features shows that the Mg-sulfate features are predominant in the lower part of the section, suggesting local modification of the sediments by early diagenetic fluids. Conversely, light-toned Ca-sulfate veins occur in the whole section and cross-cut all other features. A relatively late stage shift in geochemical conditions could explain this observation. The Pahrump Hills diagenetic features have no equivalent compared to targets analyzed in other locations at Gale crater. Only the light-toned Ca-sulfate veins are present elsewhere, along Curiosity's path, suggesting they formed through a common late-stage process that occurred at over a broad area.« less

Chemistry of diagenetic features analyzed by ChemCam at Pahrump Hills, Gale crater, Mars

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nachon, M.; Mangold, N.; Forni, O.

The Curiosity rover's campaign at Pahrump Hills provides the first analyses of lower Mount Sharp strata. We report ChemCam elemental composition of a diverse assemblage of post-depositional features embedded in, or cross-cutting, the host rock. ChemCam results demonstrate their compositional diversity, especially compared to the surrounding host rock: (i) Dendritic aggregates and relief enhanced features, characterized by a magnesium enhancement and sulfur detection, and interpreted as Mg-sulfates; (ii) A localized observation that displays iron enrichment associated with sulfur, interpreted as Fe-sulfate; (iii) Dark raised ridges with varying Mg- and Ca-enriched compositions compared to host rock; (iv) Several dark-toned veins withmore » calcium enhancement associated with fluorine detection, interpreted as fluorite veins. (v) Light-toned veins with enhanced calcium associated with sulfur detection, and interpreted as Ca-sulfates. The diversity of the Pahrump Hills diagenetic assemblage suggests a complex post-depositional history for fine-grained sediments for which the origin has been interpreted as fluvial and lacustrine. Assessment of the spatial and relative temporal distribution of these features shows that the Mg-sulfate features are predominant in the lower part of the section, suggesting local modification of the sediments by early diagenetic fluids. Conversely, light-toned Ca-sulfate veins occur in the whole section and cross-cut all other features. A relatively late stage shift in geochemical conditions could explain this observation. The Pahrump Hills diagenetic features have no equivalent compared to targets analyzed in other locations at Gale crater. Only the light-toned Ca-sulfate veins are present elsewhere, along Curiosity's path, suggesting they formed through a common late-stage process that occurred at over a broad area.« less

Quantitative geochemical modeling along a transect off Peru: Carbon cycling in time and space, and the triggering factors for carbon loss and storage

NASA Astrophysics Data System (ADS)

Arning, Esther T.; van Berk, Wolfgang; Schulz, Hans-Martin

2012-12-01

Early diagenetic processes in Peruvian shelf and slope sediments are numerically reproduced by applying chemical thermodynamics in a complex, universal approach using the PHREEQC (version 2) computer code. The reaction kinetics of organic carbon remineralization are integrated into a set of equilibrium reactions by defining the type and the amount of converted organic matter in a certain time step. We calculate the most intense remineralization of organic carbon for present-day shelf sites, and the final carbon pool is dominated by secondary carbonates. This serves to highlight the influence of organic matter degradation and anaerobic oxidation of methane (AOM) on diagenetic mineral formation. The enrichment of aqueous methane and the formation of methane hydrate only takes place in slope sediments with high sedimentation rates that prevent diffusive loss of methane (e.g., Sites 682 and 688). Moreover, AOM prevents the diffusion of dissolved methane into overlying seawater. Throughout the Miocene period, these sites were located on a former shelf and the total carbon loss from the sediments was significantly higher in comparison with the present-day. Compared with the present-day shelf site, organic matter remineralization is high, and methane is produced but not stored within the sediments. Our model calculations rule out the possibility of present-day and former shelf site sediments off the coast of Peru as methane reservoirs. Remineralized TOC has to be considered, particularly in older sediments, when interpreting TOC profiles and calculating mass accumulation rates of total organic carbon (MARTOC). The more organic matter has been remineralized during the depositional history, the larger the difference between MARTOC calculated from measured TOC data, and from the sum of modeled and measured TOC data. Consequently, most reliable primary productivity calculations are based on the sum of measured relict TOC and the amount of remineralized organic carbon

Manganese carbonates in the Upper Jurassic Georgiev Formation of the Western Siberian marine basin

NASA Astrophysics Data System (ADS)

Eder, Vika G.; Föllmi, Karl B.; Zanin, Yuri N.; Zamirailova, Albina G.

2018-01-01

Manganese (Mn) carbonate rocks are a common lithological constituent of the Upper Oxfordian to Lower Tithonian (Volgian) Georgiev Formation of the Western Siberian marine basin (WSMB). The Mn carbonates in the Georgiev Formation are present in the form of massive sediments, stromatolites, and oncolites, and are associated with glauconite and partly also phosphate-rich clay- and siltstones. Unlike most Mn carbonates, they are not directly associated with organic-rich sediments, but occur below an organic-rich succession (Bazhenov Formation). The Mn carbonate occurrences can be traced from the western central area of the WSMB to its center along a distance of at least 750 km. The thickness of the Mn carbonates and their Mn contents becomes reduced in an eastward direction, related to increased detrital input. The geochemical and mineralogical heterogeneity within the Mn carbonates indicates that they were deposited stepwise in a diagenetic regime characterized by steep gradients in Mn, Ca, and Mg. A first step consisted in the replacement of initial sediments within the microbialites during an early diagenetic stage, followed by a second step where massive sediments were transformed into Mn carbonate. During both steps, the decomposition of organic matter was an important source of the newly formed carbonate. During a further step, voids were cemented by Mn carbonates, which are rich in pyrite. This last generation may only have formed once the organic-rich sediments of the overlying Bazhenov Formation were deposited. Accumulation of the Mn carbonates in the Upper Jurassic WSMB was controlled by the proximity of Mn-enriched parent rocks, likely in the Ural, which were subjected to intense geochemical weathering during the Late Jurassic.

Geochemical characteristics and early diagenesis of recent carbonate mound sediments in the Gulf of Cadiz

NASA Astrophysics Data System (ADS)

Hamaekers, Helen; Foubert, Anneleen; Wienberg, Claudia; Hebbeln, Dierk; Swennen, Rudy

2010-05-01

Cold-water coral carbonate mounds occur in patches along the continental margin of the North Atlantic Ocean, from northern Norway down to Mauretania. Recent research has been focused on carbonate mounds in the Gulf of Cadiz, especially along the Moroccan margin. The Pen Duick, the Renard and the Vernadsky carbonate mound provinces in the Gulf of Cádiz are only some of the mound provinces which have been the subject of several recent research projects (Foubert et al., 2008; Wienberg et al., 2009). No living scleractinians could be found on top of those carbonate mounds. During cruise 64PE284 of RV Pelagia, gravity cores have been taken through carbonate mounds in the Carbonate Mound Provinces (CMP) SE of Yuma mud volcano and N of Meknes mud volcano. These cores have been analysed by several methods such as Magnetic Susceptibility (MS), X-Ray Fluorescence (XRF), Inductive Coupled Plasma Optical Emission Spectroscopy (ICP-OES) and X-Ray Diffraction (XRD) to determine the geochemical characteristics of carbonate mounds, which can be used to quantify the effects of early diagenetic processes which may have altered the palaeo-environmental characteristics of the carbonate mounds. Dating has been done with 14C and U/Th methods pointing to mound growth phases being restricted to glacial periods. XRF and ICP-OES measurements give both qualitative and quantitative data of the chemical composition of the core. The main elements that have been analysed are Ca, Si, Fe, Sr, Al, K, Mg, Ti. According to the trend they follow, they can be devided in two groups, representative for the two encountered fraction types. These two fraction types (biogenic carbonate-rich fraction and terrigenous silicate-rich fraction) can be coupled to interglacial/glacial palaeo-environmental conditions. XRD measurements give an overview of the mineralogical composition of the cores. Thin sections, analysed by cathodeluminescence and classical optical petrography, and micro-CT scans are used to

Structural and diagenetic evolution of deformation bands in contractional and extensional tectonic regimes

NASA Astrophysics Data System (ADS)

Eichhubl, P.; O'Brien, C. M.; Elliott, S. J.

2016-12-01

Mechanisms of brittle deformation of sediments and sedimentary rock change with burial because of increasing confining stress, change in pore fluid chemical and temperature conditions, and diagenetic state. In the field, these changes are observed in a transition from early non-cataclastic to later cataclastic deformation bands and to joint-based structures. Jurassic eolian sandstones in the San Rafael monocline and adjacent San Rafael Desert region, Utah, allow comparison of deformation band structures and their diagenetic attributes in contractional and extensional tectonic settings in close proximity. In the Entrada and Navajo Sandstones, we observe up to six generations of deformation bands, with earliest non-cataclastic bands having diffuse boundaries to host rock, and short and irregular traces. Later bands are cataclastic, more sharply defined, with long and straight traces. Cataclastic bands in the San Rafael monocline are interpreted to form as reverse faults during progressive rotation of the steeply dipping fold limb, resulting in an array of bands of varying dip. Bands in the San Rafael Desert form as normal faults with a narrower dip range. Although structural characteristics of bands differ in extensional and contractional tectonic regimes, cataclastic bands in either regime have comparable amount of porosity loss and quartz cementation indicating that tectonic regime does not influence band diagenesis. Abundance of quartz cement in bands, determined by point counting of SEM images, increases from earlier to later generations of bands and, within a single generation, with increasing slip along the band, reaching up to 24% of band volume. This trend is attributed to an increase in cataclasis with increasing host rock cementation and confining stress during burial, and, within the same generation, with increasing slip. Porosity loss by cementation tends to dominate over porosity loss by mechanical compaction. These findings demonstrate that quartz

Analysis and Characterization of Organic Carbon in Early Holocene Wetland Paleosols using Ramped Pyrolysis 14C and Biomarkers

NASA Astrophysics Data System (ADS)

Vetter, L.; Schreiner, K. M.; Fernandez, A.; Rosenheim, B. E.; Tornqvist, T. E.

2014-12-01

Radiocarbon analyses are a key tool for quantifying the dynamics of carbon cycling and storage in both modern soils and Quaternary paleosols. Frequently, bulk 14C dates of paleosol organic carbon provide ages older than the time of soil burial, and 14C dates of geochemical fractions such as alkali and acid extracts (operationally defined as humic acids) can provide anomalously old ages when compared to coeval plant macrofossil dates. Ramped pyrolysis radiocarbon analysis of sedimentary organic material has been employed as a tool for investigating 14C age spectra in sediments with multiple organic carbon sources. Here we combine ramped pyrolysis 14C analysis and biomarker analysis (lignin-phenols and other cupric oxide products) to provide information on the source and diagenetic state of the paleosol organic carbon. We apply these techniques to immature early Holocene brackish wetland entisols from three sediment cores in southeastern Louisiana, along with overlying basal peats. Surprisingly, we find narrow 14C age spectra across all thermal aliquots from both paleosols and peats. The weighted bulk 14C ages from paleosols and overlying peats are within analytical error, and are comparable to independently analyzed 14C AMS dates from charcoal fragments and other plant macrofossils from each peat bed. Our results suggest high turnover rates of carbon in soils relative to input of exogenous carbon sources. These data raise broader questions about processes within the active soil and during pedogenesis and burial of paleosols that can effectively homogenize radiocarbon content in soils across the thermochemical spectrum. The concurrence of paleosol and peat 14C ages also suggests that, in the absence of peats with identifiable plant macrofossils, ramped pyrolysis 14C analyses of paleosols may be used to provide ages for sea-level indicators.

Early diagenetic processes of saline meromictic Lake Kai-ike, southwest Japan: III. Sulfur speciation and isotopes

NASA Astrophysics Data System (ADS)

Sakai, N.; Yamaguchi, K. E.; Oguri, K.

2014-12-01

., 2010; Palaeo3). Geochemical characteristics of sulfur in the uppermost part of Lake Kai-ike sediment were significantly modified during early diagenesis. Such diagenetic modification for sulfur isotopes should be fully taken into account to better reconstruct past anoxic environment such as Cretaceous OAEs and Archean oceans.

Geochemistry of Precambrian carbonates. V - Late Paleoproterozoic seawater

NASA Technical Reports Server (NTRS)

Veizer, Jan; Plumb, K. A.; Clayton, R. N.; Hinton, R. W.; Grotzinger, J. P.

1992-01-01

A study of mineralogy, chemistry, and isotopic composition of the Coronation Supergroup (about 1.9 Ga, NWT), Canada, and the McArthur Group (about 1.65 NT), Australia, is reported in order to obtain better constrained data for the first- and second-order variations in the isotopic composition of late Paleoproterozoic (1.9 +/- 0.2 Ga) seawater. Petrologically, both carbonate sequences are mostly dolostones. The McArthur population contains more abundant textural features that attest to the former presence of sulfates and halite, and the facies investigated represent ancient equivalents of modern evaporitic sabkhas and lacustrine playa lakes. It is suggested that dolomitization was an early diagenetic event and that the O-18 depletion of the Archean to late Paleoproterozoic carbonates is not an artifact of postdepositional alteration.

The stable isotope composition of nitrogen and carbon and elemental contents in modern and fossil seabird guano from Northern Chile - Marine sources and diagenetic effects.

PubMed

Lucassen, Friedrich; Pritzkow, Wolfgang; Rosner, Martin; Sepúlveda, Fernando; Vásquez, Paulina; Wilke, Hans; Kasemann, Simone A

2017-01-01

Seabird excrements (guano) have been preserved in the arid climate of Northern Chile since at least the Pliocene. The deposits of marine organic material in coastal areas potentially open a window into the present and past composition of the coastal ocean and its food web. We use the stable isotope composition of nitrogen and carbon as well as element contents to compare the principal prey of the birds, the Peruvian anchovy, with the composition of modern guano. We also investigate the impact of diagenetic changes on the isotopic composition and elemental contents of the pure ornithogenic sediments, starting with modern stratified deposits and extending to fossil guano. Where possible, 14C systematics is used for age information. The nitrogen and carbon isotopic composition of the marine prey (Peruvian anchovy) of the birds is complex as it shows strong systematic variations with latitude. The detailed study of a modern profile that represents a few years of guano deposition up to present reveals systematic changes in nitrogen and carbon isotopic composition towards heavier values that increase with age, i.e. depth. Only the uppermost, youngest layers of modern guano show compositional affinity to the prey of the birds. In the profile, the simultaneous loss of nitrogen and carbon occurs by degassing, and non-volatile elements like phosphorous and calcium are passively enriched in the residual guano. Fossil guano deposits are very low in nitrogen and low in carbon contents, and show very heavy nitrogen isotopic compositions. One result of the study is that the use of guano for tracing nitrogen and carbon isotopic and elemental composition in the marine food web of the birds is restricted to fresh material. Despite systematic changes during diagenesis, there is little promise to retrieve reliable values of marine nitrogen and carbon signatures from older guano. However, the changes in isotopic composition from primary marine nitrogen isotopic signatures towards very

What controls diffuse fractures in platform carbonates? Insights from Provence (France) and Apulia (Italy)

NASA Astrophysics Data System (ADS)

Lavenu, Arthur P. C.; Lamarche, Juliette

2018-03-01

Fractures are widespread in rocks and regional opening-mode arrays are commonly ascribed to major tectonic events. However, fractures occur in otherwise undeformed rocks. Some of these are early-developed features independent of tectonics and forming a background network at regional scale. To overcome this lack of understanding, two hydrocarbon reservoir analogues from platform carbonates have been targeted: the Provence (SE France), and the Apulian platform (SE Italy). In both areas, an early fracturing stage has been observed, made of high-angle-to-bedding opening-mode fractures, and bed-parallel stylolites. These features developed synchronously during the first burial stages and prior to major tectonic events. The fracture sets are not genetically related to the present-day layering. Contrarily, fractures developed in a brittle media where facies transitions were not sharp and did not act as mechanical discontinuities. Carbonate facies distribution and early diagenetic imprint constrained the mechanical stratigraphy when fractures occurred. In addition, we observed that fractures related to late tectonic inversion were partly inhibited. Indeed, rock mechanical properties change through time. Characterizing the temporal evolution of carbonate rocks has revealed that diagenesis and sedimentary facies are the prime actors for brittleness and mechanical layering in carbonates.

Genetic research of fractures in carbonate reservoir: a case study of NT carbonate reservoir in the pre-Caspian basin

NASA Astrophysics Data System (ADS)

Fan, Zifei; Wang, Shuqin; Li, Jianxin; Zhao, Wenqi; Sun, Meng; Li, Weiqiang; Li, Changhai

2018-02-01

The degree of development and characteristics of fractures are key factors for the appraisal of carbonate reservoirs. In this paper, core data and well logging data from the NT oilfield in the Pre-Caspian Basin are used to study the formation mechanism and distribution characteristics of different genetic fractures, and analyze their influence on reservoir properties. Fractures in carbonate reservoirs can be divided into three categories according to their formation mechanism; these are tectonic fracture, dissolved fracture, and diagenetic fracture,which is further divided into interlayer fracture and stylolite. Fractures of different formation mechanism influence fluid seepage in different degree, tectonic fractures possessing strong connecting ability to pores, and dissolved fractures also improving reservoir properties effectively, however, diagenetic fractures contributing relatively little to fluid seepage.

Comparison of the diagenetic and reservoir quality evolution between the anticline crest and flank of an Upper Jurassic carbonate gas reservoir, Abu Dhabi, United Arab Emirates

NASA Astrophysics Data System (ADS)

Morad, Daniel; Nader, Fadi H.; Gasparrini, Marta; Morad, Sadoon; Rossi, Carlos; Marchionda, Elisabetta; Al Darmaki, Fatima; Martines, Marco; Hellevang, Helge

2018-05-01

This petrographic, stable isotopic and fluid inclusion microthermometric study of the Upper Jurassic limestones of an onshore field, Abu Dhabi, United Arab Emirates (UAE) compares diagenesis in flanks and crest of the anticline. The results revealed that the diagenetic and related reservoir quality evolution occurred during three phases, including: (i) eogenesis to mesogenesis 1, during which reservoir quality across the field was either deteriorated or preserved by calcite cementation presumably derived from marine or evolved marine pore waters. Improvement of reservoir quality was due to the formation of micropores by micritization of allochems and creation of moldic/intragranular pores by dissolution of peloids and skeletal fragments. (ii) Obduction of Oman ophiolites and formation of the anticline of the studied field was accompanied by cementation by saddle dolomite and blocky calcite. High homogenization temperatures (125-175 °C) and high salinity (19-26 wt% NaCl eq) of the fluid inclusions, negative δ18OVPDB values (-7.7 to -2.9‰), saddle shape of dolomite, and the presence of exotic cements (i.e. fluorite and sphalerite) suggest that these carbonates were formed by flux of hot basinal brines, probably related to this tectonic compression event. (iii) Mesogenesis 2 during subsidence subsequent to the obduction event, which resulted in extensive stylolitization and cementation by calcite. This calcite cement occluded most of the remaining moldic and inter-/intragranular pores of the flank limestones (water zone) whereas porosity was preserved in the crest. This study contributes to: (1) our understanding of differences in the impact of diagenesis on reservoir quality evolution in flanks and crests of anticlines, i.e. impact of hydrocarbon emplacement on diagenesis, and (2) relating various diagenetic processes to burial history and tectonic events of foreland basins in the Arabian Gulf area and elsewhere.

The stable isotope composition of nitrogen and carbon and elemental contents in modern and fossil seabird guano from Northern Chile – Marine sources and diagenetic effects

PubMed Central

Pritzkow, Wolfgang; Rosner, Martin; Sepúlveda, Fernando; Vásquez, Paulina; Wilke, Hans; Kasemann, Simone A.

2017-01-01

Seabird excrements (guano) have been preserved in the arid climate of Northern Chile since at least the Pliocene. The deposits of marine organic material in coastal areas potentially open a window into the present and past composition of the coastal ocean and its food web. We use the stable isotope composition of nitrogen and carbon as well as element contents to compare the principal prey of the birds, the Peruvian anchovy, with the composition of modern guano. We also investigate the impact of diagenetic changes on the isotopic composition and elemental contents of the pure ornithogenic sediments, starting with modern stratified deposits and extending to fossil guano. Where possible, 14C systematics is used for age information. The nitrogen and carbon isotopic composition of the marine prey (Peruvian anchovy) of the birds is complex as it shows strong systematic variations with latitude. The detailed study of a modern profile that represents a few years of guano deposition up to present reveals systematic changes in nitrogen and carbon isotopic composition towards heavier values that increase with age, i.e. depth. Only the uppermost, youngest layers of modern guano show compositional affinity to the prey of the birds. In the profile, the simultaneous loss of nitrogen and carbon occurs by degassing, and non-volatile elements like phosphorous and calcium are passively enriched in the residual guano. Fossil guano deposits are very low in nitrogen and low in carbon contents, and show very heavy nitrogen isotopic compositions. One result of the study is that the use of guano for tracing nitrogen and carbon isotopic and elemental composition in the marine food web of the birds is restricted to fresh material. Despite systematic changes during diagenesis, there is little promise to retrieve reliable values of marine nitrogen and carbon signatures from older guano. However, the changes in isotopic composition from primary marine nitrogen isotopic signatures towards very

Numerical modelling of fluid-rock interactions: Lessons learnt from carbonate rocks diagenesis studies

NASA Astrophysics Data System (ADS)

Nader, Fadi; Bachaud, Pierre; Michel, Anthony

2015-04-01

Quantitative assessment of fluid-rock interactions and their impact on carbonate host-rocks has recently become a very attractive research topic within academic and industrial realms. Today, a common operational workflow that aims at predicting the relevant diagenetic processes on the host rocks (i.e. fluid-rock interactions) consists of three main stages: i) constructing a conceptual diagenesis model including inferred preferential fluids pathways; ii) quantifying the resulted diagenetic phases (e.g. depositing cements, dissolved and recrystallized minerals); and iii) numerical modelling of diagenetic processes. Most of the concepts of diagenetic processes operate at the larger, basin-scale, however, the description of the diagenetic phases (products of such processes) and their association with the overall petrophysical evolution of sedimentary rocks remain at reservoir (and even outcrop/ well core) scale. Conceptual models of diagenetic processes are thereafter constructed based on studying surface-exposed rocks and well cores (e.g. petrography, geochemistry, fluid inclusions). We are able to quantify the diagenetic products with various evolving techniques and on varying scales (e.g. point-counting, 2D and 3D image analysis, XRD, micro-CT and pore network models). Geochemical modelling makes use of thermodynamic and kinetic rules as well as data-bases to simulate chemical reactions and fluid-rock interactions. This can be through a 0D model, whereby a certain process is tested (e.g. the likelihood of a certain chemical reaction to operate under specific conditions). Results relate to the fluids and mineral phases involved in the chemical reactions. They could be used as arguments to support or refute proposed outcomes of fluid-rock interactions. Coupling geochemical modelling with transport (reactive transport model; 1D, 2D and 3D) is another possibility, attractive as it provides forward simulations of diagenetic processes and resulting phases. This

Sedimentological and diagenetic patterns of anhydrite deposits in the Badenian evaporite basin of the Carpathian Foredeep, southern Poland

NASA Astrophysics Data System (ADS)

Kasprzyk, Alicja

2003-05-01

Anhydrite deposits are widely distributed in the Middle Miocene Badenian evaporite basin of Poland, including the marginal sulphate platform and adjacent salt depocenter. Particular sedimentological, petrographic and geochemical characteristics of these anhydrite deposits and especially common pseudomorphic features, inherited from the precursor gypsum deposits, allow the interpretation of the original sedimentary facies. The observed facies distribution and succession (lower and upper members) reveal three distinct facies associations that record a range of depositional environments from nearshore to deeper basinal settings. Platform sulphates were deposited in subaerial and shallow-marine environments (shoreline and inner platform-lagoon system) mainly as autochthonous selenitic gypsum. This was reworked and redistributed into deeper waters (outer platform-lagoon, slope and the proximal basin floor system) to form resedimented facies composed mostly of allochthonous clastic gypsum and minor anhydrite. The general variation in petrographic and geochemical compositions of anhydrite lithofacies of the lower and upper members reflects the brine evolution, as the result of interactions between seawater, meteoric runoff and highly saline, residual pore fluids. The results indicate the importance of synsedimentary and diagenetic anhydritisation processes in formation of the Badenian anhydrite lithofacies, all of which preserve the original depositional features of the former gypsum. This also applies to the basinal anhydrite previously interpreted to have a depositional genesis. Two different genetic patterns of anhydrite have been reinforced by this study: (1) synsedimentary anhydritisation of gypsum deposits by highly concentrated brines or elevated temperatures in surficial to shallow-burial environments (lower member), and (2) successive phases (syndepositional de novo growth, early diagenetic to late diagenetic replacement of former gypsum) of anhydrite formation

Investigating Interactions between the Silica and Carbon Cycles during Precipitation and Early Diagenesis of Authigenic Clay/Carbonate-Mineral Associations in the Carbonate Rock Record

NASA Astrophysics Data System (ADS)

McKenzie, J. A.; Francisca Martinez Ruiz, F.; Sanchez-Roman, M.; Anjos, S.; Bontognali, T. R. R.; Nascimento, G. S.; Vasconcelos, C.

2017-12-01

The study of authigenic clay/carbonate-mineral associations within carbonate sequences has important implications for the interpretation of scientific problems related with rock reservoir properties, such as alteration of potential porosity and permeability. More specifically, when clay minerals are randomly distributed within the carbonate matrix, it becomes difficult to predict reservoir characteristics. In order to understand this mineral association in the geological record, we have undertaken a comparative study of specially designed laboratory experiments with modern environments, where clay minerals have been shown to precipitate together with a range of carbonate minerals, including calcite, Mg-calcite and dolomite. Two modern dolomite-forming environments, the Coorong lakes, South Australia and Brejo do Espinho Rio de Janeiro, Brazil, were selected for this investigation. For comparative evaluation, enrichment microbial culture experiments, using natural pore water from Brejo do Espinho as the growth medium to promote mineral precipitation, were performed under both aerobic and anaerobic conditions. To establish the environmental parameters and biological processes facilitating the dual mineral association, the experimental samples have been compared with the natural minerals using HRTEM measurements. The results demonstrate that the clay and carbonate minerals apparently do not co-precipitate, but the precipitation of the different minerals in the same sample has probably occurred under different environmental conditions with variable chemistries, e.g., hypersalinity versus normal salinity resulting from the changing ratio of evaporation versus precipitation. Thus, the investigated mineral association is not a product of diagenetic processes but of sequential in situ precipitation processes related to changes in the silica and carbon availability. Implications for ancient carbonate formations will be presented and discussed in the context of a specific

Origin of stratiform sediment-hosted manganese carbonate ore deposits: Examples from Molango, Mexico, and TaoJiang, China

USGS Publications Warehouse

Okita, P.M.; Shanks, Wayne C.

1992-01-01

space, suggest they were formed similarly by MnO2 precipitation at the margins of dysaerobic to anoxic marine basins. Mn-carbonate formed predominantly by early-diagenetic reduction of Mn-oxides via oxidation of organic matter in near-surface sediments. In addition to MnCO3 precipitation, organic matter oxidation reactions resulted in oxidation of FeS to Fe-oxides such as magnetite, maghemite and hematite. The latter process explains anomalously low pyrite content and abundant Fe-oxide minerals in ore zones dominated by rhodochrosite. ?? 1992.

Analytical electron microscopy of biogenic and inorganic carbonates

NASA Technical Reports Server (NTRS)

Blake, David F.

1989-01-01

In the terrestrial sedimentary environment, the mineralogically predominant carbonates are calcite-type minerals (rhombohedral carbonates) and aragonite-type minerals (orthorhombic carbonates). Most common minerals precipitating either inorganically or biogenically are high magnesium calcite and aragonite. High magnesium calcite (with magnesium carbonate substituting for more than 7 mole percent of the calcium carbonate) is stable only at temperatures greater than 700 C or thereabouts, and aragonite is stable only at pressures exceeding several kilobars of confining pressure. Therefore, these carbonates are expected to undergo chemical stabilization in the diagenetic environment to ultimately form stable calcite and dolomite. Because of the strong organic control of carbonate deposition in organisms during biomineralization, the microchemistry and microstructure of invertebrate skeletal material is much different than that present in inorganic carbonate cements. The style of preservation of microstructural features in skeletal material is therefore often quite distinctive when compared to that of inorganic carbonate even though wholesale recrystallization of the sediment has taken place. Microstructural and microchemical comparisons are made between high magnesium calcite echinoderm skeletal material and modern inorganic high magnesium calcite inorganic cements, using analytical electron microscopy and related techniques. Similar comparisons are made between analogous materials which have undergone stabilization in the diagenetic environment. Similar analysis schemes may prove useful in distinguishing between biogenic and inorganic carbonates in returned Martian carbonate samples.

Depositional and diagenetic history and petroleum geology of the Jurassic Norphlet Formation of the Alabama coastal waters area and adjacent federal waters area

USGS Publications Warehouse

Kugler, R.L.; Mink, R.M.

1999-01-01

The discovery of deep (>20,000 ft) gas reservoirs in eolian sandstone of the Upper Jurassic Norphlet Formation in Mobile Bay and offshore Alabama in the late 1970s represents one of the most significant hydrocarbon discoveries in the nation during the past several decades. Estimated original proved gas from Norphlet reservoirs in the Alabama coastal waters and adjacent federal waters is 7.462 trillion ft3 (Tcf) (75% recovery factor). Fifteen fields have been established in the offshore Alabama area. Norphlet sediment was deposited in an arid environment in alluvial fans, alluvial plains, and wadis in updip areas. In downdip areas, the Norphlet was deposited in a broad desert plain, with erg development in some areas. Marine transgression, near the end of Norphlet deposition, resulted in reworking of the upper part of the Norphlet Formation. Norphlet reservoir sandstone is arkose and subarkose, consisting of a simple assemblage of three minerals, quartz, albite, and K-feldspar. The present framework grain assemblage of the Norphlet is dominantly diagenetic, owing to albitization and dissolution of feldspar. Despite the simple framework composition, the diagenetic character of the Norphlet is complex. Important authigenic minerals include carbonate phases (calcite, dolomite, Fe-dolomite, and breunnerite), feldspar (albite and K-feldspar), evaporite minerals (anhydrite and halite), clay minerals (illite and chlorite), quartz, and pyrobitumen. The abundance and distribution of these minerals varies significantly between onshore and offshore regions of Norphlet production. The lack of sufficient internal sources of components for authigenic minerals, combined with unusual chemical compositions of chloride (Mg-rich), breunnerite, and some minor authigenic minerals, suggests that Louann-derived fluids influenced Norphlet diagenesis. In offshore Alabama reservoirs, porosity is dominantly modified primary porosity. Preservation of porosity in deep Norphlet reservoirs is due

Geochemical and petrographical characterization of fine-grained carbonate particles along proximal to distal transects

NASA Astrophysics Data System (ADS)

Turpin, Mélanie; Emmanuel, Laurent; Immenhauser, Adrian; Renard, Maurice

2012-12-01

The origin of carbonate ooze particles is often poorly understood. This is due to their polygenic origin and potential post-depositional alteration. Here, the outcome of a physical separation study with regard to different component classes of micritic carbonates is shown. The focus is on grain size and morphology, mineralogy and isotope signatures. Two contrasting proximal-to-distal transects were investigated: (1) the Miocene leeward margin of Great Bahama Bank (ODP Leg 166) and (2) the transition between the Maiella platform and the Umbria-Marche basin in central Italy near the Cenomanian-Turonian boundary. In both case settings, carbonate particles of biogenic origin include at least three groups of organisms: (i) planktonic foraminifera, (ii) calcareous nannofossils and (iii) fragments of unspecified neritic skeletal material. Two further particle types lack diagnostic structures, and based on particle size and mineralogy, are here referred to as (iv) macroparticles (5-20 μm, mainly xenomorphic) and (v) microparticles (< 12 μm, mainly automorphic to sub-automorphic). Macro- and microparticles represent 50 to 80% of the carbonate phase in slope and toe-of-slope domains and share characteristic carbon and oxygen isotope signatures. Macro- and microparticles are considered shallow-water precipitation products subsequently exported into the slope and toe-of-slope domains. Macroparticles are probably related to the fragmentation of neritic skeletal components while microparticles point to inorganic and/or bioinduced precipitation in the water column. In some cases, macro- and microparticles may have an early diagenetic origin. The identification of the origin of fine-grained particles allows for a quantitative assessment of exported, in situ and diagenetic carbonate materials in periplatform environments. The data shown here represent an important step towards a more complete characterization of carbonate ooze and micrite.

High-resolution Campanian-Maastrichtian carbon and oxygen stable isotopes of bulk-rock and skeletal components: palaeoceanographic and palaeoenvironmental implications for the Boreal shelf sea

NASA Astrophysics Data System (ADS)

Wilmsen, Markus; Niebuhr, Birgit

2017-03-01

A high-resolution latest Early Campanian to Early Maastrichtian carbon and oxygen stable isotope record from the northern German Boreal shelf sea based on 537 analyses of co-occurring belemnites, brachiopods, inoceramids, oysters, and bulk rock samples is presented. All samples are precisely related to their stratigraphic, systematic and facies backgrounds and form an integrated, nearly 10-myr-long dataset with considerable palaeoenvironmental and palaeoceanographical implications. Petrographic studies indicate that low-magnesium calcitic coccoliths and calcispheres (i.e., planktic carbonate) predominate the bulk-rock data (marl-limestone rhythmites and chalks), thus representing a sea-surface water signal, and that only minor diagenetic alteration of the carbonate muds took place. Based on TL and CL microscopy, the investigated belemnites are extraordinarily well preserved, which may in part be explained by their early diagenetic surficial silicification (container effect), while the other macroinvertebrate groups are all less well preserved. The (plankton-dominated) δ13C values of the marl-limestone rhythmites and chalks (+1.1 to +2.5 ‰), recording a surface water signal, compare well with the δ18C data of inoceramids while δ13Cbrach. values (+1.5 to +3.0 ‰) are heavier than the bulk rock data. The large variation in the δ13Cbel. (-0.1 to +3.6 ‰) is attributed to isotopic disequilibrium of the biogenic carbonate formed by the belemnite animal. The bulk rock δ18O values show a remarkable low scatter, supporting petrographic observation of only minor diagenetic stabilisation/cementation, and can be approximated with northern German shelf sea-surface temperatures of ca. 20°C for the Late Campanian (ca. -2 ‰ δ18O), being slightly cooler during the Early Maastrichtian. The δ18O values of the belemnite rostra are even less variable and quite rich in heavier 18O (-0.7 to +0.6 with a mean of -0.1 ‰ δ18Obel.) in comparison to bulk rock and other

Molar tooth structures in calcareous nodules, early Neoproterozoic Burovaya Formation, Turukhansk region, Siberia

NASA Astrophysics Data System (ADS)

Pope, Michael C.; Bartley, Julie K.; Knoll, Andrew H.; Petrov, Peter Yu.

2003-05-01

Molar tooth structures are abundant in large (1-2 m diameter) carbonate nodules within fine-grained, subtidal carbonates of the early Neoproterozoic (lower Upper Riphean) Burovaya Formation along the Sukhaya Tunguska River, Turukhansk Uplift, northwestern Siberia. Although molar tooth structures are regionally abundant in this unit, here they occur only within the nodules. Stable isotopic compositions of molar-tooth-filling dolomicrospar cements and of thinly bedded dolomicrite within and surrounding the nodules are indistinguishable from one another. The carbon isotopic compositions (mean δ13C=+2.8‰ PDB±0.4) reflect mean average oceanic surface water composition during their formation; the light oxygen isotopic compositions (mean δ18O=-6.4‰ PDB±2.2) are generally similar to those of other little-altered Meso- to Neoproterozoic limestones and dolostones. These molar tooth structures have no features that would support a tectonic origin; they more likely formed through bacterial processes. Carbonate cement filling of these voids occurred soon after their formation, but the mechanism responsible for this carbonate precipitation is currently uncertain. Local restriction of molar tooth structures to early diagenetic nodules suggests that penecontemporaneous lithification was required for the formation, or at least preservation, of these widespread Mesoproterozoic to Neoproterozoic features.

Impact of diagenetic alteration on sea urchin (Echinodermata) magnesium isotope signatures: Comparison of experimental and fossil data

NASA Astrophysics Data System (ADS)

Riechelmann, Sylvia; Mavromatis, Vasileios; Buhl, Dieter; Dietzel, Martin; Hoffmann, René; Jöns, Niels; Eisenhauer, Anton; Immenhauser, Adrian

2017-04-01

Due to their thermodynamically instable high-Mg calcite mineralogy, the skeletal elements of echinoderms are often regarded as unreliable archives of Phanerozoic marine climate dynamics. Nevertheless, traditional and non-traditional isotope and elemental proxy data from echinoderms have been used to reconstruct global changes in palaeoseawater composition (Sandberg-cycles). Recently, these data and the interpretation have been controversially discussed in context with ancient seawater properties. This paper tests the sensitivity of echinoderm skeletal hardparts, specifically sea urchin spines to diagenetic alteration based on magnesium isotope data. We apply a dual approach by: (i) performing hydrothermal alteration experiments using meteoric, marine, and burial reactive fluids; and (ii) comparing these data with fossil sea urchin hardparts. The degree of alteration of experimentally altered and fossil sea urchin hardparts is assessed by a combination of optical (fluorescence, cathodoluminescence (CL), scanning electron microscopy (SEM)) and geochemical tools (elemental distribution, carbon, oxygen and magnesium isotopes). Although initial fluid chemistry of the experiments did not allow the detection of diagenetic overprint by elemental distribution (Fe, Mn) and cathodoluminescence, other tools such as fluorescence, SEM, delta18O, Mg concentration and delta26Mg display alteration effects, which respond to differential fluid temperature, chemistry, and experiment duration time. At experiments run under meteoric conditions with no Mg in the initial fluid, the solid is enriched in the heavier Mg isotopomer due to preferential dissolution of the lighter isotope. In contrast, initial burial and marine fluids have medium to high Mg concentrations. There, the Mg concentration and the delta26Mg values of the altered sea urchin spines increase. Fossil sea urchin hardparts display partly very strong diagenetic overprint as observed by their elemental distribution

The diagenetic fate of taraxer-14-ene and oleanene isomers

NASA Astrophysics Data System (ADS)

ten Haven, H. L.; Rullkötter, J.

1988-10-01

The extractable organic matter in Holocene to early Miocene deep-sea sediments from Site 645 (ODP Leg 105) in Baffin Bay contains almost exclusively biological markers of terrigenous origin. Pentacyclic triterpenoids of the α-(ursene) and β-amyrin (oleanene) type often occur as the most abundant compounds in the aliphatic hydrocarbon, ketone and alcohol fractions of the sediment extract. A specific diagenetic reaction involves the conversion of taraxer-14-ene into olean-12-ene in the upper 700 metres of the sedimentary sequence. The taraxerene-to-oleanene conversion is complete before the onset of isomerisation of diasterenes at C-20. In the sediment as well as in laboratory simulation experiments, olean-12-ene further isomerises to olean-13(18)-ene and olean-18-ene, the latter of which may be the direct precursor of 18β(H)- and 18α(H)-oleanane found in sediments containing more mature organic matter and in crude oils. The subsurface interconversion of these triterpenoid skeletons indicate that oleanane does not necessarily start life as an oleanoid.

Community replacement instead of drowning: Evolution of proto-North Atlantic carbonate-platform production in the run-up to of the Early Aptian OAE1a

NASA Astrophysics Data System (ADS)

Huck, Stefan; Stein, Melody; Adatte, Thierry; Föllmi, Karl B.; Immenhauser, Adrian; Heimhofer, Ulrich

2014-05-01

In the proto-North Atlantic realm (Lusitanian Basin, Portugal), carbonate platform production witnessed a major biotic turnover during the Early Aptian. Here, Urgonian-type rudist-nerinid dominated limestones were replaced by an orbitolinid-rich, oyster and serpulid-bearing marly facies. Integrated biostratigraphic-chemostratigraphic studies (Burla et al., 2008; Huck et al., 2012) provided evidence that this change coincides with the Early Aptian carbonate platform drowning episode in the run-up of oceanic anoxic event (OAE) 1a (transition D. forbesi to D. deshayesi ammonite zones), which has been recorded, from many localities in the Tethyan Ocean (Godet, 2013). Unlike Helvetic and Arabian carbonate platforms, which are characterised by a punctuated mass occurrence of orbitolinids marking the onset of the Aptian (Rawil and Hawar members, respectively), orbitolinids are an abundant constituent of the proto-North Atlantic carbonate platform community from the Late Barremian onwards. Orbitolinid-rich packstones and marls showing mass-occurrences of orbitolinids indicate repeated short-term installation of specific environmental conditions (eutrophication and/or deepening). In order to critically assess the influence of regional palaeoenvironmental against global palaeoclimatic and palaeoceanographic changes on the Proto-North Atlantic carbonate platform evolution, several outcrop successions in the Lusitanian Basin covering the critical interval have been investigated in detail with regard to facies and petrographic characteristics and geochemical (C-/O-isotopes, P content, bulk-rock and clay mineralogy,) inventory. The aims of the present study are three-fold: (1) to characterise proto-North Atlantic Lower Aptian shallow-water carbonates with respect to diagenetic history, microfacies, and distribution of fossils useful for the analysis of palaeoenvironments (corals, rudists and orbitolinids); (2) to evaluate the influence of sea-level and humidity changes

Compaction bands in high temperature/pressure diagenetically altered unconventional shale gas reservoirs

NASA Astrophysics Data System (ADS)

Regenauer-Lieb, K.; Veveakis, M.; Poulet, T.

2014-12-01

Unconventional energy and mineral resources are typically trapped in a low porosity/permeability environment and are difficult to produce. An extreme end-member is the shale gas reservoir in the Cooper Basin (Australia) that is located at 3500-4000 m depth and ambient temperature conditions around 200oC. Shales of lacustrine origin (with high clay content) are diagenetically altered. Diagenesis involves fluid release mineral reactions of the general type Asolid ↔ Bsolid +Cfluid and switches on suddenly in the diagenetic window between 100-200oC. Diagenetic reactions can involve concentrations of smectite, aqueous silica compound, illite, potassium ions, aqueous silica, quartz, feldspar, kerogen, water and gas . In classical petroleum engineering such interlayer water/gas release reactions are considered to cause cementation and significantly reduce porosity and permeability. Yet in contradiction to the expected permeability reduction gas is successfully being produced. We propose that the success is based on the ductile equivalent of classical compaction bands in solid mechanics. The difference being that that the rate of the volumetric compaction is controlled by the diagenetic reactions. Ductile compaction bands are forming high porosity fluid channels rather than low porosity crushed grains in the solid mechanical equivalent. We show that this new type of volumetric instability appears in rate-dependent heterogenous materials as Cnoidal waves. These are nonlinear and exact periodic stationary waves, well known in the shallow water theory of fluid mechanics. Their distance is a direct function of the hydromechanical diffusivities. These instabilities only emerge in low permeability environment where the fluid diffusivity is about an order of magnitude lower than the mechanical loading. The instabilities are expected to be of the type as shown in the image below. The image shows a CT-scan of a laboratory experiment kindly provided by Papamichos (pers

Silicification of trace fossils in carbonates; evidence from Permian Kaibab Formation, southwestern Utah

DOE Office of Scientific and Technical Information (OSTI.GOV)

Whidden, K.J.; Bottjer, D.J.

Silicification in carbonates, particularly silicified trace fossils, has received relatively little previous study. Chert comprises a significant percentage of the upper Fossil Mountain Member of the Kaibab Formation, a Permian epicontinental limestone. Distribution and origin of this chert were studied from outcrops in southwestern Utah. The origin of much of this chert is believed to be as silicified Thalassinoides burrows. Field evidence for trace fossil silicification includes (1) silicified cylindrical tubes with Y-shaped branching patterns as well as hollow tubes, and (2) polygonal box-work patterns of tubes. In addition, brachiopods, bryozoans, and abundant specimens of the sponge Actinocelia maendrina Finksmore » are also silicified. Recognition of silicified trace fossils in carbonates provides a different approach to the study of early diagenetic silica precipitation. These silicified trace fossils also represent new information on bioturbation in ancient carbonates, a subject that has, until recently, been relatively unstudied.« less

3D modeling of carbonates petro-acoustic heterogeneities

NASA Astrophysics Data System (ADS)

Baden, Dawin; Guglielmi, Yves; Saracco, Ginette; Marié, Lionel; Viseur, Sophie

2015-04-01

Characterizing carbonate reservoirs heterogeneity is a challenging issue for Oil & Gas Industry, CO2 sequestration and all kinds of fluid manipulations in natural reservoirs, due to the significant impact of heterogeneities on fluid flow and storage within the reservoir. Although large scale (> meter) heterogeneities such as layers petrophysical contrasts are well addressed by computing facies-based models, low scale (< meter) heterogeneities are often poorly constrained because of the complexity in predicting their spatial arrangement. In this study, we conducted petro-acoustic measurements on cores of different size and diameter (Ø = 1", 1.5" and 5") in order to evaluate anisotropy or heterogeneity in carbonates at different laboratory scales. Different types of heterogeneities which generally occur in carbonate reservoir units (e.g. petrographic, diagenetic, and tectonic related) were sampled. Dry / wet samples were investigated with different ultrasonic apparatus and using different sensors allowing acoustic characterization through a bandwidth varying from 50 to 500 kHz. Comprehensive measurements realized on each samples allowed statistical analyses of petro-acoustic properties such as attenuation, shear and longitudinal wave velocity. The cores properties (geological and acoustic facies) were modeled in 3D using photogrammetry and GOCAD geo-modeler. This method successfully allowed detecting and imaging in three dimensions differential diagenesis effects characterized by the occurrence of decimeter-scale diagenetic horizons in samples assumed to be homogeneous and/or different diagenetic sequences between shells filling and the packing matrix. We then discuss how small interfaces such as cracks, stylolithes and laminations which are also imaged may have guided these differential effects, considering that understanding the processes may be taken as an analogue to actual fluid drainage complexity in deep carbonate reservoir.

Detection of diagenetic processes in bones: the case of Arkoudospilia cave, N. Greece

NASA Astrophysics Data System (ADS)

Zisi, Nikoleta; Dotsika, Elissavet; Tsoukala, Evangelia; Psomiadis, David

2010-05-01

Diagenesis of bone material over geological time is a highly complex phenomenon involving the physical, chemical, histological and mechanical alterations that occur at different time scales from the time of death to present and depend on the local geochemical conditions. The significance of diagenesis and the information that can provide its decoding, led to its study by a variety of physicochemical techniques. Despite serious research efforts, a detailed scenario of bone diagenesis remains elusive. The δ18O of the carbonate material of hydroxyapatite of the bones is though to be a good indicator of the δ18O of the local water precipitation and therefore can be used for palaeoclimatic reconstraction, while δ13C is used for definition of palaeodiet habits. The study of isotopic composition requires the detection of the diagenetic degree, because both δ18O and δ13C can be contaminated by these processes. Stable carbon and oxygen isotope values (δ13C, δ18O) were obtained for structural carbonate in the hydroxy-apatite of bear bones from Arkoudospilia Cave, Pella, N. Greece. The age range of the fossil layers is from 32ka BP to a maximum of 38ka BP (radiocarbon dating). The findings belong to Ursus ingressus, an extinct cave bear. The difficulty in studying an extinct species lies to the fact that it cannot be easily correlated with a present one, so it is impossible to determine the diagenesis by the analytical deviation. However, in order to include the environmental and climatic differences of the past and modern bear habitats, the isotopic composition of the water should be also included in the study. Cave bears are considered to be endemic in Europe. The shortage of data in literature concerning cave bears isotopic analyses in combination with the burden of the difficulties in spotting and sampling such rare materials makes difficult to compare the results of a study. The diet and the physiology of this species are not well known. However the morphology of

Relationship between karstification and burial dolomitization in Permian platform carbonates (Lower Khuff - Oman)

NASA Astrophysics Data System (ADS)

Beckert, Julia; Vandeginste, Veerle; John, Cédric M.

2016-08-01

Large breccia fabrics associated with karst constitute an important structure in massive limestone successions. The dimensions and shapes of breccia structures are controlled by the initial fracture pattern of the limestone and preferential pathways of the karstifying fluids, but subsequently breccia fabrics can also govern the migration of later fluids. Therefore, breccias are highly relevant features to capture for reservoir characterisation. Outcrop analogues for Lower Khuff units in the Middle East present in the Central Oman Mountains reveal brecciated fabrics up to 10s of metres in diameter. These brecciated units are closely associated with dolomite bodies of late diagenetic origin. Based on an integrated set of data, the breccias are interpreted as collapsed karst cavities either formed by meteoric or hypogenic fluids. The exact origin of the fluids could not be constrained due to an overprint by later dolomitizing fluids. Based on the composition of the clasts and matrix in the breccias, two dolomitization events are interpreted to have affected the succession, one prior to (early diagenetic [ED] dolomite) and one after brecciation (late diagenetic [DT2] dolomite). Dolomite of shallow burial origin (ED dolomite) was only observed as clasts within breccia and is much more frequent than late diagenetic (medium to deep burial) dolomite clasts. Thus, the timing of the brecciation and collapse is assumed to postdate shallow burial early diagenetic dolomitization. Late diagenetic replacive dolomite (DT2 dolomite) forms 90% of the matrix in the breccia fabrics with the exception of a small area that was not affected by dolomitization, but is rarely present as clasts. Stable isotope measurements [δ18O: - 2.5‰ to - 6‰ VPDB and δ13C: 2.9‰ to 4.8‰ VPDB] suggest a burial origin for the late diagenetic dolomite potentially with the participation of hydrothermal fluids. The dolomitized matrix indicates a migration of late dolomitizing fluids subsequent to or

Diagenetic controls on reservoir heterogeneity in St. Peter Sandstone, deep Michigan basin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barnes, D.A.; Turmelle, T.M.; Adam, R.

1989-03-01

The St. Peter Sandstone is a highly productive gas and condensate reservoir throughout the central part of the Michigan basin. Production occurs in several intervals: a laterally continuous zone at the top of the formation typified in the Woodville, Falmouth, and Rose City fields and less continuous intervals lower in the formation typified in the Ruwe Gulf zone of the Reed City field. Porosity is not limited to hydrocarbon productive zones, however. Diagenesis has dramatically modified primary mineralogy and textures in the formation. Dominant diagenetic components are quartz, dolomite, and clay authigenic cements, extensive chemical compaction, and pervasive mineral leaching.more » Their model for sandstone diagenesis is consistent throughout the basin. Variation in the significance of these diagenetic components is strongly templated by stratigraphically predictable facies variations within the St. Peter Sandstone.« less

dSED: A database tool for modeling sediment early diagenesis

NASA Astrophysics Data System (ADS)

Katsev, S.; Rancourt, D. G.; L'Heureux, I.

2003-04-01

Sediment early diagenesis reaction transport models (RTMs) are becoming powerful tools in providing kinetic descriptions of the metal and nutrient diagenetic cycling in marine, lacustrine, estuarine, and other aquatic sediments, as well as of exchanges with the water column. Whereas there exist several good database/program combinations for thermodynamic equilibrium calculations in aqueous systems, at present there exist no database tools for classification and analysis of the kinetic data essential to RTM development. We present a database tool that is intended to serve as an online resource for information about chemical reactions, solid phase and solute reactants, sorption reactions, transport mechanisms, and kinetic and equilibrium parameters that are relevant to sediment diagenesis processes. The list of reactive substances includes but is not limited to organic matter, Fe and Mn oxides and oxyhydroxides, sulfides and sulfates, calcium, iron, and manganese carbonates, phosphorus-bearing minerals, and silicates. Aqueous phases include dissolved carbon dioxide, oxygen, methane, hydrogen sulfide, sulfate, nitrate, phosphate, some organic compounds, and dissolved metal species. A number of filters allow extracting information according to user-specified criteria, e.g., about a class of substances contributing to the cycling of iron. The database also includes bibliographic information about published diagenetic models and the reactions and processes that they consider. At the time of preparing this abstract, dSED contained 128 reactions and 12 pre-defined filters. dSED is maintained by the Lake Sediment Structure and Evolution (LSSE) group at the University of Ottawa (www.science.uottawa.ca/LSSE/dSED) and we invite input from the geochemical community.

3D climate-carbon modelling of the early Earth

NASA Astrophysics Data System (ADS)

Charnay, B.; Le Hir, G.; Fluteau, F.; Forget, F.; Catling, D.

2017-09-01

We revisit the climate and carbon cycle of the early Earth at 3.8 Ga using a 3D climate-carbon model. Our resultsfavor cold or temperate climates with global mean temperatures between around 8°C (281 K) and 30°C (303 K) and with 0.1-0.36 bar of CO2 for the late Hadean and early Archean.

Diagenesis of lower Cretaceous pelagic carbonates, North Atlantic: Paleoceanographic signals obscured

USGS Publications Warehouse

Frank, T.D.; Arthur, M.A.; Dean, W.E.

1999-01-01

The stable isotope and minor element geochemistry of Neocomian (Lower Cretaceous) pelagic carbonates of the North Atlantic Basin (Deep Sea Drilling Project Sites 105, 367, 387, 391, and 603) was examined to develop a diagenetic model for pelagic limestones. In particular, we hoped to test the fidelity of whole-rock geochemical records as paleoceanographic indicators for pelagic deposits of pre-Aptian age, in which individual microfossils are not available for analysis. Data indicate that in addition to depth of burial, rhythmic variations in primary carbonate content have strongly controlled diagenetic patterns and associated geochemical signatures in these Neocomian sequences. Samples become increasingly depleted in Sr and 18O with increasing CaCO3 content. Within individual sedimentary sections, substantial decreases in Sr/Ca ratios and ??18O values are evident over a range of 4 to 98% CaCO3. However, even over a relatively narrow range of 50 to 98% CaCO3 a 2.5%c variation in ??18O values and a change of a factor of 1.7 in Sr/Ca ratios are observed. Carbon isotope compositions do not vary as extensively with CaCO3 content, but carbonate-rich intervals tend to be relatively depleted in 13C. Petrographic analysis reveals that these geochemical patterns are related to the transfer of CaCO3 from carbonate-poor intervals (calcareous shales and marlstones) to adjacent carbonate-rich intervals (limestones) during burial compaction and pressure solution. This process results in the addition of diagenetic cement to carbonate-rich intervals to produce a bulk composition that is relatively depleted in Sr and 18O and, at the same time, enables the retention of more-or-less primary carbonate that is relatively enriched in Sr and 18O in adjacent carbonate-poor intervals. Thus, although cyclic variations in CaCO3 content are primary in the Neocomian sequences examined, measured variations in Sr/Ca ratios and ??18O values are not and, as such, do not provide reliable proxies for

Bacterially mediated diagenetic origin for chert-hosted manganese deposits in the Franciscan Complex, California Coast Ranges

NASA Astrophysics Data System (ADS)

Hein, James R.; Koski, Randolph A.

1987-08-01

Numerous manganese deposits in the Franciscan Complex, California, occur as conformable lenses within bedded radiolarian chert-argillite sequences that are, in turn, intercalated within thicker sections of sandstone and shale. The field relations, composition, and petro-graphic and isotopic characteristics indicate that the manganese was concentrated by diagenetic reconstitution of siliceous and hemipelagic sediment during burial. The ore lenses are Mn-rich and Fe-poor assemblages consisting largely of rhodochrosite, manganese silicates, opal-CT (disordered cristobalite-tridymite), and quartz. Highly negative δ13C values for the carbonate carbon in rhodochrosite indicate that CO2 likely originated from oxidation of methane; less negative values result from mixing of methanogenic carbon and CO2 derived from bacterial degradation of organic matter. The δ18O values for the carbonate of rhodochrosite indicate temperatures of formation between 12 and 100 °C. The oxidation of methane prior to carbonate precipitation may have used the minor (0.4% 0.5%) Mn and Fe oxyhydroxides and oxides deposited with the sediment. The mobilization of manganese from biogenic and terrigenous sources in the sediment column into discrete horizons and the fractioriation of manganese from iron reflect the presence of oxidation-reduction boundaries and gradients in the sediment column. Fluids derived from compaction and silica-dehydration reactions in the transformation of opal-A (X-ray amorphous biogenic silica) to quartz were involved in transportation of principal components. Sedimentary and geochemical attributes suggest that the deposits formed in a deep-water environment in a zone of oceanic upwelling near a continental margin.

Carbonate concretions as a significant component of ancient marine carbon cycles: Insights from paired organic and inorganic carbon isotope analyses of a Cretaceous shale

NASA Astrophysics Data System (ADS)

Loyd, S. J.

2014-12-01

Carbonate concretions often occur within fine-grained, organic-rich sedimentary rocks. This association reflects the common production of diagenetic minerals through biologic cycling of organic matter. Chemical analysis of carbonate concretions provides the rare opportunity to explore ancient shallow diagenetic environments, which are inherently transient due to progressive burial but are an integral component of the marine carbon cycle. The late Cretaceous Holz Shale (~80 Ma) contains abundant calcite concretions that exhibit textural and geochemical characteristics indicative of relatively shallow formation (i.e., near the sediment-water interface). Sampled concretions contain between 5.4 and 9.8 wt.% total inorganic carbon (TIC), or ~45 and 82 wt.% CaCO3, compared to host shale values which average ~1.5 wt.% TIC. Organic carbon isotope compositions (δ13Corg) are relatively constant in host and concretion samples ranging from ­-26.3 to -24.0‰ (VPDB). Carbonate carbon isotope compositions (δ13Ccarb) range from -22.5 to -3.4‰, indicating a significant but not entirely organic source of carbon. Concretions of the lower Holz Shale exhibit considerably elevated δ13Ccarb values averaging -4.8‰, whereas upper Holz Shale concretions express an average δ13Ccarb value of -17.0‰. If the remaining carbonate for lower Holz Shale concretions is sourced from marine fluids and/or dissolved marine carbonate minerals (e.g., shells), a simple mass balance indicates that ~28% of concretion carbon was sourced from organic matter and ~72% from late Cretaceous marine inorganic carbon (with δ13C ~ +2.5‰). Upper Holz Shale calculations indicate a ~73% contribution from organic matter and a ~27% contribution from inorganic carbon. When normalized for carbonate, organic contents within the concretions are ~2-13 wt.% enriched compared to host contents. This potentially reflects the protective nature of cementation that acts to limit permeability and chemical destruction of

Perspectives on geochemical proxies: The impact of model and parameter selection on the quantification of carbonate recrystallization rates

NASA Astrophysics Data System (ADS)

Huber, Christian; Druhan, Jennifer L.; Fantle, Matthew S.

2017-11-01

Diagenetic reactions in marine sediments, such as the recrystallization of carbonates, can impact the accuracy of paleo-environmental and paleo-climatic reconstructions by geochemical proxies. The extent to which the recrystallization of carbonates affects the chemistry of sedimentary archives depends on the reaction rate, extent of isotopic disequilibrium, and duration of reaction. The reaction rate, which is obviously critical, can be constrained by the elemental and isotopic compositions of pore fluids. Such constraints are affected by assumptions regarding the temperature in the sedimentary column relative to the temperature of formation, the burial rate, pore fluid advection, the composition of the sediments (carbonate-rich versus siliciclastic), and the porosity of the sediment column. In this study, we use a steady-state analytical solution to the diagenetic equations to constrain depth-dependent reaction rates (and extents of recrystallization) based on the Ca isotopic compositions of pore fluids in sedimentary columns at multiple ocean drilling sites (Sites 807, 984, 1170, and 1171), which encompass a diverse range of sedimentary compositions and conditions. We find that carbonates in siliciclastic sediments are generally less altered by diagenesis than their carbonate-rich counterparts. The discrepancy in recrystallization rates between siliciclastic and carbonate-rich sedimentary sections is, however, significantly smaller than previously estimated, suggesting that siliciclastic archives are not immune to diagenetic effects. While we find that diagenesis can decouple contemporaneous proxies of sea surface temperature (Mg/Ca and δ18O), our calculations also reveal that δ18O-based temperature estimates are more robust in siliciclastic sections relative to carbonate-rich sections. Sensitivity tests of the calculated extent of recrystallization suggest that uncertainties in porosity and burial rate are generally the greatest sources of error to proxy

Early atmospheric detection of carbon dioxide from carbon capture and storage sites

PubMed Central

Pak, Nasrin Mostafavi; Rempillo, Ofelia; Norman, Ann-Lise; Layzell, David B.

2016-01-01

ABSTRACT The early atmospheric detection of carbon dioxide (CO2) leaks from carbon capture and storage (CCS) sites is important both to inform remediation efforts and to build and maintain public support for CCS in mitigating greenhouse gas emissions. A gas analysis system was developed to assess the origin of plumes of air enriched in CO2, as to whether CO2 is from a CCS site or from the oxidation of carbon compounds. The system measured CO2 and O2 concentrations for different plume samples relative to background air and calculated the gas differential concentration ratio (GDCR = −ΔO2/ΔCO2). The experimental results were in good agreement with theoretical calculations that placed GDCR values for a CO2 leak at 0.21, compared with GDCR values of 1–1.8 for the combustion of carbon compounds. Although some combustion plume samples deviated in GDCR from theoretical, the very low GDCR values associated with plumes from CO2 leaks provided confidence that this technology holds promise in providing a tool for the early detection of CO2 leaks from CCS sites.  Implications: This work contributes to the development of a cost-effective technology for the early detection of leaks from sites where CO2 has been injected into the subsurface to enhance oil recovery or to permanently store the gas as a strategy for mitigating climate change. Such technology will be important in building public confidence regarding the safety and security of carbon capture and storage sites. PMID:27111469

Early atmospheric detection of carbon dioxide from carbon capture and storage sites.

PubMed

Pak, Nasrin Mostafavi; Rempillo, Ofelia; Norman, Ann-Lise; Layzell, David B

2016-08-01

The early atmospheric detection of carbon dioxide (CO2) leaks from carbon capture and storage (CCS) sites is important both to inform remediation efforts and to build and maintain public support for CCS in mitigating greenhouse gas emissions. A gas analysis system was developed to assess the origin of plumes of air enriched in CO2, as to whether CO2 is from a CCS site or from the oxidation of carbon compounds. The system measured CO2 and O2 concentrations for different plume samples relative to background air and calculated the gas differential concentration ratio (GDCR = -ΔO2/ΔCO2). The experimental results were in good agreement with theoretical calculations that placed GDCR values for a CO2 leak at 0.21, compared with GDCR values of 1-1.8 for the combustion of carbon compounds. Although some combustion plume samples deviated in GDCR from theoretical, the very low GDCR values associated with plumes from CO2 leaks provided confidence that this technology holds promise in providing a tool for the early detection of CO2 leaks from CCS sites. This work contributes to the development of a cost-effective technology for the early detection of leaks from sites where CO2 has been injected into the subsurface to enhance oil recovery or to permanently store the gas as a strategy for mitigating climate change. Such technology will be important in building public confidence regarding the safety and security of carbon capture and storage sites.

Rare earth elements in Japan Sea sediments and diagenetic behavior of Ce/Ce∗: results from ODP Leg 127

USGS Publications Warehouse

Murray, R.; Buchholtz ten Brink, Marilyn R.; Brumsack, Hans-Juergen; Gerlach, David C.; Russ III, G. Price

1991-01-01

Ce/Ce* profiles at all three sites increase monotonically with depth, and record progressive diagenetic LREE fractionation. The observed Ce/Ce* record does not respond to changes in oxygenation state of the overlying water, and Ce/Ce* correlated slightly better with depth than with age. The downhole increase in Ce/Ce* at Site 794 and Site 797 is a passive response to diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and L(ln/Ybnsuggests that other processes are occurring which mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column, and that an additional ~38% is recycled at or near the seafloor (data from Masuzawa and Koyama, 1989). Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce* is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply-buried interstitial waters.

Chemistry of diagenetically altered tuffs at a potential nuclear waste repository, Yucca Mountain, Nye County, Nevada

DOE Office of Scientific and Technical Information (OSTI.GOV)

Broxton, D.E.; Warren, R.G.; Hagan, R.C.

1986-10-01

The chemistry of diagenetically altered tuffs at a potential nuclear waste repository, Yucca Mountain, Nevada is described. These tuffs contain substantial amounts of zeolites that are highly sorptive of certain radionuclides. Because of their widespread distribution, the zeolitic tuffs could provide important barriers to radionuclide migration. Physical properties of these tuffs and of their constituent zeolites are influenced by their chemical compositions. This study defines the amount of chemical variability within diagenetically altered tuffs and within diagenetic minerals at Yucca Mountain. Zeolitic tuffs at Yucca Mountain formed by diagenetic alteration of rhyolitic vitric tuffs. Despite their similar starting compositions, thesemore » tuffs developed compositions that vary both vertically and laterally. Widespread chemical variations were the result of open-system chemical diagenesis in which chemical components of the tuffs were mobilized and redistributed by groundwaters. Alkalies, alkaline earths, and silica were the most mobile elements during diagenesis. The zeolitic tuffs can be divided into three compositional groups: (1) calcium- and magnesium-rich tuffs associated with relatively thin zones of alteration in the unsaturated zone; (2) tuffs in thick zones of alteration at and below the water table that grade laterally from sodic compositions on the western side of Yucca Mountain to calcic compositions on the eastern side; and (3) potassic tuffs at the north end of Yucca Mountain. Physical properties of tuffs and their consistuent zeolites at Yucca Mountain may be affected by variations in compositions. Properties important for assessment of repository performance include behavior and ion exchange.« less

Isotope and elemental geochemistry of Cretaceous fossiliferous concretions (Santana Formation, Brazil)

NASA Astrophysics Data System (ADS)

Heimhofer, Ulrich; Meister, Patrick; Bernasconi, Stefano M.; Ariztegui, Daniel; Martill, David M.; Schwark, Lorenz

2014-05-01

Exceptional three-dimensional fossil preservation (incl. phosphatization of soft-tissues) within organic carbon-rich mudstones is often associated with the formation of a protective carbonate shell surrounding the fossil specimen. Examples for this type of preservation are the Early Cretaceous fishes, turtles and pterosaurs from the Brazilian Santana Formation. Numerous studies proposed different conceptual models for concretion formation. Having new state-of-the-art geochemical tools at hand we revisited these models for the Santana Formation as an exemplary case. Differential compaction clearly indicates early precipitation of micritic calcite surrounding a central cavity containing the still decomposing fossil. The presence of pyrite forming a circular rim around the fossil and carbonate with negative carbon isotope compositions suggest intense sulphate reduction whereby the production of ammonium from the decay of proteins led to an increased alkalinity, which induced early carbonate precipitation. By means of micro-XRF scanning we found that pyrite is absent from the interior part of the concretions and that total iron content is very low, which indicate absence of sulphate reduction at the center of the concretions and possibly local onset of methanogenesis. We postulate that the central cavity may even have been filled with methane gas that evolved from the decaying animal. Methane diffusing outward was anaerobically oxidized in the surrounding sulphate reduction zone. Carbonate clumped isotopes revealed that micritic calcite formed early, but that these early precipitates are overprinted by two different late diagenetic cements precipitated at elevated temperatures. The occurrence of an outermost "cone-in-cone" calcite rim can be associated with burial showing temperatures of up to 60°C. Strontium-isotope ratios of matrix calcite and cement phases show radiogenic values (0.710416 to 0.712465), which are significantly higher than typical marine Cretaceous

Bacterial and Thermochemical Sulfate Reduction in Diagenetic Settings - Old and New Insights

NASA Astrophysics Data System (ADS)

Machel, H.

2006-12-01

The association of dissolved sulfate and hydrocarbons is thermodynamically unstable in virtually all diagenetic environments. Hence, redox-reactions occur, whereby sulfate is reduced by hydrocarbons either bacterially (bacterial sulfate reduction = BSR) or inorganically (thermochemical sulfate reduction = TSR). Based on empirical evidence, BSR and TSR occur in two mutually exclusive thermal regimes, i.e., low-T and high-T diagenetic environments, respectively. BSR is common in diagenetic settings at T = 0 - 80 ° C. Above this T range, almost all sulfate reducers cease to metabolize. Those few types of hyperthermophiles that can form H2S at higher T appear to be very rare and do not normally occur and/or metabolize in geologic settings that are otherwise conducive to BSR. TSR appears to be common in geologic settings at T = 100 - 140 ° C, but in some settings T up to 180 ° C appears to be necessary. TSR does not have a sharply defined, generally valid minimum T because the onset and rate of TSR are governed by several factors that vary from place to place, i.e., the composition of the available organic reactants, kinetic inhibitors and/or catalysts, anhydrite dissolution rates, wettability, as well as migration and diffusion rates of the major reactants. A well- defined, specific minimum T for TSR can be expected only where the reservoir conditions are fairly homogeneous on the scale of a field or a play. BSR is geologically instantaneous in most geologic settings. Rates of TSR are much lower, but still geologically significant. TSR may form sour gas reservoirs and/or MVT deposits in several tens of thousands to a few million years at T = 100 - 140 ° C. BSR and TSR may be exothermic or endothermic, depending mainly on the presence or absence of specific organic reactants. The main organic reactants for BSR are organic acids and other products of aerobic or fermentative biodegradation, and those for TSR are branched and n-alkanes, followed by cyclic and mono

Stratigraphic correlations in mid- to late-Proterozoic carbonates of the Democratic Republic of Congo using magnetic susceptibility

NASA Astrophysics Data System (ADS)

Delpomdor, Franck R. A.; Devleeschouwer, Xavier; Spassov, Simo; Préat, Alain R.

2017-04-01

In this paper, we have tested the application of magnetic susceptibility measurements in Cu-Ag-Zn-Pb-(Fe)-mineralized carbonates of the BIe subgroup (Democratic Republic of Congo) as an efficient tool for regional and global high-resolution stratigraphic correlations in the Neoproterozoic marine carbonates. To achieve this goal, we integrate the low-field magnetic susceptibility (XLF) data with facies analyses, geochemistry and isotope stratigraphy. The microfacies analyses of two cores, Tshinyama#S70 and Kafuku#15, drilled in the early Neoproterozoic carbonates of the Mbuji-Mayi Supergroup reveal a deep carbonate ramp setting associated with a microbial/stromatolitic mid-ramp environment. High-resolution stratigraphic correlations using magnetic susceptibility and C-isotope curves established for both cores, 190 km apart, suggest a sedimentary hiatus at the base of the Tshinyama#S70 succession. C-O and Sr isotopes and Sr/Ca and Fe abundances show that a diagenetic meteoric overprint affected the series of the Tshinyama#S70 core and a thermal effect related to mineralizing fluids affected the Kafuku#15 core carbonates.

Carbonate replacement of lacustrine gypsum deposits in two Neogene continental basins, eastern Spain

NASA Astrophysics Data System (ADS)

Anadón, P.; Rosell, L.; Talbot, M. R.

1992-07-01

Bedded nonmarine gypsum deposits in the Miocene Teruel and Cabriel basins, eastern Spain, are partly replaced by carbonate. The Libros gypsum (Teruel Graben) is associated with fossiliferous carbonate wackestones and finely laminated, organic matter-rich mudstones which accumulated under anoxic conditions in a meromictic, permanent lake. The gypsum is locally pseudomorphed by aragonite or, less commonly, replaced by calcite. Low δ 13C values indicate that sulphate replacement resulted from bacterial sulphate reduction processes that were favoured by anacrobic conditions and abundant labile organic matter in the sediments. Petrographic evidence and oxygen isotopic composition suggest that gypsum replacement by aragonite occurred soon after deposition. A subsequent return to oxidising conditions caused some aragonite to be replaced by diagenetic gypsum. Native sulphur is associated with some of these secondary gypsum occurrences. The Los Ruices sulphate deposits (Cabriel Basin) contain beds of clastic and selenitic gypsum which are associated with limestones and red beds indicating accumulation in a shallow lake. Calcite is the principal replacement mineral. Bacterial sulphate reduction was insignificant in this basin because of a scarcity of organic matter. Stable isotope composition of diagenetic carbonate indicates that gypsum replacement occurred at shallow burial depths due to contact with dilute groundwaters of meteoric origin. Depositional environment evidently has a major influence upon the diagenetic history of primary sulphate deposits. The quantity of preserved organic matter degradable by sulphate-reducing bacteria is of particular importance and, along with groundwater composition, is the main factor controlling the mechanism of gypsum replacement by carbonate.

Factors influencing the biogeochemistry of sedimentary carbon and phosphorus in the Sacramento-San Joaquin Delta

USGS Publications Warehouse

Nilsen, E.B.; Delaney, M.L.

2005-01-01

This study characterizes organic carbon (Corganic) and phosphorus (P) geochemistry in surface sediments of the Sacramento-San Joaquin Delta, California. Sediment cores were collected from five sites on a sample transect from the edge of the San Francisco Bay eastward to the freshwater Consumnes River. The top 8 cm of each core were analyzed (in 1-cm intervals) for Corganic, four P fractions, and redox-sensitive trace metals (uranium and manganese). Sedimentary Corganic concentrations and Corganic:P ratios decreased, while reactive P concentrations increased moving inland in the Delta. The fraction of total P represented by organic P increased inland, while that of authigenic P was higher bayward than inland reflecting increased diagenetic alteration of organic matter toward the bayward end of the transect. The redox indicator metals are consistent with decreasing sedimentary suboxia inland. The distribution of P fractions and C:P ratios reflect the presence of relatively labile organic matter in upstream surface sediments. Sediment C and P geochemistry is influenced by site-specific particulate organic matter sources, the sorptive power of the sedimentary material present, physical forcing, and early diagenetic transformations presumably driven by Corganic oxidation. ?? 2005 Estuarine Research Federation.

Carbon cycle perturbations recorded by δ13C of bulk organic matter: the Carnian Pluvial Event in the Dolomites, northern Italy

NASA Astrophysics Data System (ADS)

Preto, Nereo; Breda, Anna; Dal Corso, Jacopo; Rigo, Manuel; Roghi, Guido; Spötl, Christoph

2015-04-01

A period of increased rainfall occurred in the Carnian (Late Triassic), known as Carnian Pluvial Event (CPE), which is evidenced by major lithological changes in continental and marine successions at tropical latitudes. Increased continental weathering and erosion led to the supply of large amounts of siliciclastics into the marginal basins of the Tethys. Seawater anoxia is also observed locally in semi-restricted basins. Simultaneously, microbial factories on high-relief carbonate platforms were replaced by metazoan factories, forming low-relief carbonate ramps and mixed low-gradient shelves. This environmental change has been shown to be closely associated with a negative carbon isotope excursion. A negative δ13C shift is recorded by bulk organic matter in the Milieres section (central Dolomites) and parallels a coeval excursion in carbon-isotope records of higher plant and marine algal biomarker, thus testifying a global change in the isotopic composition of carbon dioxide in the atmosphere and of dissolved inorganic carbon (DIC) in the ocean. This isotopic excursion was identified in organic carbon records throughout the western Tethys, but so far could not be reproduced convincingly using carbon isotope records from carbonate. A long carbon isotope record was produced from bulk organic matter of the early to late Carnian Milieres - Dibona section in the Dolomites, northern Italy. Carbon isotope analyses of carbonate (limestone and dolomite) were also obtained. This new carbon isotope record illustrates the structure of this complex carbon cycle perturbation related to the CPE. But while sharp carbon isotope oscillations are evident in the bulk organic carbon record, there is no evidence of a similar pattern in carbonate record. It can be shown that the carbon isotope record of carbonates is influenced by fractionation and diagenetic processes that completely obliterated the original δ13C signal. We conclude that the Carnian carbonates of the Dolomites do not

Sulfurized carbohydrates: an important sedimentary sink for organic carbon?

NASA Astrophysics Data System (ADS)

Sinninghe Damsté, Jaap S.; Kok, Marika D.; Köster, Jürgen; Schouten, Stefan

1998-12-01

In contrast to the general belief that carbohydrate carbon (C CHO) is preferentially degraded and is not extensively preserved in the sedimentary record, it is shown here that C CHO forms a large fraction of the organic matter (OM) of the total organic carbon (TOC)-rich upper Jurassic Kimmeridge Clay Formation as a result of early diagenetic sulfurization, a previously unrecognized pathway of OM preservation. This is evident from both changes in the molecular composition of the insoluble OM and from δ 13C TOC shifts of 6‰ with varying C CHO contents. Furthermore, experiments simulating the natural sulfurization of the C CHO-rich alga Phaeocystis spp. demonstrated that sulfurization can indeed lead to a substantial preservation of C CHO with a molecular fingerprint identical to that of the Kimmeridge Clay and many other Recent and ancient marine OM-rich sediments. These results imply that preservation of C CHO can exert a fundamental control on δ 13C TOC in OM-rich sediments, complicating the interpretation of δ 13C TOC records with regard to estimating terrestrial versus aquatic OM fractions, reconstruction of past atmospheric CO 2 levels and global carbon budget models.

Methane-derived authigenic carbonates along the North Anatolian fault system in the Sea of Marmara (Turkey)

NASA Astrophysics Data System (ADS)

Crémière, Antoine; Pierre, Catherine; Blanc-Valleron, Marie-Madeleine; Zitter, Tiphaine; Çağatay, M. Namik; Henry, Pierre

2012-08-01

The Marnaut cruise (May-June 2007) investigated the submerged part of the North Anatolian fault system, an active tectonic area in the Sea of Marmara. Already known and new fluid venting sites along the fault system were visited by submersible diving. Cold seeps present a considerable diversity of geochemical background associated with occurrences of authigenic carbonate crusts outcropping at the seafloor. Buried carbonate concretions were also recovered by coring within the sediments of the Tekirdağ Basin and of the Western-High ridge that separates the Tekirdağ and Central Basins. Interestingly, numerous of these early diagenetic carbonates were found within the transitional sediments from lacustrine to marine environment deposited after the late glacial maximum. The authigenic carbonates are mainly composed of aragonite, Mg-calcite and minor amounts of dolomite, and are often associated with pyrite and barite. The carbon isotopic compositions of carbonates present a wide range of values from -50.6‰ to +14.2‰ V-PDB indicating different diagenetic settings and complex mixtures of dissolved inorganic carbon from different sources. The low δ13C values of the seafloor crusts and of most buried concretions indicate that the carbon source was a mixture of microbial and thermogenic methane and possibly other hydrocarbons that were oxidized by anaerobic microbial processes. The positive δ13C values of a few buried concretions from the Western-High ridge reflect the mineralization of heavy CO2, which is thought to represent the residual by-product of oil biodegradation in a subsurface petroleum reservoir that migrated up with brines. Most of the oxygen isotopic compositions of seafloor carbonates are close to the isotopic equilibrium with the present-day bottom water conditions but a few values as low as -1.9‰ V-PDB indicate precipitation from brackish waters. In buried carbonate concretions, δ18O values as high as +4.9‰ V-PDB reflect the contribution of

Early dolomitization in the Lower Cretaceous shallow-water carbonates of Southern Apennines (Italy): Clues about palaeoclimatic fluctuations in western Tethys

NASA Astrophysics Data System (ADS)

Vinci, Francesco; Iannace, Alessandro; Parente, Mariano; Pirmez, Carlos; Torrieri, Stefano; Giorgioni, Maurizio

2017-12-01

A multidisciplinary study of the dolomitized bodies present in the Lower Cretaceous platform carbonates of Mt. Faito (Southern Apennines - Italy) was carried out in order to explore the connection between early dolomite formation and fluctuating climate conditions. The Berriasian-Aptian investigated succession is 466 m thick and mainly consists of shallow-water lagoonal limestones with frequent dolomite caps. The dolomitization intensity varies along the succession and reaches its peak in the upper Hauterivian-lower Barremian interval, where it is present a completely dolomitized interval about 100-m-thick. Field relations, petrography, mineralogy, and geochemistry of the analyzed dolomite bodies allowed identifying two populations of early dolomites, a fine-medium crystalline (FMdol) and a coarse crystalline dolomite (Cdol), both interpreted as the product of mesohaline water reflux. According to our interpretation, FMdol precipitated from concentrated brines in the very early stage of the reflux process, producing typical sedimentary features as dolomite caps. In the successive step of the process, the basin-ward 'latent' reflux precipitated Cdol from less concentrated brines. A peculiar feature of the studied succession is the great consistency between stratigraphic distribution of dolomite bodies and their geochemical signature. The completely dolomitized Hauterivian-Barremian interval, in fact, is characterized by geochemical values suggesting an origin from distinctly saltier brines. Considering that the observed near-surface dolomitization process is controlled by physical and chemical parameters reflecting the paleoenvironmental and paleoclimatic conditions during dolomite formation, we propose that the stratigraphically controlled dolomitization intensity reflects periodic fluctuations in the salinity of dolomitizing fluid, in turn controlled by long-term climate oscillations. The present work highlights that the stratigraphic distribution of early

Formation of Mg-aluminosilicates During Early Diagenesis of Carbonate Sediments in the Volcanic Crater Lake of Dziani Dzaha (Mayotte - Indian Ocean)

NASA Astrophysics Data System (ADS)

Milesi, V. P.; Jezequel, D.; Debure, M.; Marty, N.; Guyot, F. J.; Claret, F.; Virgone, A.; Gaucher, E.; Ader, M.

2017-12-01

Authigenic clays are increasingly reported in ancient carbonate rocks, but their origin remains poorly understood, strongly limiting paleoenvironmental interpretations. To tackle this issue, the carbonate sediments of the volcanic crater lake Dziani Dzaha are studied and reactive transport modeling is performed to assess the processes originating carbonate sediments associated with Mg-rich silicates during early diagenesis. The Dziani Dzaha is characterized by CO2-rich gases bubbling in three different locations, a high primary productivity leading to organic carbon contents of up to 30wt.% in the sediment, an alkalinity of 0.26 molal in the water column and pH values of 9 to 9.5. Characterization of bulk samples and clay fraction (<2µm) from the first meter of sediment with X-ray powder diffraction and X-ray fluorescence spectrometry indicates aragonite and hydromagnesite in surface sediment. The contents of hydromagnesite and organic matter decrease at depth while saponite, a Mg- and Al-rich trioctahedral smectite, accumulates to reach up to 25wt.% of mineral phases. Concurrently, chemical analyses of pore waters show a decrease of pH values from 9 to 8.3. Modeling of these diagenetic evolutions is performed with the reactive transport code Crunchflow, taking into account the sediment burial. High pH values combined with the alteration of alkaline feldspars and clinopyroxenes from the volcanic catchment allow supersaturation of lake waters relative to aragonite, hydromagnesite and saponite. Kinetic limitations in the formation of saponite explain its accumulation at depth. Production of CO2 associated with organic matter mineralization accounts for the pH decrease of pore waters, which induces hydromagnesite destabilisation leaving behind a saponite-aragonite mineral assemblage. The main driving force for the observed sequence is the intense primary productivity partly fueled by inputs of CO2-rich volcanic gases, which generates high pH, promoting the formation

Preservation of primary lake signatures in alkaline earth carbonates of the Eocene Green River Wilkins Peak-Laney Member transition zone

NASA Astrophysics Data System (ADS)

Murphy, John T.; Lowenstein, Tim K.; Pietras, Jeffrey T.

2014-12-01

Significant changes in carbonate mineralogy, texture, and stable isotope composition occur at the transition from the Wilkins Peak Member to the Laney Member in the Eocene Green River Formation, Bridger Basin, Wyoming, which reflect evolution of inflow waters, lake waters, and paleoenvironments. The top of the Wilkins Peak Member contains heterogeneous laminae of calcite and dolomite. Evaporites associated with these layers suggest deposition in hypersaline lakes. Diagenetic carbonate mineral textures include euhedral cement overgrowths and interlocking mosaics of calcite and dolomite crystals, 20-70 μm in size. Electron microprobe analyses indicate diagenetic overgrowth of Fe-rich dolomite on cloudy Fe-poor cores. δ18O values of carbonate laminae in the upper Wilkins Peak Member vary by ~ 6‰ with no depth dependent or mineralogic trends, which also suggests diagenetic overprinting. Alternating organic-rich and primary aragonite, calcite, and dolomite laminae were identified from the lower Laney Member. Primary lacustrine aragonite consists of well sorted, prismatic crystals 5-10 μm in length, with micro-lamination defined by crystal size variation. Primary precipitated calcite and dolomite laminae are monominerallic, with well sorted polyhedral crystals, ~ 10 μm in size. Primary mineralogy of the lower Laney Member changes from calcite to aragonite and dolomite stratigraphically upward. Along the same 15 m thick stratigraphic interval, δ18O values decrease upward by ~ 3‰, all of which suggests (1) lake waters underwent evaporative concentration, which together with calcite precipitation increased the lake water Mg/Ca ratios and led to formation of aragonite and dolomite, (2) source waters became lower in δ18O, possibly as inflow changed to higher altitude foreland rivers. The results from this study show that understanding the primary lacustrine versus diagenetic origin of Green River carbonate minerals is essential for paleoenvironmental and

Geochemistry of ferromanganese nodules from DOMES site a, Northern Equatorial Pacific: Multiple diagenetic metal sources in the deep sea

USGS Publications Warehouse

Calvert, S.E.; Piper, D.Z.

1984-01-01

The major and minor element composition of ferromanganese nodules from DOMES Site A has been determined by X-ray fluorescence methods. Three phases appear to control the bulk compositions: Mn and Fe oxyhydroxides and aluminosilicates. Relatively wide compositional variations are evident throughout the area. Nodules with high Mn/Fe ratios, high Cu, Mg, Mo, Ni and Zn concentrations and high todorokite/??-MnO2 ratios have granular surface textures and are confined to an east-west trending depression with thin Quaternary sediment cover. Nodules with low Mn/Fe ratios, high concentrations of As, Ca, Ce, Co, La, P, Sr, Ti, V, Y and Zr and low todorokite/??-MnO2 ratios have smooth surfaces and are confined to shallower areas with relatively thick Quaternary sediment to the north and south of the depression. All nodules in the area have compositions which are influenced by diagenesis, but those with the most marked diagenetic signature (high Mn/Fe and Cu/Ni ratios, low Ce/La ratios and more todorokite) are found in areas of very slow or non-existent sedimentation; many of these nodules are actually in contact with outcropping Tertiary sediment. This paradox may be resolved by postulating, by analogy with some shallow-water occurrences, that the nodules accrete from bottom waters which have enhanced particulate and dissolved metal contents derived from diagenetic reaction in areas remote from the site of nodule formation. The metals are supplied in a bottom flow (probably Antarctic Bottom Water) which also erodes, or prevents modern sedimentation in, the depression. Nodules on the flanks of the depression are not evidently affected by this flow and derive at least pan of their constituent metals from diagenetic reaction in the underlying Quaternary sediment. Apparently, abyssal diagenetic nodules can have an immediate and a remote diagenetic metal source. Metal fluxes derived from pore water dissolved metal gradients may not be relevant to particular accreting nodules if a

Palaeo-equatorial temperatures and carbon-cycle evolution at the Triassic- Jurassic boundary: A stable isotope perspective from shallow-water carbonates from the UAE

NASA Astrophysics Data System (ADS)

Honig, M. R.; John, C. M.

2013-12-01

to blocky calcite, bulk carbonate, oyster shells and echinoids. Assuming a pristine depositional signal can be extracted from one of the components, clumped isotopes will either shed light on the palaeoenvironmental conditions and the isotopic composition of a tropical ocean during the Late Triassic / Early Jurassic, or on the diagenetic history of the platform. We gratefully acknowledge funding from Qatar Petroleum, Shell, and Qatar Science & Technology Park.

Authigenic carbonates from active methane seeps offshore southwest Africa

NASA Astrophysics Data System (ADS)

Pierre, Catherine; Blanc-Valleron, Marie-Madeleine; Demange, Jérôme; Boudouma, Omar; Foucher, Jean-Paul; Pape, Thomas; Himmler, Tobias; Fekete, Noemi; Spiess, Volkhard

2012-12-01

The southwest African continental margin is well known for occurrences of active methane-rich fluid seeps associated with seafloor pockmarks at water depths ranging broadly from the shelf to the deep basins, as well as with high gas flares in the water column, gas hydrate accumulations, diagenetic carbonate crusts and highly diverse benthic faunal communities. During the M76/3a expedition of R/V METEOR in 2008, gravity cores recovered abundant authigenic carbonate concretions from three known pockmark sites—Hydrate Hole, Worm Hole, the Regab pockmark—and two sites newly discovered during that cruise, the so-called Deep Hole and Baboon Cluster. The carbonate concretions were commonly associated with seep-benthic macrofauna and occurred within sediments bearing shallow gas hydrates. This study presents selected results from a comprehensive analysis of the mineralogy and isotope geochemistry of diagenetic carbonates sampled at these five pockmark sites. The oxygen isotope stratigraphy obtained from three cores of 2-5 m length indicates a maximum age of about 60,000-80,000 years for these sediments. The authigenic carbonates comprise mostly magnesian calcite and aragonite, associated occasionally with dolomite. Their very low carbon isotopic compositions (-61.0 < δ13C ‰ V-PDB < -40.1) suggest anaerobic oxidation of methane (AOM) as the main process controlling carbonate precipitation. The oxygen isotopic signatures (+2.4 < δ18O ‰ V-PDB < +6.2) lie within the range in equilibrium under present-day/interglacial to glacial conditions of bottom seawater; alternatively, the most positive δ18O values might reflect the contribution of 18O-rich water from gas hydrate decomposition. The frequent occurrence of diagenetic gypsum crystals suggests that reduced sulphur (hydrogen sulphide, pyrite) from sub-seafloor sediments has been oxidized by oxygenated bottom water. The acidity released during this process can potentially induce the dissolution of carbonate, thereby

Authigenic minerals related to carbon and sulfur biogeochemical cycling from deep-sea active methane seeps offshore South-West Africa

NASA Astrophysics Data System (ADS)

Pierre, C.; Blanc-Valleron, M.; Demange, J.; Boudouma, O.; Pape, T.; Himmler, T.; Fekete, N.; Spiess, V.

2011-12-01

The South-West African continental margin is well known for occurrences of active methane-rich fluid seeps that are associated with seafloor pockmarks in a broad range of water depths, from the shelf to the deep basins. High gas flares in the water column, luxurious oases of benthic fauna, gas hydrate accumulations and diagenetic carbonate crusts have been observed at these seeps. During the M76/3a expedition of R/V METEOR (summer 2008) gravity cores recovered abundant authigenic carbonate concretions from five pockmarks of the South-West African margin including previously studied sites (Hydrate Hole, Worm Hole, Regab Pockmark) and two sites (Deep Hole, Baboon Cluster) newly discovered during the cruise. Carbonate concretions were mostly associated to sediments settled by seep-associated benthic macrofauna and bearing shallow gas hydrates. We present new results of the comprehensive analysis of the mineralogy and isotope geochemistry of the diagenetic carbonates sampled in the five pockmarks. The mineralogy of authigenic carbonates is dominated by magnesian calcite and aragonite, associated occasionally with dolomite. The oxygen and carbon isotopic compositions of authigenic carbonates (+2.4 < δ18O % V-PDB < +6.2 ; -61.0 < δ13C % V-PDB < -40.1) indicate that microbial anaerobic oxidation of methane (AOM) was the main process controling carbonate precipitation within sub-seafloor sediments deposited from the glacial-time up to the present. The frequent occurrence of diagenetic gypsum crystals within the sediments demonstrates that bio-irrigation with oxygenated bottom water by the burrowing activity of benthic fauna caused the secondary oxidation of reduced sulfur (hydrogen sulfide and pyrite) that was produced by sulfate reducting bacteria as a by-product of AOM; during the sulfide oxidation process, the released acidity induced the partial dissolution of carbonates. Our results demonstrate also the strong link that existed between the carbon and sulfur cycles

Chemical Composition of Diagenetic Features at Lower Aeolis Mons, Mars as Measured by Curiosity's APXS

NASA Astrophysics Data System (ADS)

Berger, J. A.; Schmidt, M. E.; Gellert, R.; Boyd, N.; Campbell, J. L.; Desouza, E.; Fisk, M. R.; Perrett, G. M.; Thompson, L. M.; VanBommel, S.; Yen, A. S.

2015-12-01

Curiosity's APXS investigation of the Murray Fm. (sols 755 - 950) at lower Aeolis Mons (Mt. Sharp) in Gale Crater, Mars has revealed (Mg, Ni)-sulfate diagenetic features and dark gray Ca-rich veins. The (Mg, Ni)-sulfate features occur as ~2 cm wide dendritic and botryoidal concretions that stand out in relief ~1 cm above the mudstone surface. APXS rasters over the features (Moenkopi, Mammoth, Morrison, Rosamond, Potatoe; sols 758 - 810) resulted in 1:1 molar variation of S and Mg consistent with a MgSO4 phase. The sulfate is not pure; the features are a mixture of 10 - 15% MgSO4 with the host mudstone. This mixture suggests the sulfates precipitated within pre-existing pore spaces, or were partially dissolved and replaced by sediment, preserving the crystal morphology. The sulfate features are enriched in Ni (2000 - 4250 ppm), indicating Ni-sulfate. The Murray Fm. mudstones that host the diagenetic features range to high SiO2 (60-73 wt%) and have bulk elemental signatures that are consistent with alteration by acid leaching. Low MgO (3.0 wt%) and low Ni (100 - 300 ppm) in the most apparently altered (highest SiO2) mudstones may link the acidic alteration with the fluids that formed the (Mg, Ni)-sulfates. Diagenetic Ca-sulfate-bearing veins that were abundant across Aeolis Palus persist at lower Aeolis Mons. A new vein type containing dark gray material as a separate crystalline phase within white Ca-sulfate veins was discovered in a cluster of veins in the Murray Fm. (Coalville, Alvord Mt., Amboy; sols 930 - 948). APXS rasters of the dark-toned material indicate high CaO (20 - 30 wt%) without concomitant increases in SO3. Ge (up to 650 ppm; 6.5X surrounding bedrock) and MnO (up to 1.0 wt%; 4X surrounding bedrock) are both enriched in the dark veins. These chemical observations are consistent with fluorite, although F (L.O.D. >5%) is not detectable in APXS spectra. The diagenetic features indicate that Ca, Mg, and Ni were mobilized with S in aqueous fluids, and that

Composition and origin of Early Cambrian Tiantaishan phosphorite-Mn carbonate ores, Shaanxi Province, China

USGS Publications Warehouse

Hein, J.R.; Fan, D.; Ye, J.; Liu, T.; Yeh, H.-W.

1999-01-01

The Tiantaishan phosphorite-Mn carbonate ores occur in the Early Cambrian Tananpo Formation in complexly folded and faulted rocks located in southern Shaanxi Province. About 65 x 106 tonnes of 17% P2O5 ore reserves exist and Mn-ore reserves are about 8.3 x 106 tonnes of +18% Mn. The stratigraphic sequence in ascending order consists of black phyllite, black to gray phosphorite ore, black phyllite, rhodochrostone ore, Mn mixed-carbonates, and dolostone. Data are presented from microprobe mineral chemistry, whole-rock chemistry, stable isotopes of carbonates, X-ray mineralogy, petrographic and SEM observations, and statistical analysis of chemical data. The dominant ore-forming minerals are hydroxy- and carbonate fluorapatite and Ca rhodochrosite, with Mg kutnahorite and dolomite comprising the Mn mixed-carbonate section. Pyrite occurs in all rock types and alabandite (MnS) occurs throughout the rhodochrostone section. The mean P2O5 content of phosphorite is 31% and argillaceous phosphorite is 16%, while the mean MnO content of rhodochrostone ore is 37%. Phosphorite ores are massive, spheroidal, laminated, and banded, while rhodochrostone ores have oolitic, spheroidal, and granular fabrics. The most distinguishing characteristics of the ores are high total organic carbon (TOC) contents (mean 8.4%) in the phosphorite and high P2O5 contents (mean 2.7%) in the rhodochrostone ore. The atypically high TOC contents in the Tiantaishan phosphorite probably result from very strong productivity leading to high sedimentation rates accompanied by weak reworking of sediments; poor utilization of the organic matter by bacteria; and/or partial replacement of bacterial or algal mats by the apatite. The depositional setting of the ores was the margin of an epicontinental seaway created as a direct consequence of global processes that included break-up of a supercontinent, formation of narrow seaways, creation of extensive continental shelves, overturn of stagnant, metal-rich deep

Parameterization of biogeochemical sediment-water fluxes using in-situ measurements and a steady-state diagenetic model

EPA Science Inventory

Diagenetic processes are important drivers of water column biogeochemistry in coastal areas. For example, sediment oxygen consumption can be a significant contributor to oxygen depletion in hypoxic systems, and sediment–water nutrient fluxes support primary productivity in ...

Divergent response of the neritic carbonate factory to environmental changes during the Early Bajocian Event

NASA Astrophysics Data System (ADS)

Bodin, Stephane; Hönig, Martin; Krencker, Francois-Nicolas; Danisch, Jan; Kabiri, Lahcen

2017-04-01

The Early Bajocian witnessed a global environmental perturbation, characterized by faunal and floral turnovers and a positive carbon isotope excursion. In Italy, this environmental perturbation coincided with an eutrophication event and a carbonate crisis, but this has so far not been adequately reported from other settings, leaving doubt about the extent and nature of these phenomena. Here, we are reporting on an extensive neritic carbonate factory demise that occurs in the upper Lower Bajocian of the Central High Atlas of Morocco, more precisely in the upper Propinquans - lower Humphriesianum Zones. This demise coincided with the acme of the global carbon isotope perturbation, recorded by a 3‰ positive carbon isotope excursion in the bulk organic matter of Morocco. Recovery of the neritic carbonate system occurs during the Early to Late Bajocian transition. The duration of the neritic carbonate factory demise was therefore in the order of 1 Myr. Furthermore, we observe that the Lower Bajocian of Morocco is relatively enriched in arenitic siliciclastic deposits, suggesting increased weathering and nutrient levels along the northwestern margin of Africa during the Early Bajocian. However, comparison with neighboring European basins highlights the non-uniqueness and different timing of the response of shallow-water carbonates to the Early Bajocian environmental perturbations, as some regions present no sign of carbonate factory crisis. Hence, we postulate that local factors were important in mediating the response of neritic carbonate factories to this global environmental perturbation. We notably highlight the role of large Early Bajocian sea-level fluctuation as a trigger for carbonate factory change and demise in Morocco. Indeed, in the Central High Atlas Basin, transgressive intervals are seeing the development of a mud-dominated carbonate factory whereas regressive intervals are associated with grain-dominated carbonate factory. We speculate that the

Carbon and oxygen isotope variations of the Middle-Late Triassic Al Aziziyah Formation, northwest Libya

NASA Astrophysics Data System (ADS)

Moustafa, Mohamed S. H.; Pope, Michael C.; Grossman, Ethan L.; Mriheel, Ibrahim Y.

2016-06-01

This study presents the δ13C and δ18O records from whole rock samples of the Middle-Late Triassic (Ladinian-Carnian) Al Aziziyah Formation that were deposited on a gently sloping carbonate ramp within the Jifarah Basin of Northwest Libya. The Al Aziziyah Formation consists of gray limestone, dolomite, and dolomitic limestone interbedded with shale. The Ghryan Dome and Kaf Bates sections were sampled and analyzed for carbon and oxygen isotope chemostratigraphy to integrate high-resolution carbon isotope data with an outcrop-based stratigraphy, to provide better age control of the Al Aziziyah Formation. This study also discusses the relation between the facies architecture of the Al Aziziyah Formation and the carbon isotope values. Seven stages of relative sea level rise and fall within the Ghryan Dome were identified based on facies stacking patterns, field observations and carbon stable isotopes. The Al Aziziyah Formation δ13C chemostratigraphic curve can be partially correlated with the Triassic global δ13C curve. This correlation indicates that the Al Aziziyah Formation was deposited during the Ladinian and early Carnian. No straight-forward relationship is seen between δ13C and relative sea level probably because local influences complicated systematic environmental and diagenetic isotopic effects associated with sea level change.

Raised Ridges in the Sheepbed Member as Evidence for Early Subaqueous Diagenesis at Yellowknife Bay, Gale Crater, Mars

NASA Astrophysics Data System (ADS)

Siebach, K. L.; Grotzinger, J. P.; Kah, L. C.; Stack, K.; Leveille, R. J.; Sumner, D. Y.; Edgar, L. A.; Team, M.

2013-12-01

Spatially restricted clusters of erosion-resistant, ridged fracture fills have been found throughout the fine-grained clay-rich Sheepbed member of the Yellowknife Bay Formation where the Mars Science Laboratory rover recently drilled. These 'raised ridge' features are characterized by 1-6 mm thick fractures filled with 2-4 subparallel resistant ridges. The ridges have been mapped throughout the Sheepbed member on Mastcam mosaics from sols 137 to 194 and are shown to be constrained to relatively dense, spatially localized clusters within the unit. The ridges have highly variable attitudes, ranging in dip from vertical to sub-horizontal, and striking in all directions, indicating that the original fractures formed in a mechanically isotropic setting. The fractures are generally short (<50 cm), have spindle-shaped terminations, and do not form regular polygons. The individual ridges are approximately a millimeter across and separated by at least a millimeter of less-resistant material. Based on the geometry of these features and lateral fabric variability within the unit, these are interpreted as early diagenetic synaeresis cracks, likely formed by gas expansion prior to final lithification of the Sheepbed member. Based on the isopachous nature of both the resistant and less-resistant fracture fills, the fracture-filling also occurred subaqueously, in the phreatic zone, and was likely a very early diagenetic process. This is supported by the observation that later diagenetic features, including light-toned sulfate-rich veins, cross-cut raised ridges. Investigation into the characteristics and distribution of these features, and comparison with synaeresis cracks on Earth, provide insight into the formation of the Sheepbed member and early aqueous and diagenetic processes in Gale Crater.

Organic carbon accumulation and reactivity in central Swedish lakes during the Holocene

NASA Astrophysics Data System (ADS)

Chmiel, H.; Kokic, J.; Niggemann, J.; Dittmar, T.; Sobek, S.

2012-04-01

Sedimentation and burial of particulate organic carbon (POC), received from terrestrial sources and from lake internal primary production, are responsible for the progressive accumulation and long-term storage of organic matter in lake basins. For lakes in the boreal zone of central Sweden it can be presumed, that the onset of POC accumulation occurred during the early Holocene (˜8000 BP.) after the retreat of the Scandinavian ice sheet. In this study we investigated carbon mass accumulation rates (CMARs), as well as sources and reactivity of deposited organic material, for seven lakes in central Sweden (60°N, 15°E), in order to obtain a detailed temporal resolution of carbon burial and preservation in boreal lakes. Sediment long-cores were sampled in March 2011 from the ice, and CMARs were calculated from water contents, dry bulk densities, carbon contents and radiocarbon (14C) ages of the depth profiles. To indicate the sources of the organic material and characterize its diagenetic state, we determined carbon-nitrogen ratios (C/N) as well as amounts and compositions of lignin phenols. The transitions from organic rich sediment layers to glacial till deposits were found to be in sediment depths of ˜3 m in each lake. POC contents were on average highest (25-34 wt. % C), in small lakes (≤ 0.07 km2) and lowest (10-18 wt. % C) in the larger lakes (≥ 165 km2). The CMARs over the Holocene showed significant variations and were on average lower in the early Holocene, compared to recent accumulation rates. C/N values and the composition of lignin phenols further provided indications of important changes in organic matter source and reactivity over the Holocene. In summary, our data suggest that boreal lake sediments were a significantly stronger sink for organic carbon during the last ~150 years than during earlier periods of the Holocene.

Constraining pathways of microbial mediation for carbonate concretions of the Miocene Monterey Formation using carbonate-associated sulfate

NASA Astrophysics Data System (ADS)

Loyd, Sean J.; Berelson, William M.; Lyons, Timothy W.; Hammond, Douglas E.; Corsetti, Frank A.

2012-02-01

Carbonate concretions can form as a result of organic matter degradation within sediments. However, the ability to determine specific processes and timing relationships to particular concretions has remained elusive. Previously employed proxies (e.g., carbon and oxygen isotopes) cannot uniquely distinguish among diagenetic alkalinity sources generated by microbial oxidation of organic matter using oxygen, nitrate, metal oxides, and sulfate as electron acceptors, in addition to degradation by thermal decarboxylation. Here, we employ concentrations of carbonate-associated sulfate (CAS) and δ 34S CAS (along with more traditional approaches) to determine the specific nature of concretion authigenesis within the Miocene Monterey Formation. Integrated geochemical analyses reveal that at least three specific organo-diagenetic reaction pathways can be tied to concretion formation and that these reactions are largely sample-site specific. One calcitic concretion from the Phosphatic Shale Member at Naples Beach yields δ 34S CAS values near Miocene seawater sulfate (˜+22‰ VCDT), abundant CAS (ca. 1000 ppm), depleted δ 13C carb (˜-11‰ VPDB), and very low concentrations of Fe (ca. 700 ppm) and Mn (ca. 15 ppm)—characteristics most consistent with shallow formation in association with organic matter degradation by nitrate, iron-oxides and/or minor sulfate reduction. Cemented concretionary layers of the Phosphatic Shale Member at Shell Beach display elevated δ 34S CAS (up to ˜+37‰), CAS concentrations of ˜600 ppm, mildly depleted δ 13C carb (˜-6‰), moderate amounts of Mn (ca. 250 ppm), and relatively low Fe (ca. 1700 ppm), indicative of formation in sediments dominated by sulfate reduction. Finally, concretions within a siliceous host at Montaña de Oro and Naples Beach show minimal CAS concentrations, positive δ 13C values, and the highest concentrations of Fe (ca. 11,300 ppm) and Mn (ca. 440 ppm), consistent with formation in sediments experiencing

A porous silica rock ("tripoli") in the footwall of the Jurassic Úrkút manganese deposit, Hungary: composition, and origin through carbonate dissolution

USGS Publications Warehouse

Polgari, Marta; Szabo, Zoltan; Szabo-Drubina, Magda; Hein, James R.; Yeh, Hsueh-Wen

2005-01-01

The mineralogical, chemical, and isotopic compositions were determined for a white tripoli from the footwall of the Jurassic Úrkút Mn-oxide ore deposit in the Bakony Mountains, Hungary. The tripoli consists of quartz and chalcedony, with SiO2 contents up to 100 wt.%; consequently, trace-element contents are very low. Oxygen isotopes and quartz crystallinity indicate a low-temperature diagenetic origin for this deposit. The tripoli was formed by dissolution of the carbonate portion of the siliceous (sponge spicules) Isztimér Limestone. Dissolution of the carbonate was promoted by inorganic and organic acids generated during diagensis and left a framework composed of diagenetic silica that preserved the original volume of the limestone layer. The relative enrichment of silica and high porosity is the result of that carbonate dissolution. The silty texture of this highly friable rock is due to the structurally weak silica framework.

Diagenetic changes in Concholepas concholepas shells (Gastropoda, Muricidae) in the hyper-arid conditions of Northern Chile - implications for palaeoenvironmental reconstructions

NASA Astrophysics Data System (ADS)

Guzmán, N.; Dauphin, Y.; Cuif, J. P.; Denis, A.; Ortlieb, L.

2009-02-01

Variations in the chemical composition of fossil biogenic carbonates, and in particular of mollusc shells, have been used in a range of palaeoenvironmental reconstructions. It is of primary importance, therefore, to detect and understand the diagenetic processes that may modify the original chemical signature. This microstructural and biogeochemical study focuses on modern and fossil (Holocene and Pleistocene) shells of a littoral gastropod of Northern Chile, and on the characterization of mineral component transformations at the nanometric scale and concomitant intracrystalline organic compound modifications. The inner aragonite layer of the shell exhibits more complex deteriorations than the calcite layer. This preliminary study confirms that physical and chemical alterations of various components of mollusc shell biocrystals are complex and might manifest in different ways even within a single individual. The single criterion of determining the mineralogical composition to verify the conservation state of shell samples is insufficient.

Diagenetic changes in Concholepas concholepas shells (Gastropoda, Muricidae) in the hyper-arid conditions of Northern Chile - implications for palaeoenvironmental reconstructions

NASA Astrophysics Data System (ADS)

Guzman, N.; Dauphin, Y.; Cuif, J. P.; Denis, A.; Ortlieb, L.

2008-02-01

Variations on chemical composition in fossil biogenic carbonates, and in particular of mollusk shells, have been used in a range of palaeoenvironmental reconstructions. Therefore, it is of primary importance to detect and understand the diagenetic processes that may modify the original chemical signature. This microstructural and biogeochemical study focuses on modern and fossil (Pleistocene and Holocene) shells of a littoral gastropod of Northern Chile, and on the characterization of mineral component transformations at the nanometric scale and concomitant intracrystalline organic compound modifications. The inner aragonite layer of the shell exhibits more complex deteriorations than the calcite layer. This preliminary study confirms that physical and chemical alterations of various components of mollusk shell biocrystals are complex and might manifest in different ways even within a single individual. The single criterion of determining the mineralogical composition to attest shell sample conservation state should not be considered as sufficient.

Correlation of aptian-albian carbon isotope excursions in continental strata of the cretaceous Foreland Basin, Eastern Utah, U.S.A.

USGS Publications Warehouse

Ludvigson, Greg A.; Joeckel, R.M.; Gonzalez, Luis A.; Gulbranson, E.L.; Rasbury, E.T.; Hunt, G.J.; Kirkland, J.I.; Madsen, S.

2010-01-01

Nodular carbonates ("calcretes") in continental foreland-basin strata of the Early Cretaceous Cedar Mountain Formation (CMF) in eastern Utah yield ??13C and ??O records of changes in the exogenic carbon cycle related to oceanic anoxic events (OAEs), and terrestrial paleoclimate. Chemostratigraphic profiles of both forebulge and foredeep sections show two prominent positive ??13C excursions, each with a peak value of -3% VPDB, and having background ??13C values of about -6% VPDB. These excursions correlate with the global early Aptian (Ap7) and late Aptian-early Albian (Apl2-All) carbon isotope excursions. Aptian-Albian positive ??13C excursions in the CMF also correspond to 3-4 per mil increases in carbonate ??18O. These phenomena record local aridification events. The chemostratigraphic profile on the thinner forebulge section of the CMF is calibrated, for the first time, by a radiogenic U-Pb date of 119.4 ?? 2.6 Ma on a carbonate bed, and by detrital zircon U-Pb dates on two bounding sandstone units (maximum depositional ages of 146 Ma and 112 Ma). P??trographie observations and diagenetic analyses of micritic to microsparitic carbonates from nodules indicate palustrine origins and demonstrate that they crystallized in shallow early meteoric phreatic environments. Meteoric calcite lines derived from CMF carbonates have ??18O values ranging between -8.1 to -7.5%o VPDB, supporting an estimate of zonal mean groundwater ??18O of -6% VSMOW for an Aptian-Albian paleolatitude of 34?? N. Furthermore, our two chemostratigraphic profiles exhibit a generally proportionate thinning of correlative strata from the foredeep on to the forebulge, suggesting that there were consistently lower rates of accumulation on the forebulge during the Aptian-Albian. Identification of the global Aptian-Albian ??13C excursions in purely continental strata, as demonstrated in this paper, opens a new avenue of research by identifying specific stratigraphie intervals that record the terrestrial

Significance of nodule formation for the interpretation of matrix micrite C and O isotope ratios in Upper Jurassic Ammonitico Rosso limestones (Betic Cordillera, SE Spain)

NASA Astrophysics Data System (ADS)

Coimbra, R.; Immenhauser, A.; Olóriz, F.

2009-04-01

Three Ammonitico Rosso (AR) sections from the Betic Cordillera in SE Spain were analysed to obtain stable isotope records and access paleoenvironmental information. The study area corresponded to a Late Jurassic distal epioceanic setting and is characterized by the occurrence of more or less calcareous AR horizons ranging from greyish to redish colour. The carbonate materials under scope where retrieved from the Cardador, Salcedo and Cañada del Hornillo sections and consist on matrix micrite, carbonate cements and skeletals and were analysed for their carbon and oxygen isotope signature. At least one bulk sample per ammonite biozone was retrieved under a strict biochronostratigraphic control. The degree of diagenetic imprint was acessed by cathodoluminiscence analysis and carbonate ultrastructure was analysed by scanning electron microscope. Micrite matrix showed dull luminiscence, revealing a low degree of diagenetic overprint, as oposite to carbonate cements and skekeltal materials, that presented bright orange luminiscence. The identification of coccoliths and filaments under SEM attested for the good degree of preservation of the carbonate ultrastructure. The carbon isotope chemostratigraphy resembles the known trends for Jurassic northern Tethyan margins and absolute values (from 1.1 to 3.3 permil) are within the range usually reported for well preserved material. Oxygen isotopes of matrix micrite samples present higher values than those expected for Upper Jurassic materials (ranging from -0.3 to 0.9 permil for the Cardador and Salcedo sections and from -2.1 to 0.4 permil at the Cañada del Hornillo section), whilts commonly well preserved low-Mg calcite skeletal materials, such as belemenite rostra present lower values than matrix micrite, acompanied by a very bright orange luminiscence. In contrast to what is usually reported, matrix micrite presents values closer to what would be the original isotopic composition and skeletal material is more affected by

The diagenetic behavior of cutin acids in buried conifer needles and sediments from a coastal marine environment

NASA Astrophysics Data System (ADS)

Goñi, Miguel A.; Hedges, John I.

1990-11-01

Whole green, litter, and sedimentary fir, hemlock, and cedar needles and bulk sediments collected from the Dabob Bay region in Washington state were analyzed for their cutin-derived CuO reaction products. All samples yielded dihydroxyhexadecanoic acid isomers (x,ω-C 16), 16-hydroxyhexa-decanoic acid (ω-C 16), 14-hydroxytetradecanoic acid (ω-C 14), and 18-hydroxyoctadec-9-enoic acid (ω-C 18: 1) as the major cutin acids. Fir/hemlock needle mixtures were characterized by a high abundance of the 9,16-dihydroxyhexadecanoic acid positional isomer, while cedar needles produced primarily the 10,16-dihydroxy counterpart. Cutin acids accounted for ~3% of tissue C in green needles, ~4% in needle litter, 0.5-1.5% in sedimentary needles, and about 0.1% of the organic carbon (OC) in bulk sediments. Approximately 80% of the original cutin acids in fresh green needles were lost from the deepest (~100 years old) sedimentary tissues. Cutin was more reactive than lignin and polysaccharides, but more stable than the cyclitol components of the same needles. Comparative diagenetic losses of the individual cutin acids were not uniform and suggest that additional hydroxy groups and the presence of C double bonds both increase overall reactivity. The relative stability series derived for all the molecular constituents measured is: total vanillyl phenols > total P- hydroxy phenols, ferulic acid, most aldoses, bulk organic matter > mannose, ω-C 14, ω-C 16 ⩾ ω-C 18:1 > glucose, p- coumaric acid, x, ω-C 16 > all cyclitols. Diagenetically induced changes in the various cutin parameters used to characterize nonwoody vascular plant tissues were not large enough to confuse degraded conifer tissues with other cutin sources. Based on these trends, the finely disseminated cutin-bearing tissues in Dabob Bay sediments appear to be comprised approximately of equal amounts of highly degraded fir/hemlock and cedar needle fragments. According to this estimate, nonwoody vascular plant debris

Diagenetic changes in the elemental composition of unrecrystallized mollusk shells

USGS Publications Warehouse

Ragland, P.C.; Pilkey, O.H.; Blackwelder, B. W.

1979-01-01

The Mg, Sr, Mn, Fe, Na and K contents were determined for 230 apparently unrecrystallized mollusk shells (gastropods and bivalves) ranging in age from late Cretaceous to Holocene. Consistent differences between the Holocene and fossil shells with respect to concentrations of all these elements are attributed to postburial diagenetic changes. Fossil-Holocene shell comparisons are made on the intergeneric level, a more severe test of compositional differences than was previous work involved with few species. The observed differences re-emphasize the need for extreme caution in the use of the many geochemical tools which assume that no compositional changes have taken place prior to recrystallization of calcareous materials. ?? 1979.

Persistence of carbon release events through the peak of early Eocene global warmth

NASA Astrophysics Data System (ADS)

Kirtland Turner, Sandra; Sexton, Philip F.; Charles, Christopher D.; Norris, Richard D.

2014-10-01

The Early Eocene Climatic Optimum (53-50 million years ago) was preceded by approximately six million years of progressive global warming. This warming was punctuated by a series of rapid hyperthermal warming events triggered by the release of greenhouse gases. Over these six million years, the carbon isotope record suggests that the events became more frequent but smaller in magnitude. This pattern has been suggested to reflect a thermodynamic threshold for carbon release that was more easily crossed as global temperature rose, combined with a decrease in the size of carbon reservoirs during extremely warm conditions. Here we present a continuous, 4.25-million-year-long record of the stable isotope composition of carbonate sediments from the equatorial Atlantic, spanning the peak of early Eocene global warmth. A composite of this and pre-existing records shows that the carbon isotope excursions that identify the hyperthermals exhibit continuity in magnitude and frequency throughout the approximately 10-million-year period covering the onset, peak and termination of the Early Eocene Climate Optimum. We suggest that the carbon cycle processes behind these events, excluding the largest event, the Palaeocene-Eocene Thermal Maximum (about 56 million years ago), were not exceptional. Instead, we argue that the hyperthermals may reflect orbital forcing of the carbon cycle analogous to the mechanisms proposed to operate in the cooler Oligocene and Miocene.

The early cretaceous evolution of carbonate platforms from northern Oman

DOE Office of Scientific and Technical Information (OSTI.GOV)

Masse, J.P.; Borgomano, J.; Maskiry, S.Al.

1993-09-01

In northern Oman (Jebel Akhdar and foothills) Hauterivian to early Aptian shallow carbonate platforms are widely extending and pass laterally to slope and basin environments in the Nakhl zone. Progradational geometries are identified in that zone where significant correlation between thickness and sediment types supports a prominent tectonic control. The platform records four main sedimentary breaks (drowning events). Early Barremian (lower Lekhwair Formation), Late Barremian (basal Kharaib Formation), lowermost early Aptian (upper Kharaib Formation) and middle Aptian (Shuaiba-Al Hassanat formations boundary). The late Aptian-early Albian hiatus (pre-Nahr Umr unconformity) is regarded as an early Albian tectonically driven erosion. In themore » Nakhl zone, coral-rudist limestones of late Aptian-early Albian (lower Al Hassanat Formation) document an east-west ribbon platform, the southward extension of which was obscured by the middle Albian erosions and rudist limestones of middle to late Albian (upper Al Hassanat Formation), a lateral equivalent of the Nahr Umr circa littoral shaly sediments, document an east-west-trending linear platform. The foregoing points out a northward progradation coeval with a southward transgressive major trend for the Hauterivian-early Aptian interval, a faulted margin corresponding with the Nakhl zone active during the Aptian-Albian, a late Aptian ribbon platform coeval with the Bab basin initiation southward, a regional uplifting and truncation during the early-Albian (Austrian phase), whereas shallow-water carbonates are still forming at the edge of the former platform, and an active linear platform at the northern edge of the Nahr Umr basin, the corresponding drowning contemporaneous with the onset of the Cenomanian platform eastward.« less

Development and Application of a Paleomagnetic/Geochemical Method for Constraining the Timing of Burial Diagenetic and Fluid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elmore, Richard D.; Engel, Michael H.

2005-03-10

Studies of diagenesis caused by fluid migration or other events are commonly hindered by a lack of temporal control. Our results to date demonstrate that a paleomagnetic/geochemical approach can be used to date fluid migration as well as burial diagenetic events. Our principal working hypothesis is that burial diagenetic processes (e.g., maturation of organic-rich sediments and clay diagenesis) and the migration of fluids can trigger the authigenesis of magnetic mineral phases. The ages of these events can be constrained by comparing chemical remanent magnetizations (CRMs) to independently established Apparent Polar Wander Paths. While geochemical (e.g. stable isotope and organic analyses)more » and petrographic studies provide important clues for establishing these relationships, the ultimate test of this hypothesis requires the application of independent dating methods to verify the paleomagnetic ages. Towards this end, we have used K-Ar dating of illitization as an alternative method for constraining the ages of magnetic mineral phases in our field areas.« less

Preservation of carbonate clumped isotopes in sedimentary paleoclimate archives

NASA Astrophysics Data System (ADS)

Henkes, G. A.; Passey, B. H.; Grossman, E. L.; Shenton, B.; Perez-Huerta, A.

2014-12-01

Carbonate clumped isotope thermometry is increasingly used to reconstruct paleotemperatures of ancient terrestrial environments. One promising application is elucidating paleoelevation from carbonate archives such as paleosols, lacustrine marls, and fossil freshwater shells. Unlike conventional stable isotope approaches (e.g., mineral δ18O or δD), clumped isotope thermometry is independent of the isotopic composition of the precipitating waters and can therefore be used to reconstruct elevation by both the temperature-altitude relationship and the rainfall δ18O-altitude relationship. However, interpretation of clumped isotope data is not without its own complications. Like conventional stable isotopes, clumped isotope paleotemperatures can be effectively reset to warmer values by dissolution/reprecipitation-type diagenesis during sedimentary burial. It is also known that carbonate clumped isotope bonds (i.e., 13C-18O) are susceptible to 'reordering' in the solid mineral lattice at warmer burial temperatures, with laboratory studies of natural carbonates indicating activation of this phenomenon at temperatures as low as 100 °C over geologic timescales. A challenge in applying carbonate clumped isotope thermometry to natural samples is now evaluating terrestrial archives with respect to both types of alteration: 'open-system' alteration and 'closed-system' bond reordering. In this talk we will review our experimental efforts to constrain the kinetics of clumped isotope reordering, with relevance to low-temperature carbonates like fossil shells and early diagenetic minerals, and present new laboratory data that further inform our theoretical framework for the mechanism(s) of 13C-18O bond reordering. Together with traditional analytical and petrographic screening for recrystallization, empirical and laboratory studies of carbonate clumped isotope reordering represent the next steps in evaluating isotopic records of paleoclimate, paleobiology, and paleoelevation

Rare earth elements in Japan Sea sediments and diagenetic behavior of Ce/Ce∗: Results from ODP Leg 127

NASA Astrophysics Data System (ADS)

Murray, Richard W.; Buchholtzten Brink, Marilyn R.; Brumsack, Hans J.; Gerlach, David C.; Russ, G. Price

1991-09-01

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the recorded rare earth element (REE) chemistry of Japan Sea sediments are evaluated by investigating REE total abundances and relative fractionations in 59 samples from Ocean Drilling Program Leg 127. REE total abundances (ΣREE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 (Yamato Basin) overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO2 within the late Miocene-Pliocene diatomaceous sequence. Eu/Eu∗ values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu∗ with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. ΣREE at Site 795 (Japan Basin) also is affiliated strongly with aluminosilicate phases, yet is diluted only slightly by siliceous input. At Site 797 (Yamato Basin), REE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. The biogenic influence is largest at Site 794, moderately developed at Site 797, and of only minor importance at Site 795, reflecting basinal contrasts in productivity such that the Yamato Basin records greater biogenic input than the Japan Basin, while the most productive waters overlie the easternmost sequence of Site 794. Ce/Ce∗ profiles at all three sites increase monotonically with depth, and record progressive diagenetic LREE fractionation. The observed Ce/Ce∗ record does not respond to changes in oxygenation state of the overlying water, and Ce/Ce∗ correlates slightly better with depth than with age. The downhole increase in Ce

Evaluating Uranium Isotopes in Carbonates and Implications for Reconstructing Marine Paleoredox Conditions

NASA Astrophysics Data System (ADS)

Aharony, Ofer; Gubser, Steven S.; Maldacena, Juan; Ooguri, Hirosi; Oz, Yaron

2016-12-01

Uranium isotope ratios (238U/235U, reported as δ238U) have emerged as a promising proxy for marine redox conditions. This proxy relies on isotopic fractionation that occurs during reduction of soluble U(VI) to insoluble U(IV), wherein 238U is preferentially reduced and incorporated via authigenic processes into anoxic sediments, leaving the residual seawater U and resulting carbonates 238U-depleted. Because carbonates are generally well preserved in the rock record, they are useful archives of seawater chemistry throughout Earth history, including δ238U. In principle, the long residence time of U in the ocean permits quantitative inferences of global paleoredox conditions using carbonate δ238U records. To assess the performance of the proxy, we compile all published δ238U measurements from carbonate rocks and sediments, which span the Cryogenian through the modern. The potential for δ238U to serve as a quantitative, global paleoredox proxy is supported by reproducible trends across depositional environments and paleogeographic regions in the Cryogenian non-glacial interlude and across the Permian-Triassic and Triassic-Jurassic boundaries, although carbonates deposited in deeper waters (>200 m) may be subject to local effects. Using a box model, we highlight the key levers associated with seawater δ238U and the timescales of such variability. Like all sedimentary archives, carbonate rocks are prone to diagenetic alteration and additional controls that cause δ238U in carbonates to deviate from global seawater values. Specifically, the U isotopic composition of carbonate sediments can be influenced by diagenesis, carbonate mineralogy, dolomitization, detrital input, local organic matter deposition, and pore water chemistry. We evaluate indicators of these factors in the context of a diagenetic model to assess the sensitivity of carbonate δ238U to local syndepositional or post-depositional processes. These results improve the framework for interpreting

P-wave velocity anisotropy related to sealed fractures reactivation tracing the structural diagenesis in carbonates

NASA Astrophysics Data System (ADS)

Matonti, C.; Guglielmi, Y.; Viseur, S.; Garambois, S.; Marié, L.

2017-05-01

Fracture properties are important in carbonate reservoir characterization, as they are responsible for a large part of the fluid transfer properties at all scales. It is especially true in tight rocks where the matrix transfer properties only slightly contribute to the fluid flow. Open fractures are known to strongly affect seismic velocities, amplitudes and anisotropy. Here, we explore the impact of fracture evolution on the geophysical signature and directional Vp anisotropy of fractured carbonates through diagenesis. For that purpose, we studied a meter-scale, parallelepiped quarry block of limestone using a detailed structural and diagenetic characterization, and numerous Vp measurements. The block is affected by two en-échelon fracture clusters, both being formed in opening mode (mode 1) and cemented, but only one being reactivated in shear. We compared the diagenetic evolution of the fractures, which are almost all 100% filled with successive calcite cements, with the P-wave velocities measured across this meter-scale block of carbonate, which recorded the tectonic and diagenetic changes of a South Provence sedimentary basin. We found that a directional Vp anisotropy magnitude as high as 8-16% correlates with the reactivated fractures' cluster dip angle, which is explained by the complex filling sequence and softer material present inside the fractures that have been reactivated during the basin's tectonic inversion. We show that although a late karstification phase preferentially affected these reactivated fractures, it only amplified the pre-existing anisotropy due to tectonic shear. We conclude that Vp anisotropy measurements may help to identify the fracture sealing/opening processes associated with polyphased tectonic history, the anisotropy being independent of the current stress-state. This case shows that velocity anisotropies induced by fractures resulted here from a cause that is different from how these features have often been interpreted

Coniacian-Turonian Carbonates of the Miskar Field, offshore Tunisia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Knott, I.; Moody, R.; Sandman, R.

1995-08-01

The R1 and R1 Superior Carbonates of the Miskar Field, offshore Tunisia are of Coniacian-Turonian age. These ages are constrained by several biostratigraphic events including a rapid increase in ostracod diversity at the base of the overlying Aleg Formation and the occurrence of several diagnostic benthonic foraminifera including Rotalia algeriana. The indication is that the R1 and R1 Superior Carbonates are the lateral equivalents, in part, of the Douleb Formation which is a known reservoir, onshore Tunisia. During the Coniacian-Turonian the area of the Miskar Field was subject to regional extension with the opening of several major North-South trending fractures.more » These culminate in the contemporaneous outpouring of submarine serpentinized volcanics during deposition of the R1 Superior/Aleg Formation. The R1 lithologies are deposited in a shallow water regime and consist of rudist buildup and debraic carbonates overlain by lagoonal facies in the North with an increase in beach/sabkha facies to the South. The indication is for a shallowing upward sequence and a general progradation of lithofacies northwards across a tilted block. In contrast the R1 Superior is indicative of a flooding event with relative sea-level changes reflected in variations of both lithofacies and biofacies. Overall the lithofacies are dominated by calcispheric/bioclastic wackestone-packstones probably deposited in a mid-platform setting. The diagenetic history of the R1 is the more complex of the two carbonate sequences reflecting several phases of fluid movement through the constituent lithologies. Original depositional characteristics and subsequent diagenetic meditation result in the development of highly variable reservoir properties.« less

Carbonate deposition during the late Proterozoic Era: an example from Spitsbergen

NASA Technical Reports Server (NTRS)

Knoll, A. H.; Swett, K.

1990-01-01

Carbonate sediments reflect the physico-chemical and biological circumstances of their formation; thus, features of limestones and dolomites may provide insights into both environmental and evolutionary change through geological time. The Upper Proterozoic (approx 800-700 Ma) Akademikerbreen Group, Spitsbergen, comprises 2000 m of carbonates, with only minor intercalations of quartz arenite and shale. Although Proterozoic carbonates are often seen as predominantly dolomitic, the Akademikerbreen Group is about 45 percent limestone. Stromatolites are conspicuous in outcrop but constitute only 25 percent of the total section. Micrites and coarser intraclastic carbonates derived mainly from micritric precursors comprise 60 percent of the group, while oolites make up the remaining 15 percent. Distinctive sedimentary features of the group include giant (up to 16 mm) ooids, very early diagenetic calcite nodules and cements, micrites containing subaqueous shrinkage cracks filled with equant microspar cement, and strong 13C enrichment in both carbonates and co-occurring organic matter. The principal features of Akademikerbreen carbonates are widely distributed in coeval successions. However, these rocks appear to differ from older limestones and dolomites in their relative abundance of grainstones and, perhaps, micrites, as well as their paucity of tufa-like laminates and columnar or coniform stromatolites that preserve petrographic evidence of in situ precipitation as a dominant means of carbonate accretion. Upper Proterozoic carbonates also differ from Paleozoic accumulations, but the transition is not abrupt. Most changes accompanying the Proterozoic/Phanerozoic transition can be interpreted in terms of the consequences rather than the causes of metazoan and metaphyte evolution, including the evolution of biomineralization. Carbonate sedimentology reinforces data from other sources which indicate the last 200 to 300 Ma of the Proterozoic Eon was a distinctive interval of

Large Carbonate Associated Sulfate isotopic variability between brachiopods, micrite, and other sedimentary components in Late Ordovician strata

NASA Astrophysics Data System (ADS)

Present, Theodore M.; Paris, Guillaume; Burke, Andrea; Fischer, Woodward W.; Adkins, Jess F.

2015-12-01

Carbonate Associated Sulfate (CAS) is trace sulfate incorporated into carbonate minerals during their precipitation. Its sulfur isotopic composition is often assumed to track that of seawater sulfate and inform global carbon and oxygen budgets through Earth's history. However, many CAS sulfur isotope records based on bulk-rock samples are noisy. To determine the source of bulk-rock CAS variability, we extracted CAS from different internal sedimentary components micro-drilled from well-preserved Late Ordovician and early Silurian-age limestones from Anticosti Island, Quebec, Canada. Mixtures of these components, whose sulfur isotopic compositions vary by nearly 25‰, can explain the bulk-rock CAS range. Large isotopic variability of sedimentary micrite CAS (34S-depleted from seawater by up to 15‰) is consistent with pore fluid sulfide oxidation during early diagenesis. Specimens recrystallized during burial diagenesis have CAS 34S-enriched by up to 9‰ from Hirnantian seawater, consistent with microbial sulfate reduction in a confined aquifer. In contrast to the other variable components, brachiopods with well-preserved secondary-layer fibrous calcite-a phase independently known to be the best-preserved sedimentary component in these strata-have a more homogeneous isotopic composition. These specimens indicate that seawater sulfate remained close to about 25‰ (V-CDT) through Hirnantian (end-Ordovician) events, including glaciation, mass extinction, carbon isotope excursion, and pyrite-sulfur isotope excursion. The textural relationships between our samples and their CAS isotope ratios highlight the role of diagenetic biogeochemical processes in setting the isotopic composition of CAS.

Preservation of overmature, ancient, sedimentary organic matter in carbonate concretions during outcrop weathering.

PubMed

Loyd, S J

2017-01-01

Concretions are preferentially cemented zones within sediments and sedimentary rocks. Cementation can result from relatively early diagenetic processes that include degradation of sedimentary organic compounds or methane as indicated by significantly 13 C-depleted or enriched carbon isotope compositions. As minerals fill pore space, reduced permeability may promote preservation of sediment components from degradation during subsequent diagenesis, burial heating and outcrop weathering. Discrete and macroscopic organic remains, macro and microfossils, magnetic grains, and sedimentary structures can be preferentially preserved within concretions. Here, Cretaceous carbonate concretions of the Holz Shale are shown to contain relatively high carbonate-free total organic carbon (TOC) contents (up to ~18.5 wt%) compared to the surrounding host rock (with <2.1 wt%). TOC increases with total inorganic carbon (TIC) content, a metric of the degree of cementation. Pyrite contents within concretions generally correlate with organic carbon contents. Concretion carbonate carbon isotope compositions (δ 13 C carb ) range from -22.5 to -3.4‰ (VPDB) and do not correlate strongly with TOC. Organic carbon isotope compositions (δ 13 C org ) of concretions and host rock are similar. Thermal maturity data indicate that both host and concretion organic matter are overmature and have evolved beyond the oil window maturity stage. Although the organic matter in general has experienced significant oxidative weathering, concretion interiors exhibit lower oxygen indices relative to the host. These results suggest that carbonate concretions can preferentially preserve overmature, ancient, sedimentary organic matter during outcrop weathering, despite evidence for organic matter degradation genetic mechanisms. As a result, concretions may provide an optimal proxy target for characterization of more primary organic carbon concentrations and chemical compositions. In addition, these findings

Perspectives on Proterozoic surface ocean redox from iodine contents in ancient and recent carbonate

NASA Astrophysics Data System (ADS)

Hardisty, Dalton S.; Lu, Zunli; Bekker, Andrey; Diamond, Charles W.; Gill, Benjamin C.; Jiang, Ganqing; Kah, Linda C.; Knoll, Andrew H.; Loyd, Sean J.; Osburn, Magdalena R.; Planavsky, Noah J.; Wang, Chunjiang; Zhou, Xiaoli; Lyons, Timothy W.

2017-04-01

The Proterozoic Eon hosted the emergence and initial recorded diversification of eukaryotes. Oxygen levels in the shallow marine settings critical to these events were lower than today's, although how much lower is debated. Here, we use concentrations of iodate (the oxidized iodine species) in shallow-marine limestones and dolostones to generate the first comprehensive record of Proterozoic near-surface marine redox conditions. The iodine proxy is sensitive to both local oxygen availability and the relative proximity to anoxic waters. To assess the validity of our approach, Neogene-Quaternary carbonates are used to demonstrate that diagenesis most often decreases and is unlikely to increase carbonate-iodine contents. Despite the potential for diagenetic loss, maximum Proterozoic carbonate iodine levels are elevated relative to those of the Archean, particularly during the Lomagundi and Shuram carbon isotope excursions of the Paleo- and Neoproterozoic, respectively. For the Shuram anomaly, comparisons to Neogene-Quaternary carbonates suggest that diagenesis is not responsible for the observed iodine trends. The baseline low iodine levels in Proterozoic carbonates, relative to the Phanerozoic, are linked to a shallow oxic-anoxic interface. Oxygen concentrations in surface waters would have at least intermittently been above the threshold required to support eukaryotes. However, the diagnostically low iodine data from mid-Proterozoic shallow-water carbonates, relative to those of the bracketing time intervals, are consistent with a dynamic chemocline and anoxic waters that would have episodically mixed upward and laterally into the shallow oceans. This redox instability may have challenged early eukaryotic diversification and expansion, creating an evolutionary landscape unfavorable for the emergence of animals.

Texture-specific Si isotope variations in Barberton Greenstone Belt cherts record low temperature fractionations in early Archean seawater

NASA Astrophysics Data System (ADS)

Stefurak, Elizabeth J. T.; Fischer, Woodward W.; Lowe, Donald R.

2015-02-01

diagenesis and metamorphism, although fractionations during diagenetic phase transformations may have affected certain textures. We interpret these systematic variations to reflect fractionation during silica precipitation as well as isotopically distinct fluids from which later phases originated. SIMS δ18O values fall in a range from 16.39‰ to 23.39‰ (n = 381), similar to previously published data from bulk gas source mass spectrometry of Onverwacht cherts. We observed only limited examples of texture-related variation in δ18O and did not observe correlation of δ18O with δ30Si trends. This is consistent with hypotheses that Si isotope ratios are more resistant to alteration under conditions of rock-buffered diagenesis (Marin-Carbonne et al., 2011). Our results indicate that low temperature processes fractionated silicon isotopes in early Archean marine basins, a behavior that probably precludes the application of chert δ30Si as a robust paleothermometer. The values we observe for facies that sedimentological and petrographic observations indicate formed as primary and earliest diagenetic silica precipitates from seawater are more 30Si-rich than that expected for bulk silicate Earth. This is consistent with the hypothesis that the silicon isotope budget is balanced by the coeval deposition of 30Si-enriched cherts and 30Si-depleted iron formation lithologies. Precipitation of authigenic clay minerals in both terrestrial and marine settings may have also comprised a large 30Si-depleted sink, with the corollary of an important non-carbonate alkalinity sink consuming cations released by silicate weathering.

Follow the Carbon: Isotopic Labeling Studies of Early Earth Aerosol.

PubMed

Hicks, Raea K; Day, Douglas A; Jimenez, Jose L; Tolbert, Margaret A

2016-11-01

Despite the faint young Sun, early Earth might have been kept warm by an atmosphere containing the greenhouse gases CH 4 and CO 2 in mixing ratios higher than those found on Earth today. Laboratory and modeling studies suggest that an atmosphere containing these trace gases could lead to the formation of organic aerosol haze due to UV photochemistry. Chemical mechanisms proposed to explain haze formation rely on CH 4 as the source of carbon and treat CO 2 as a source of oxygen only, but this has not previously been verified experimentally. In the present work, we use isotopically labeled precursor gases and unit-mass resolution (UMR) and high-resolution (HR) aerosol mass spectrometry to examine the sources of carbon and oxygen to photochemical aerosol formed in a CH 4 /CO 2 /N 2 atmosphere. UMR results suggest that CH 4 contributes 70-100% of carbon in the aerosol, while HR results constrain the value from 94% to 100%. We also confirm that CO 2 contributes approximately 10% of the total mass to the aerosol as oxygen. These results have implications for the geochemical interpretations of inclusions found in Archean rocks on Earth and for the astrobiological potential of other planetary atmospheres. Key Words: Atmosphere-Early Earth-Planetary atmospheres-Carbon dioxide-Methane. Astrobiology 16, 822-830.

Facies analysis, diagenesis and sequence stratigraphy of the carbonate-evaporite succession of the Upper Jurassic Surmeh Formation: Impacts on reservoir quality (Salman Oil Field, Persian Gulf, Iran)

NASA Astrophysics Data System (ADS)

Beigi, Maryam; Jafarian, Arman; Javanbakht, Mohammad; Wanas, H. A.; Mattern, Frank; Tabatabaei, Amin

2017-05-01

This study aims to determine the depositional facies, diagenetic processes and sequence stratigraphic elements of the subsurface carbonate-evaporite succession of the Upper Jurassic (Kimmeridgian-Tithonian) Surmeh Formation of the Salman Oil Field (the Persian Gulf, Iran), in an attempt to explore their impacts on reservoir quality. The Surmeh Formation consists mainly of carbonate rocks, intercalated with evaporite layers. Petrographically, the Surmeh Formation consists of nine microfacies (MF1-MF9). These microfacies are grouped into three facies associations related to three depositional environments (peritidal flat, lagoon and high-energy shoal) sited on the inner part of a homoclinal carbonate ramp. The recorded diagenetic processes include dolomitization, anhydritization, compaction, micritization, neomorphism, dissolution and cementation. Vertical stacking patterns of the studied facies reveal the presence of three third-order depositional sequences, each of which consists of transgressive systems tract (TST) and highstand systems tract (HST). The TSTs comprise intertidal and lagoon facies whereas the HSTs include supratidal and shoal facies. In terms of their impacts on reservoir quality, the shoal facies represent the best reservoir quality, whereas the peritidal and lagoonal facies exhibit moderate to lowest reservoir quality. Also, poikilotopic anhydrite cement played the most significant role in declining the reservoir quality, whereas the widespread dissolution of labile grains and formation of moldic and vuggy pores contributed in enhancing the reservoir quality. In addition, the HSTs have a better reservoir quality than the TSTs. This study represents an approach to use the depositional facies, diagenetic alterations and sequence stratigraphic framework of carbonate -evaporite succession for a more successful reservoir characterization.

Modeling the effects of diagenesis on carbonate clumped-isotope values in deep- and shallow-water settings

NASA Astrophysics Data System (ADS)

Stolper, Daniel A.; Eiler, John M.; Higgins, John A.

2018-04-01

The measurement of multiply isotopically substituted ('clumped isotope') carbonate groups provides a way to reconstruct past mineral formation temperatures. However, dissolution-reprecipitation (i.e., recrystallization) reactions, which commonly occur during sedimentary burial, can alter a sample's clumped-isotope composition such that it partially or wholly reflects deeper burial temperatures. Here we derive a quantitative model of diagenesis to explore how diagenesis alters carbonate clumped-isotope values. We apply the model to a new dataset from deep-sea sediments taken from Ocean Drilling Project site 807 in the equatorial Pacific. This dataset is used to ground truth the model. We demonstrate that the use of the model with accompanying carbonate clumped-isotope and carbonate δ18O values provides new constraints on both the diagenetic history of deep-sea settings as well as past equatorial sea-surface temperatures. Specifically, the combination of the diagenetic model and data support previous work that indicates equatorial sea-surface temperatures were warmer in the Paleogene as compared to today. We then explore whether the model is applicable to shallow-water settings commonly preserved in the rock record. Using a previously published dataset from the Bahamas, we demonstrate that the model captures the main trends of the data as a function of burial depth and thus appears applicable to a range of depositional settings.

Chemical, experimental, and morphological evidence for diagenetically altered melanin in exceptionally preserved fossils.

PubMed

Colleary, Caitlin; Dolocan, Andrei; Gardner, James; Singh, Suresh; Wuttke, Michael; Rabenstein, Renate; Habersetzer, Jörg; Schaal, Stephan; Feseha, Mulugeta; Clemens, Matthew; Jacobs, Bonnie F; Currano, Ellen D; Jacobs, Louis L; Sylvestersen, Rene Lyng; Gabbott, Sarah E; Vinther, Jakob

2015-10-13

In living organisms, color patterns, behavior, and ecology are closely linked. Thus, detection of fossil pigments may permit inferences about important aspects of ancient animal ecology and evolution. Melanin-bearing melanosomes were suggested to preserve as organic residues in exceptionally preserved fossils, retaining distinct morphology that is associated with aspects of original color patterns. Nevertheless, these oblong and spherical structures have also been identified as fossilized bacteria. To date, chemical studies have not directly considered the effects of diagenesis on melanin preservation, and how this may influence its identification. Here we use time-of-flight secondary ion mass spectrometry to identify and chemically characterize melanin in a diverse sample of previously unstudied extant and fossil taxa, including fossils with notably different diagenetic histories and geologic ages. We document signatures consistent with melanin preservation in fossils ranging from feathers, to mammals, to amphibians. Using principal component analyses, we characterize putative mixtures of eumelanin and phaeomelanin in both fossil and extant samples. Surprisingly, both extant and fossil amphibians generally exhibit melanosomes with a mixed eumelanin/phaeomelanin composition rather than pure eumelanin, as assumed previously. We argue that experimental maturation of modern melanin samples replicates diagenetic chemical alteration of melanin observed in fossils. This refutes the hypothesis that such fossil microbodies could be bacteria, and demonstrates that melanin is widely responsible for the organic soft tissue outlines in vertebrates found at exceptional fossil localities, thus allowing for the reconstruction of certain aspects of original pigment patterns.

Chemical, experimental, and morphological evidence for diagenetically altered melanin in exceptionally preserved fossils

PubMed Central

Colleary, Caitlin; Dolocan, Andrei; Gardner, James; Singh, Suresh; Wuttke, Michael; Rabenstein, Renate; Habersetzer, Jörg; Schaal, Stephan; Feseha, Mulugeta; Clemens, Matthew; Jacobs, Bonnie F.; Currano, Ellen D.; Jacobs, Louis L.; Sylvestersen, Rene Lyng; Gabbott, Sarah E.; Vinther, Jakob

2015-01-01

In living organisms, color patterns, behavior, and ecology are closely linked. Thus, detection of fossil pigments may permit inferences about important aspects of ancient animal ecology and evolution. Melanin-bearing melanosomes were suggested to preserve as organic residues in exceptionally preserved fossils, retaining distinct morphology that is associated with aspects of original color patterns. Nevertheless, these oblong and spherical structures have also been identified as fossilized bacteria. To date, chemical studies have not directly considered the effects of diagenesis on melanin preservation, and how this may influence its identification. Here we use time-of-flight secondary ion mass spectrometry to identify and chemically characterize melanin in a diverse sample of previously unstudied extant and fossil taxa, including fossils with notably different diagenetic histories and geologic ages. We document signatures consistent with melanin preservation in fossils ranging from feathers, to mammals, to amphibians. Using principal component analyses, we characterize putative mixtures of eumelanin and phaeomelanin in both fossil and extant samples. Surprisingly, both extant and fossil amphibians generally exhibit melanosomes with a mixed eumelanin/phaeomelanin composition rather than pure eumelanin, as assumed previously. We argue that experimental maturation of modern melanin samples replicates diagenetic chemical alteration of melanin observed in fossils. This refutes the hypothesis that such fossil microbodies could be bacteria, and demonstrates that melanin is widely responsible for the organic soft tissue outlines in vertebrates found at exceptional fossil localities, thus allowing for the reconstruction of certain aspects of original pigment patterns. PMID:26417094

Contrasting diagenetic histories of concretions vs. host rocks, Lion Mountain Member, Riley formation (upper Cambrian), Texas

DOE Office of Scientific and Technical Information (OSTI.GOV)

McBride, E.F.

1988-02-01

White, elliptical, calcite-cemented concretion nuclei up to 1 m long contrast markedly in color, composition, and diagenetic history from more glauconite-rich concretion rinds and from dark-green glaucarenite host rocks. Concretion nuclei are loosely packed deposits of trilobite carapaces and minor quartz and glauconite that have intergranular volumes of 58%. The nuclei are shell-lag deposits that were cemented by calcite at the sea floor or after burial of a few meters. Concretion rinds, composed of subequal amounts of quartz and compactionally deformed glauconite, have an intergranular volume of only 32% and minor quartz overgrowths that preceded pore-occluding calcite cement. The rindsmore » underwent burial for several million years to tens of millions of years to depths of several hundred meters before they were cemented. The host rock is predominately glauconite with very minor quartz and calcite cement. Strontium isotopic ratios of host-rock calcite cement are variable (0.7084 to 0.7093), but the lowest value suggests precipitation during the Middle Ordovician. In the absence of significant amounts of carbonate cement, the host rock underwent complete dissolution of trilobite carapaces and maximum compaction with total loss of porosity through squashing of glauconite grains. Maximum burial during this stage was completed by the end of Ordovician time.« less

Characterization of diagenetic siderites formed in recent and ancient ferruginous sediments of Lake Towuti, Indonesia.

NASA Astrophysics Data System (ADS)

Vuillemin, Aurele; Kallmeyer, Jens; Wagner, Dirk; Kemnitz, Helga; Wirth, Richard; Luecke, Andreas; Mayr, Christoph

2016-04-01

Authigenic minerals in lacustrine settings can be formed in the water column and within the sediment, abiotically and/or triggered by biological activity. Such minerals have been used as paleosalinity and paleoproductivity proxies, reflecting trophic state, and/or early diagenetic conditions. They have also been considered as potential biosignatures of past and present microbial activity. Here we present a study from Lake Towuti, a deep tectonic basin in Sulawesi, Indonesia. Its geographic position makes it a prime location to record paleoclimatic changes in the tropical Western Pacific warm pool in its sedimentary sequence. The ultramafic rocks and surrounding lateritic soils in the catchment area supply considerable amounts of iron and other metals to the lake. These elements further restrain primary productivity along with the development of specific microbial metabolic pathways involved in early diagenesis. Lake Towuti is stratified with anoxic conditions below 130 m, allowing metal reduction processes to take place in the hypolimnion. The extreme scarcity of sulphate and nitrate/nitrite make Lake Towuti's bottom waters a modern analogue for the Archaean Ocean. It was therefore chosen as a drilling target by the International Continental Drilling Program (ICDP). In May to July 2015, the Towuti Drilling Project recovered a total >1000 m of sediment core from three drilling sites, including a 114 m long core drilled with a contamination tracer dedicated to geomicrobiological studies. Heavy mineral fractions were extracted from core catcher samples and siderite crystals (FeCO3) were selected from different depths. Characterization of their habitus was achieved via SEM and TEM imaging. Preliminary results show that siderites grow from amorphous into nanocrystalline phases and form twinned aggregates developing into mosaic monocrystals with depth. Gradual filling of vugs and microporosity were observed along with inclusions of magnetite nanocrystals. Work in

A Perspective on Diagenetic Geometries and Patterns of Iron Oxide Cement and Coloration: Understanding Challenges and Complexities

NASA Astrophysics Data System (ADS)

Chan, M. A.; Wang, Y.

2015-12-01

Diagenetic records of fluid flow are underutilized proxies of water and environmental conditions in sedimentary rocks on Earth as well as Mars. The terrestrial iron-oxide records can be highly varied from faint wisps of coloration, to heavily cemented masses and layers. Other than vein cements, concretionary forms are some of the most prominent, yet enigmatic records. Concretions can have various mineral cement compositions with sizes that can span three orders of magnitude from mm, to cm, and m scales, in remarkably consistent, common spheroidal forms. Concretion geometries and banding may indicate directions and timings of fluid flow and precipitation, but deciphering the origins can be difficult with limited analytical tools. Definite complexities are the possibilities of: 1) overprinted events in an open system; 2) the role of organics in the nucleation and precipitation of authigenic minerals; and 3) multiple fluids, pathways, or processes that may produce similar-looking end products. In near-surface environments, likely any water since the Proterozoic has contained microbial life, and thus it seems highly probable that microbes play a significant role in the precipitation of diagenetic minerals due to the interactions of the biosphere and geosphere. However, recognition of ancient biosignatures that may have poor preservation potential remains a challenge. Iron oxides are particularly common, valuable indicators of near-surface iron cycling and are recognizable because the visual coloration. Our recent studies in Jurassic sandstones indicate preserved records of fingering at the interface of two immiscible fluids. The integration of geochemical self-organization models and field data provides new insights to understanding diagenetic fluid compositions, their relative densities, and flow direction flux and movement. These studies can have valuable implications and applications for understanding past fluid flow history, and reservoir characterization for CO2

Natural flows of H2-rich fluids in the ophiolites of Oman and the Philippines: Tectonic control of migration pathways and associated diagenetic processes

NASA Astrophysics Data System (ADS)

Deville, E. P.; Prinzhofer, A.; Vacquand, C.; Chavagnac, V.; Monnin, C.; Ceuleneer, G.; Arcilla, C. A.

2009-12-01

We compare the geological environments of sites of emission of natural hydrogen in the Oman ophiolite and the Zambales ophiolite (Luzon, Philippines). The genesis of natural H2 results from the interaction between ultrabasic rocks and aqueous solutions circulating in deep fracture networks, by oxidation of metals (Fe2+, Mn2+) and reduction of water, probably under high temperature conditions. This process generates very reducing conditions capable of destabilizing other molecules (notably reduction of deep CO2 being transformed into CH4 by Fisher-Tropsch type reactions). Nitrogen is also commonly associated to the H2-rich fluids. H2 flows are associated with the expulsion of hyperalkaline waters rich in ions OH- and Ca2+ and characterized by high pH (between 11 and 12). Most alkaline springs are found in the vicinity of major faults and/or lithological discontinuities like the basal thrust plane of the ophiolites and the peridotite-gabbro contact (Moho). Within the fracture networks, gas and water separate probably at shallow depth, i.e. close to the top of the upper aquifer level. Locally high flows of gas migrate vertically through fracture pathways and they are able to inflame spontaneously on the surface. Aqueous fluids tends to migrate laterally in the fracture network toward the creeks where most of the hyperalkaline springs are found. This water circulation induces a chain of diagenetic reactions starting in the fracture systems and continuing at the surface where it leads to the precipitation of calcite, aragonite, brucite and more rarely portlandite. This chain of diagenetic reactions is associated with the capture of the atmospheric CO2 during the precipitation of carbonates.

Evidence for early life in Earth's oldest hydrothermal vent precipitates.

PubMed

Dodd, Matthew S; Papineau, Dominic; Grenne, Tor; Slack, John F; Rittner, Martin; Pirajno, Franco; O'Neil, Jonathan; Little, Crispin T S

2017-03-01

Although it is not known when or where life on Earth began, some of the earliest habitable environments may have been submarine-hydrothermal vents. Here we describe putative fossilized microorganisms that are at least 3,770 million and possibly 4,280 million years old in ferruginous sedimentary rocks, interpreted as seafloor-hydrothermal vent-related precipitates, from the Nuvvuagittuq belt in Quebec, Canada. These structures occur as micrometre-scale haematite tubes and filaments with morphologies and mineral assemblages similar to those of filamentous microorganisms from modern hydrothermal vent precipitates and analogous microfossils in younger rocks. The Nuvvuagittuq rocks contain isotopically light carbon in carbonate and carbonaceous material, which occurs as graphitic inclusions in diagenetic carbonate rosettes, apatite blades intergrown among carbonate rosettes and magnetite-haematite granules, and is associated with carbonate in direct contact with the putative microfossils. Collectively, these observations are consistent with an oxidized biomass and provide evidence for biological activity in submarine-hydrothermal environments more than 3,770 million years ago.

Isotopically Light Organic Carbon in Phanerozoic Black Shales: Diagenetic, Source, or Environmental Signal?

NASA Astrophysics Data System (ADS)

Meyers, P. A.

2011-12-01

A curious depletion of 13C in the organic matter of marine black shales has been widely recognized ever since the advent of carbon isotope measurements half a century ago. Paleozoic and Mesozoic black shales commonly have del13C values between -29 and -26 permil, whereas modern marine organic matter has values between -22 and -18 permil. The black shale values mimic those of continental organic matter, yet sedimentary settings and Rock-Eval results indicate that the organic matter is marine in origin. This presentation will overview and discuss hypotheses to explain the isotopically light values of the black shales. First, the preferential removal of isotopically heavier organic matter components such as carbohydrates by diagenesis will be examined and shown to be wanting. Second, the possible oxidation of isotopically light methane released from clathrates that would have altered the DIC pool available to phytoplankton will be considered and also be found unlikely. A third possibility - that greater concentrations of CO2 in the greenhouse atmospheres that corresponded with deposition of many black shales allowed greater discrimination against 13C during photosynthesis - will be evaluated from del13C values of bulk carbon and of algal and land-plant biomarker molecules. Finally, the possibility that stronger stratification of the surface ocean may have magnified photic zone recycling of organic matter and reincorporation of its isotopically light carbon into fresh biomass will be considered. Although the fourth possibility is contrary to the conditions of vertical mixing of nutrients that exist in modern upwelling systems and that are responsible for their high productivity, it is consistent with the strongly stratified conditions that accompanied the high productivity that produced the Pliocene-Pleistocene sapropels of the Mediterranean Sea. Because the sapropels and most Phanerozic black shales share del15N values near 0 permil, nitrogen fixation evidently was

Reconstruction of a saline, lacustrine carbonate system (Priabonian, St-Chaptes Basin, SE France): Depositional models, paleogeographic and paleoclimatic implications

NASA Astrophysics Data System (ADS)

Lettéron, Alexandre; Hamon, Youri; Fournier, François; Séranne, Michel; Pellenard, Pierre; Joseph, Philippe

2018-05-01

A 220-m thick carbonate-dominated succession has been deposited in shallow-water, saline lake environments during the early to middle Priabonian (MP17A-MP18 mammal zones) in the Saint-Chaptes Basin (south-east France). The palaeoenvironmental, paleoclimatic and palaeogeographic significance of such saline lake carbonates has been deciphered on the basis of a multi-proxy analyses including: 1) depositional and diagenetic features; 2) biological components (molluscs, benthic foraminifera, characean gyrogonites, spores and pollens); 3) carbon and oxygen stable isotopes; 4) trace elements; and 5) clay mineralogy. Five stages of lacustrine system evolution have been identified: 1) fresh-water closed lake under dry climate (unit U1); 2) fresh to brackish water lacustrine deltaic system with a mixed carbonate-siliciclastic sedimentation under relatively wet climatic conditions (unit U2); 3) salt-water lacustrine carbonate system under humid climatic setting (unit U3); 4) evaporitic lake (unit U4); and 5) closed lake with shallow-water carbonate sedimentation under subtropical to Mediterranean climate with dry seasons (unit U5). Upper Eocene aridification is evidenced to have started as early as the earliest Priabonian (unit U1: MP17A mammal zone). A change from humid to dryer climatic conditions is recorded between units U3 and U4. The early to middle Priabonian saline lake is interpreted as an athalassic (inland) lake that have been transiently connected with neighboring salt lakes influenced by seawater and/or fed with sulfates deriving from recycling of evaporites. Maximum of connection with neighboring saline lakes (Mormoiron Basin, Camargue and Central grabens, Hérault Basin) likely occurred during unit U3 and at the base of unit U5. The most likely sources of salts of these adjacent basins are: 1) Triassic evaporites derived from salt-diapirs (Rhône valley) or from paleo-outcrops located east of the Durance fault or offshore in the Gulf of Lion; or 2) marine

Development and Application of a Paleomagnetic/Geochemical Method for Constraining the Timing of Burial Diagenetic Events

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elmore, Richard D.; Engel, Michael H.

2006-01-05

Studies of diagenesis caused by fluid migration or other events are commonly hindered by a lack of temporal control. Our results to date demonstrate that a paleomagnetic/geochemical approach can be used to date fluid migration as well as burial diagenetic events. Our principal working hypothesis is that burial diagenetic processes (e.g., maturation of organic-rich sediments and clay diagenesis) and the migration of fluids can trigger the authigenesis of magnetic mineral phases. The ages of these events can be constrained by comparing chemical remanent magnetizations (CRMs) to independently established Apparent Polar Wander Paths. Whilst geochemical (e.g. stable isotope and organic analyses)more » and petrographic studies provide important clues for establishing these relationships, the ultimate test of this hypothesis requires the application of independent dating methods to verify the paleomagnetic ages. Towards this end, we have used K-Ar dating of illitization as an alternative method for constraining the ages of magnetic mineral phases in our field areas. We have made significant progress toward understanding the origin and timing of chemical remagnetization related to burial diagenetic processes. For example, a recently completed field study documents a relationship between remagnetization and the maturation of organic matter (Blumstein et al., 2004). We have tested the hypothesized connection between clay diagenesis and remagnetization by conducting K-Ar dating of authigenic illites in units in Scotland and Montana with CRMs (e.g., Elliott et al., 2006a; Elliott et al., 2006b). We have also developed a fluid related model for alteration and remagnetization of Appalachian red beds that involves reduction and mobilization of iron phases by hydrocarbons and precipitation of authigenic hematite as a result of the introduction of meteoric fluid recharge (Cox et al., 2005). In addition, our recent studies of fluid-related CRMs along faults in Scotland provide

Early Diagenesis of Trace Elements in Modern Fjord Sediments of the High Arctic

NASA Astrophysics Data System (ADS)

Herbert, L.; Riedinger, N.; Aller, R. C.; Jørgensen, B. B.; Wehrmann, L.

2017-12-01

Marine sediments are critical repositories for elements that are only available at trace concentrations in seawater, such as Fe, Mn, Co, Ni, As, Mo, and U. The behavior of these trace elements in the sediment is governed by a dynamic interplay of diagenetic reactions involving organic carbon, Fe and Mn oxides, and sulfur phases. In the Arctic fjords of Svalbard, glacial meltwater delivers large amounts of reactive Fe and Mn oxides to the sediment, while organic carbon is deposited episodically and diluted by lithogenic material. These conditions result in pronounced Fe and Mn cycling, which in turn drives other diagenetic processes such as rapid sulfide oxidation. These conditions make the Svalbard fjords ideal sites for investigating trace element diagenesis because they allow resolution of the interconnections between Fe and Mn dynamics and trace element cycling. In August 2016, we collected sediment cores from three Svalbard fjords and analyzed trace elements in the pore water and solid sediment over the top meter. Initial results reveal the dynamic nature of these fjords, which are dominated by non-steady state processes and episodic events such as meltwater pulses and phytoplankton blooms. Within this system, the distribution of As appears to be strongly linked to the Fe cycle, while Co and Ni follow Mn; thus, these three elements may be released from the sediment through diffusion and bioturbation along with Fe and Mn. The pore water profiles of U and Mo indicate removal processes that are independent from Fe or Mn, and which are rather unexpected given the apparent diagenetic conditions. Our results will help elucidate the processes controlling trace element cycling in a dynamic, glacially impacted environment and will ultimately contribute to our understanding of the role of fjords in the biogeochemical cycling of trace elements in a rapidly changing Arctic Ocean.

The emergence and early evolution of biological carbon-fixation.

PubMed

Braakman, Rogier; Smith, Eric

2012-01-01

The fixation of CO₂ into living matter sustains all life on Earth, and embeds the biosphere within geochemistry. The six known chemical pathways used by extant organisms for this function are recognized to have overlaps, but their evolution is incompletely understood. Here we reconstruct the complete early evolutionary history of biological carbon-fixation, relating all modern pathways to a single ancestral form. We find that innovations in carbon-fixation were the foundation for most major early divergences in the tree of life. These findings are based on a novel method that fully integrates metabolic and phylogenetic constraints. Comparing gene-profiles across the metabolic cores of deep-branching organisms and requiring that they are capable of synthesizing all their biomass components leads to the surprising conclusion that the most common form for deep-branching autotrophic carbon-fixation combines two disconnected sub-networks, each supplying carbon to distinct biomass components. One of these is a linear folate-based pathway of CO₂ reduction previously only recognized as a fixation route in the complete Wood-Ljungdahl pathway, but which more generally may exclude the final step of synthesizing acetyl-CoA. Using metabolic constraints we then reconstruct a "phylometabolic" tree with a high degree of parsimony that traces the evolution of complete carbon-fixation pathways, and has a clear structure down to the root. This tree requires few instances of lateral gene transfer or convergence, and instead suggests a simple evolutionary dynamic in which all divergences have primary environmental causes. Energy optimization and oxygen toxicity are the two strongest forces of selection. The root of this tree combines the reductive citric acid cycle and the Wood-Ljungdahl pathway into a single connected network. This linked network lacks the selective optimization of modern fixation pathways but its redundancy leads to a more robust topology, making it more

The effect of aromatization on the isotopic compositions of hydrocarbons during early diagenesis

NASA Technical Reports Server (NTRS)

Freeman, K. H.; Boreham, C. J.; Summons, R. E.; Hayes, J. M.

1994-01-01

Polycyclic aromatic hydrocarbons with varying degrees of aromatization were isolated from the Eocene Messel Shale (Rheingraben, Germany). The high abundances of these compounds and their structural resemblances to cyclic triterpenoid lipids are consistent with derivation from microbial rather than thermal processes. Compounds structurally related to oleanane contain from five to nine double bonds; those within a series of aromatized hopanoids contain from three to nine. All are products of diagenetic reactions that remove hydrogen or methyl groups, and, in several cases, break carbon-carbon bonds to open rings. Aromatized products are on average depleted in 13C relative to possible precursors by l.2% (range: l.5% enrichment to 4% depletion, n = 9). The dependence of 13C content on the number of double bonds is not, however, statistically significant and it must be concluded that there is no strong evidence for isotopic fractionation accompanying diagenetic aromatization. Isotopic differences between series (structures related to ursane, des-A-ursane, des-A-lupane, des-A-arborane, and possibly, des-A-gammacerane are present) are much greater, indicating that 13C contents are controlled primarily by source effects. Fractionations due to chromatographic isotope effects during HPLC ranged from 0.1 to 2.8%.

Diagenetically altered fossil micrometeorites suggest cosmic dust is common in the geological record

NASA Astrophysics Data System (ADS)

Suttle, Martin D.; Genge, Matthew J.

2017-10-01

We report the discovery of fossil micrometeorites from Late Cretaceous chalk. Seventy-six cosmic spherules were recovered from Coniacian (87 ± 1 Ma) sediments of the White Chalk Supergroup. Particles vary from pristine silicate and iron-type spherules to pseudomorphic spherules consisting of either single-phase recrystallized magnetite or Fe-silicide. Pristine spherules are readily identified as micrometeorites on the basis of their characteristic mineralogies, textures and compositions. Both magnetite and silicide spherules contain dendritic crystals and spherical morphologies, testifying to rapid crystallisation of high temperature iron-rich metallic and oxide liquids. These particles also contain spherical cavities, representing weathering and removal of metal beads and irregular cavities, representing vesicles formed by trapped gas during crystallization; both features commonly found among modern Antarctic Iron-type (I-type) cosmic spherules. On the basis of textural analysis, the magnetite and Fe-silicide spherules are shown to be I-type cosmic spherules that have experienced complete secondary replacement during diagenesis (fossilization). Our results demonstrate that micrometeorites, preserved in sedimentary rocks, are affected by a suite of complex diagenetic processes, which can result in disparate replacement minerals, even within the same sequence of sedimentary beds. As a result, the identification of fossil micrometeorites requires careful observation of particle textures and comparisons with modern Antarctic collections. Replaced micrometeorites imply that geochemical signatures the extraterrestrial dust are subject to diagenetic remobilisation that limits their stratigraphic resolution. However, this study demonstrates that fossil, pseudomorphic micrometeorites can be recognised and are likely common within the geological record.

Environmental change during the Late Berriasian - Early Valanginian: a prelude to the late Early Valanginian carbon-isotope event?

NASA Astrophysics Data System (ADS)

Morales, Chloé; Schnyder, Johann; Spangenberg, Jorge; Adatte, Thierry; Westermann, Stephane; Föllmi, Karl

2010-05-01

The Valanginian period is well known for a positive excursion in marine and terrestrial δ13C records, which has been interpreted as the consequence of a major perturbation in the global carbon cycle (Lini et al., 1992; Erba et al., 2004). In contrast to the positive δ13C excursions of the Early Aptian and latest Cenomanian, marine organic-rich sediments have only been recognized from a few localities (van de Schootbrugge et al., 2003; Reboulet et al., 2003; Gröcke et al., 2005; Westermann et al., in press). The δ13C excursion began in the late Early Valanginian (campylotoxus ammonite zone) and gradually ended during the Late Valanginian. It is associated with a phase of widespread carbonate-platform drowning on the shelf (Föllmi et al., 1994) and a decline in calcareous nannofossils in the pelagic realm (Erba et al., 2004). As a triggering mechanism, numerous authors invoke the formation of the Parañà-Etendeka flood basalt. The correlation of this episode with the Valanginian δ13C event depends, however, on the absolute ages attributed to the Valanginian stage. The recent geological timescale by Ogg et al. (2008) shows that the major eruptional phase occurred during the Late Valanginian. This may imply that the late Early Valanginian δ13C event resulted from a combination of different factors. Important paleoenvironmental change occurred already in the latest Berriasian and earliest Valanginian, prior to the positive δ13C excursion. An increase in nutrient input near the onset of the δ13C excursion (campylotoxus ammonite zone), which may be considered as a trigger of the carbon cycle perturbation, has been identified in different studies, (Hennig, 2003; Duchamp-Alphonse et al., 2007; Bornemann & Mutterlose, 2008). Heterozoan faunal associations became dominant since the Early Valanginian on the northern Tethyan Helvetic platform and may indicate the beginning of sea-water eutrophication (Föllmi et al., 2007). Clay assemblages in the Tethys and Western

High-porosity Cenozoic carbonate rocks of South Florida: Progressive loss of porosity with depth

USGS Publications Warehouse

Halley, Robert B.; Schmoker, James W.

1983-01-01

Porosity measurements by borehole gravity meter in subsurface Cenozoic carbonates of south Florida reveal an extremely porous mass of limestone and dolomite which is transitional in total pore volume between typical porosity values for modern carbonate sediments and ancient carbonate rocks. A persistent decrease of porosity with depth, similar to that of chalks of the Gulf Coast, occurs in these rocks. We make no attempt to differentiate depositional or diagenetic facies which produce scatter in the porosity-depth relationship; the dominant data trends thus are functions of carbonate rocks in general rather than of particular carbonate facies. Carbonate strata with less than 20% porosity are absent from the rocks studied here.Aquifers and aquicludes cannot be distinguished on the basis of porosity. Although aquifers are characterized by great permeability and well-developed vuggy and even cavernous porosity in some intervals, they are not exceptionally porous when compared to other Tertiary carbonate rocks in south Florida. Permeability in these strata is governed more by the spacial distribution of pore space and matrix than by the total volume of porosity present.Dolomite is as porous as, or slightly less porous than, limestones in these rocks. This observation places limits on any model proposed for dolomitization and suggests that dolomitization does not take place by a simple ion-for-ion replacement of magnesium for calcium. Dolomitization may be selective for less porous limestone, or it may involve the incorporation of significant amounts of carbonate as well as magnesium into the rock.The great volume of pore space in these rocks serves to highlight the inefficiency of early diagenesis in reducing carbonate porosity and to emphasize the importance of later porosity reduction which occurs during the burial or late near-surface history of limestones and dolomites.

Evidence for early life in Earth’s oldest hydrothermal vent precipitates

USGS Publications Warehouse

Dodd, Matthew S.; Papineau, Dominic; Grenne, Tor; Slack, John F.; Rittner, Martin; Pirajno, Franco; O’Neil, Jonathan; Little, Crispin T.S.

2017-01-01

Although it is not known when or where life on Earth began, some of the earliest habitable environments may have been submarine-hydrothermal vents. Here we describe putative fossilized microorganisms that are at least 3,770 million and possibly 4,280 million years old in ferruginous sedimentary rocks, interpreted as seafloor-hydrothermal vent-related precipitates, from the Nuvvuagittuq belt in Quebec, Canada. These structures occur as micrometre-scale haematite tubes and filaments with morphologies and mineral assemblages similar to those of filamentous microorganisms from modern hydrothermal vent precipitates and analogous microfossils in younger rocks. The Nuvvuagittuq rocks contain isotopically light carbon in carbonate and carbonaceous material, which occurs as graphitic inclusions in diagenetic carbonate rosettes, apatite blades intergrown among carbonate rosettes and magnetite–haematite granules, and is associated with carbonate in direct contact with the putative microfossils. Collectively, these observations are consistent with an oxidized biomass and provide evidence for biological activity in submarine-hydrothermal environments more than 3,770 million years ago.

Deciphering the impact of diagenesis overprint on negative δ13C excursions using rock magnetism: Case study of Ediacaran carbonates, Yangjiaping section, South China

NASA Astrophysics Data System (ADS)

Macouin, Mélina; Ader, Magali; Moreau, Marie-Gabrielle; Poitou, Charles; Yang, Zhenyu; Sun, Zhimming

2012-10-01

Rock magnetism is used here to investigate the genesis of one of the puzzling negative carbon isotopic excursions of the Neoproterozoic in the Yangtze platform (South China). A detailed characterization of the magnetic mineralogy, which includes low-temperature and high-field magnetometry and classical magnetic measurement (ARM, IRM, susceptibility), was therefore performed along upper Doushantuo and lower Dengying Formations outcropping in the Yangjiaping section. The derived magnetic parameters show variations that can be interpreted as variations in magnetic grains size and in oxide contents. They show that the magnetic content is significantly reduced in samples presenting negative δ13Ccalcite values. We interpret this as a result of magnetite dissolution and secondary carbonate precipitation during early diagenesis bacterial sulfate reduction. Combined with C and O isotopic data, paleomagnetic techniques thus show that the upper Doushantuo-lower Dengying negative excursion of the Yangjiaping section is largely due to diagenesis, although the preservation of a genuine δ13C excursion of lower magnitude from +7‰ down to 0‰, instead of down to -9‰ as usually considered, cannot be ruled out. A corrected δ13Ccarbonate chemostratigraphic curve is therefore proposed. The unambiguous identification of a strong diagenetic component for this excursion casts doubts on the primary nature of other potentially time equivalent negative excursions of the Yangtze platform and thus to its correlation to negative excursions in other cratons (i.e. Shuram excursion). More generally, this study illustrates the potential of magnetic mineralogy characterization, a low cost, time efficient and non-destructive technique, as screening tool for diagenetic overprints of δ13C and δ18O.

Unravelling the Paleoenvironmental and Diagenetic History of Fluviolacustrine Sediments from a Northern Kenya Rift Basin Through Analysis of HSPDP West Turkana-Kaitio Core Material

NASA Astrophysics Data System (ADS)

Rabideaux, N. M.; Chaudhary, M. S.; Deocampo, D.; Feibel, C. S.; Cohen, A. S.

2016-12-01

The Hominin Sites and Paleolakes Drilling Project (HSPDP) collected sediment cores from six rift basins in Ethiopia and Kenya. The goal of HSPDP is to construct high-resolution records of environmental change, and to understand how those changes relate to early human evolution and cultural adaptations. The West Turkana-Kaitio (WTK) site was targeted due to the abundant archeological and paleontological artifacts and fossils discovered around the basin. We conducted XRD and XRF analyses on HSPDP-WTK core material to construct a high-resolution record of paleoenvironmental conditions in the Kenya Rift during the Early Pleistocene ( 1.9-1.35 Ma). Mineralogical and geochemical trends were also used to identify the diagenetic history of fluviolacustrine sediments in the basin. The bulk mineralogy is comprised of mostly detrital feldspars, muscovite, α-quartz, and carbonates. Zeolites are present in intervals throughout the core, possibly suggesting pulses of increased salinity. Oxides and S-bearing minerals are abundant from 100-170 mbs, which may be indicative of redox and or hydrothermal processes in that interval. The lowermost portion of the core contains α- and β-quartz, pyrite and zeolites, suggesting either low-oxygen saline conditions or hydrothermal activity. Oriented clay analysis indicated multiple intervals of diagenesis, with the illitization of smectite related to hydrothermal and or microbial activity. Clay analysis provided evidence for a low degree of illitization in the upper portion of the core, whereas mixed-layered illite-smectite (I/S) contained 30-50% illite proximal to fault breccia and up to 70% illite below the faulted section, indicative of significant alteration in the lowermost portion of the core. Coupled mineralogical and geochemical analysis revealed a complex alteration history in the basin indicated by: 1) the presence of mixed-layer I/S throughout the 216 m core; 2) pronounced alteration proximal to faulting; and 3) authigenic

On morphology of methane-derived authigenic carbonates

NASA Astrophysics Data System (ADS)

Logvina, E.; Matveeva, T.

2009-04-01

Studies of methane-derived carbonates revealed a great variety their morphological types. Although the processes of these carbonates formation is not clearly understood, it has been suggested that in general bacterially mediated processes of hydrocarbon oxidation, coupled with sulphate reduction, produce unusually high levels of alkalinity and dissolved inorganic carbon in the pore fluids that is partitioned between the precipitating carbonate and CO2 rich plumes which emanate into the water column (Aharon, 1994). These carbonates consist by three main CaCO3 polymorphs - calcite, aragonite and dolomite. Carbonates with different petrography cemented from these polymorphs can be classified according to their specific locality mode of formation and biogenic or non-biogenic origin (Greinert et al., 2002). There are classifications for the authigenic carbonates which are based on petrography, morphology, or based on age and origin. In this work we will consider the petrographical and morphological differences of authigenic carbonates. The large structures vary from 10 to 200 m size, named as chemoherm carbonates. Usually they cemented by pure aragonite with minor Mg-calcite admixture. These chemoherms rise up to 50 m above the seafloor. The structures are irregular in shape and have numerous pores and open pathways resulting from plumbing system of fluid expulsion. This type of authigenic carbonates was observed in the NE Black Sea (Michaelis et al., 2002), at the Hydrate Ridge area (Greinert et al., 2001), at Aleutian accretionary margin (Greinert et al., 2002). Diagenetic carbonates - carbonate cemented sediments both growing at the seafloor or within the sediment framework and showing a large variety of shapes (chimneys, crusts, concretions est.), with grey to dark-grey color. Petrographically the carbonate cement represents by Mg-calcite, protodolomite and dolomite. The diagenetic carbonates occur widely in the fluid venting areas. In particular, diagenetic

Influences of Sedimentary Environments and Volcanic Sources on Diagenetic Alteration of Volcanic Tuffs in South China.

PubMed

Gong, Nina; Hong, Hanlie; Huff, Warren D; Fang, Qian; Bae, Christopher J; Wang, Chaowen; Yin, Ke; Chen, Shuling

2018-05-16

Permian-Triassic (P-Tr) altered volcanic ashes (tuffs) are widely distributed within the P-Tr boundary successions in South China. Volcanic altered ashes from terrestrial section-Chahe (CH) and marine section-Shangsi (SS) are selected to further understand the influence of sedimentary environments and volcanic sources on diagenetic alterarion on volcanic tuffs. The zircon 206 Pb/ 238 U ages of the corresponding beds between two sections are almost synchronous. Sedimentary environment of the altered tuffs was characterized by a low pH and did not experience a hydrothermal process. The dominant clay minerals of all the tuff beds are illite-smectite (I-S) minerals, with minor chlorite and kaolinite. I-S minerals of CH (R3) are more ordered than SS (R1), suggesting that CH also shows a higher diagenetic grade and more intensive chemical weathering. Besides, the nature of the volcanism of the tuff beds studied is derived from different magma sources. The clay mineral compositions of tuffs have little relation with the types of source volcanism and the depositional environments. Instead, the degree of the mixed-layer clay minerals and the REE distribution are mainly dependent upon the sedimentary environments. Thus, the mixed-layer clay minerals ratio and their geochemical index can be used as the paleoenvironmental indicator.

Sedimentary sulfur geochemistry of the Paleogene Green River Formation, western USA: Implications for interpreting depositional and diagenetic processes in saline alkaline lakes

USGS Publications Warehouse

Tuttle, M.L.; Goldhaber, M.B.

1993-01-01

The sulfur geochemistry of the lacustrine Paleogene Green River Formation (Colorado, Utah, and Wyoming, USA) is unlike that of most marine and other lacustrine rocks. Distinctive chemical, isotopic, and mineralogical characteristics of the formation are pyrrhotite and marcasite, high contents of iron mineral sulfides strikingly enriched in 34S, cyclical trends in sulfur abundance and ??34S values, and long-term evolutionary trends in ??34S values. Analyses that identified and quantified these characteristics include carbonate-free abundance of organic carbon (0.13-47 wt%), total iron (0.31-13 wt%), reactive iron (>70% of total iron), total sulfur (0.02-16 wt%), acid-volatile monosulfide (SAv), disulfide (SDi > 70% of total sulfur), sulfate (SSO4) and organosulfur (SOrg); isotopic composition of separated sulfur phases (??34SDi,Av up to +49???); and mineralogy, morphology and paragenesis of sulfide minerals. Mineralogy, morphology, ??34SDi,Av, and ??34SOrg have a distinctive relation, reflecting variable and unique depositional and early diagenetic conditions in the Green River lakes. When the lakes were brackish, dissimilatory sulfate-reducing bacteria in the sediment produced H2S, which initially reacted with labile iron to form pyrite framboids and more gradually with organic matter to form organosulfur compounds. During a long-lived stage of saline lake water, the amount of sulfate supplied by inflow decreased and alkalinity and pH of lake waters increased substantially. Extensive bacterial sulfate reduction in the water column kept lake waters undersaturated with sulfate minerals. A very high H2S:SO4 ratio developed in stagnant bottom water aided by the high pH that kinetically inhibited iron sulfidization. Progressive removal of H2S by coeval formation of iron sulfides and organosulfur compounds caused the isotopic composition of the entire dissolved sulfur reservoir to evolve to ??34S values much greater than that of inflow sulfate, which is estimated to have

Early Results from the NASA Orbiting Carbon Observatory-2 (OCO-2)

NASA Astrophysics Data System (ADS)

Crisp, David; Eldering, Annmarie

2015-04-01

The Orbiting Carbon Observatory-2 (OCO-2) is NASA's first satellite designed to collect the measurements needed to estimate the column-averaged carbon dioxide (CO2) dry air mole fraction, XCO2, with the sensitivity, accuracy, and resolution needed to characterize the CO2 sources and sinks on regional scales over the globe. OCO-2 was successfully launched from Vandenberg Air Force Base in California on July 2, 2014 and joined the 705-km Afternoon Constellation (A-Train) on August 3, 2014. The three-channel imaging grating spectrometer was then cooled to its operating temperatures and a comprehensive series of characterization and calibration activities were initiated. Since early October 2014, the observatory has been routinely collecting almost 1 million soundings over the sunlit hemisphere each day. Early cloud screening results indicate that 15-30% of these measurements may be sufficiently cloud free to yield precise estimates of XCO2. Initial deliveries of calibrated, geo-located OCO-2 spectra to the NASA Goddard Earth Science Data and Information Services Center (GES DISC) began on December 30, 2014. Preliminary estimates of XCO2 retrieved from these data are currently being validated against observations from the Total Carbon Column Observing Network (TCCON) and other standards. Routine deliveries XCO2 and other products, including surface pressure and chlorophyll fluorescence, to the GES DISC are expected to begin before the end of March, 2015. This presentation will summarize the status of the OCO-2 mission and the coverage, resolution, and accuracy of its early results.

Diagenetic evidence for an epigenetic origin of the Courtbrown Zn-Pb deposit, Ireland

NASA Astrophysics Data System (ADS)

Reed, Christopher P.; Wallace, Malcolm W.

2001-08-01

Mineralisation at the Courtbrown deposit in south-western Ireland is concentrated in the basal section of the Chadian Waulsortian Limestone, immediately above the Courceyan Ballysteen Limestone. Two episodes of sulphide deposition have been identified: an early stage of minor pyrite precipitation, and a later base-metal-rich mineralisation event. Sphalerite, galena and pyrite of the later mineralisation event occur predominantly as replacement phases along stylolites, dissolution seams, and within the micritic matrix of the host limestone. These sulphide minerals also occur as cements within late stage fractures. The following diagenetic phases are present in the Waulsortian and Ballysteen Limestones in the Courtbrown area (from oldest to youngest): non-luminescent synsedimentary calcite cements, non-luminescent equant calcite cements, bright luminescent calcite cement, dull luminescent calcite cement, planar dolomite cement and replacement dolomite (regional dolomite), saddle dolomite cement, and fibrous dull luminescent calcite cement filling pressure-shadows around the sulphide minerals. Homogenisation temperatures for primary fluid inclusions within dull luminescent calcite cements (precipitated penecontemporaneously with base-metal mineralisation) range from 160 to 200 °C, with a mode at 170-180 °C. These values are unlikely to be representative of mineralisation temperatures as the fluid inclusions may have been significantly affected by heating and/or deformation during late burial (maximum paleotemperatures from Ro and CAI data around 310 °C). The observed paragenetic sequence indicates that mineralisation is completely epigenetic. As the earliest mineralisation is hosted by macro-stylolites, the sequence must have obtained a minimum burial depth of around 800 m prior to the onset of mineralisation. A burial depth of 800 m would correspond to an approximate early Chadian age for the Courtbrown area. Pressure-shadows around sphalerite further indicate

Recent Compositional Trends within the Murray Formation, Gale Crater, Mars, as seen by APXS: Implications for Sedimentary, Diagenetic and Alteration History.

NASA Astrophysics Data System (ADS)

Thompson, L. M.; Yen, A.; Spray, J. G.; Johnson, J. R.; Fraeman, A. A.; Berger, J. A.; Gellert, R.; Boyd, N.; Desouza, E.; O'Connell-Cooper, C.; VanBommel, S.

2017-12-01

The >230 m thick Murray Formation is the lower-most unit of the Mount Sharp Group, and interpreted as primarily lacustrine. Representative mudstone, siltstone and fine sandstone targets, encountered above -4330 m elevation, trend to lower Si, Al, Ti, Cr and Ca, and higher Fe, Mn, Zn, P and Mg than the Murray below. Less common, distinctive, coarser grained sandstone lenses tend to exhibit slightly different compositions to the more typical Murray but, overall, show similar elemental trends with elevation, albeit exaggerated. This suggests that the variations observed with elevation in Al, Ti, Cr, K, Fe, Mn, Zn and P within both the coarser sandstones and finer grained Murray are the result of diagenetic and/or alteration processes rather than provenance or physical sedimentary processes such as sorting. This is supported by the chemistry of obvious diagenetic, dark grey nodules, and other potential diagenetic/alteration features within this section, which show variations in the same element concentrations (i.e., P, Mn, Fe, Zn, Mg, Ca and S), distinct from diagenetic features lower down in the stratigraphy, indicating mobility of these elements within this section and changing fluid chemistry. Trends in FeO/MnO generally mimic the presence of ferric absorption features observed in visible/near infrared passive spectra from the ChemCam instrument and from CRISM orbital data, which may be consistent with changes in redox conditions as we climb up section towards Vera Rubin Ridge (Hematite Ridge). Layer-parallel CaSO4 is also common, and not observed below -4330 m. This may represent syndepositional evaporite layers, or late bedding/laminae parallel veins emplaced after lithification, in conjunction with cross-cutting veins. The overall differences in composition between the sandstone targets and finer grained Murray are attributed to distinct provenances and/or sorting during transport. We will discuss the implications of the trends and composition of the Murray above

Carbon Cycle Dynamics through the Early Eocene Climatic Optimum: Orbital Couplings to Lacustrine Cycling

NASA Astrophysics Data System (ADS)

Rosengard, S. Z.; Grogan, D. S.; Whiteside, J. H.; van Keuren, M.; Musher, D.

2010-12-01

The early Eocene represents the most recent hothouse climate state of Earth history, a period during which Earth’s surface temperatures warmed and reached a steady peak at the Early Eocene Climatic Optimum (EECO), 53.5-50 Ma. Interspersed through the primary warming interval were several hyperthermals, or rapid peaks in surface temperature and pulses of carbon dioxide into the atmosphere, followed by rapid declines, lasting 10^4 to 10^5 years. Various hypotheses have been offered to explain the climatic triggers during the hothouse interval, including changes in ocean circulation, methane release from hydrates, volcanism, and turnover of terrestrial organic matter, implicating various couplings and feedbacks in the global carbon cycle. The present study investigates the prevailing changes in carbon cycle dynamics that occurred during a specific subinterval of the Early Eocene Climatic Optimum. We sampled a carbon-rich 300-ft ( 1100 kyr) section of lacustrine Green River Formation sediments from the TOSCO core in the Uinta Basin at a one-foot resolution for organic carbon content and δ^{13}C. The compiled data comprise a high-resolution profile of total organic carbon and isotopic organic carbon composition through the section, showing cyclic patterns that we hypothesize reflect orbital signals. Bulk isotopic carbon and shale oil measurements from an earlier Fischer Assay across TOSCO’s entire 1030-ft core were then filtered using the expected frequency of a 23-kyr precession cycle. The overlaid cycles reveal δ^{13}C and oil content to be anti-phase through the 300-ft section, except for an interval of 50 feet (180 kyr) from the Mahogany Zone to the B-groove of the core, where the two measurements are in-phase. Given that shale oil, a proxy for lake primary productivity and carbon burial, and δ^{13}C typically correlate inversely, this short, 180-kyr interval of in-phase variation suggests a significant alteration in the local carbon cycle. These preliminary

Depositional and diagenetic models of some miocene evaporites on the Red Sea coast, Egypt

NASA Astrophysics Data System (ADS)

El Sayed A. A., Youssef

1986-06-01

The Miocene evaporites on the Red Sea coast, Egypt, are interpreted as a sabkha-chenier complex, which includes deposition in shallow water as well as in supratidal environments Costal sabkhas and shallow subaqueous evaporite sequences are recognised. The subaqueous sequence is represented by nodular mosaic and massive crystalline gypsum covered by a surface layer of nodular, white, dense powdery anhydrite. The sabkha sequences are represented by (a) small mounds overlying the older rock unit (Gebel El Rusas Formation) composed of fenestral stromatolitic and nodular dolomites overlain by a dolomitic limestone layer, (b) thin layer overlying the subaqueous evaporite sequence and composed of fenestral stromatolitic dolomite overlain by a nodular anhydrite layer. The nodular structure in the subaqueous as well as the sabkha sequences is formed diagenetically by transformation and recrystallization process. The dolomites in both sabkha sequences (a and b) are characterised by low Na + concentrations (143 to 755 ppm) and low values of δ 18O (- 1.85 to -8.7‰ PDB). This indicates that the dolomites were formed from saline water mixed with fresh water. These dolomites are also characterised by a low δ 13C (-12.95 to -27.1‰ PDB). This shows that the light carbon produced by the degradation of organic matter through the sulphate reduction process has played a significant role in the formation of these dolomites. Both microcrystalline and megacrystalline white dolomites are recognised in sabkha sequences. Relatively high concentrations of lead, zinc and copper are associated with the high percent of megacrystalline white dolomite.

Micron-scale Analysis of Carbonate-Associated Sulfate by Secondary Ionization Mass Spectrometry: Insights into Spatial Variability in δ34SCAS

NASA Astrophysics Data System (ADS)

Fike, D. A.; Jones, D. S.

2012-12-01

The proliferation of carbonate-associated sulfate (CAS) isotope analyses in recent years has revolutionized our understanding of marine sulfur cycling over much of Earth history. In marine carbonate rocks, δ34SCAS is thought to be a faithful recorder of the isotopic composition of marine sulfate (δ34SSO4). However, as the chemostratigraphic record becomes better resolved in time and space, reports of coeval but discordant δ34SCAS values are becoming increasingly common. These differences could arise in part from a) water column stratification or physiographic separations between separate ocean basins (i.e., paleoceanographic variability in δ34SSO4); b) syndepositional processes that decouple the relationship between δ34SSO4 and δ34SCAS during deposition or prior to lithification; or c) diagenetic alteration of the δ34SCAS signal following deposition. To help disentangle these processes, we have developed a microanalytical approach to determine the abundance and isotopic composition of CAS using secondary ionization mass spectrometry (SIMS). While our current precision (~1‰) cannot compete with that obtained from traditional bulk analysis on gas source isotope ratio mass spectrometers, we believe that the unparalleled spatial resolution can provide substantial insights into many of the fundamental questions that remain regarding the mechanisms by which CAS concentration and isotopic composition can be altered during carbonate precipitation and/or recrystallization. With a spatial resolution as low as ~ 5 μm, it is possible to analyze suites of primary and diagenetic phases, including individual carbonate allochems, muds, and cements. Preliminary results indicate that δ34SCAS can vary by as much as 10‰ between phases in a single sample. This scale of analysis allows for a rigorous evaluation of the susceptibility of δ34SCAS to syndepositional and diagenetic alteration, especially when coupled with parallel analysis of δ13Ccarb/δ18Ocarb and diagnostic

Early diagenesis of bacteriohopanepolyol derivatives: Formation of fossil homohopanoids

NASA Astrophysics Data System (ADS)

Sinninghe Damsté, Jaap S.; Van Duin, Adri C. T.; Hollander, David; Kohnen, Math E. L.; De Leeuw, Jan W.

1995-12-01

Diagenetic pathways of bacteriohopanepolyol derivatives are proposed based on the concentrations and 13C contents of homohopanes, homohop-17(21)-enes, benzohopanes, hopanoid thiophenes and sulphides, and macromolecularly S-bound homohopanes present in the extracts of twelve composite one metre samples from a 120 m core recovered from the Upper Cretaceous Jurf ed Darawish Oil Shale (Jordan). A large part (>80-95%) of the pentakishomohopane skeleton occurs in a S-bound form. This reveals the selective preservation of the C 35 hopane skeleton by sulphur sequestration and provides a theoretical basis for the homohopane index as an indicator of anoxia in past depositional environments. A smaller part (>50-80%) of the total extended hopane skeletons (C 31-C 35) occurs in a S-bound form. Of the non-sulphur-containing hopanoids the homohop-17(21)-enes dominate. These latter components show a gradual increase of 22S epimers with depth (45-52%) towards the thermodynamic equilibrium (52-53%) as calculated by molecular mechanics. Molecular mechanic calculations indicate that this increase can be explained by either isomerisation of 22R hop-17(21)-enes or by isomerisation of double bonds of homohopenes formed by dehydration of bacteriohopanepolyols "en passant" isomerising the chiral centre at C-22. A combination of these two pathways is also possible and provides an explanation for different δ13C values of pairs of 22R and 22S epimers. Isomerisation of 17β,21β(H)-homohopane to 17α,21,β(H)-homohopane carbon skeletons occurs for all compound classes in a very narrow depth span (ca. 20 m) and is probably induced by small differences in thermal history. Compound-specific carbon isotope analyses indicated that the series of homohop-17(21)-enes have in some cases significant differences in 13C content, indicating that at least two different sources have contributed to this series of components. Differences with macromolecularly S-bound C 35 hopane skeletons and free C 31

The occurrence and origin of celestite in the Abolfares region, Iran: Implications for Sr-mineralization in Zagros fold belt (ZFB)

NASA Astrophysics Data System (ADS)

Pourkaseb, Houshang; Zarasvandi, Alireza; Rezaei, Mohsen; Mahdavi, Reyhaneh; Ghanavati, Fatemeh

2017-10-01

The major celestite deposits in Zagros Fold belt are associated with coastal marine carbonate and evaporate sediments of Oligo-Miocene Asmari and Lower Miocene Ghachsaran Formations. In the Abolfares region, celestite mineralization is extended in the western limb of Bangestan anticline in the carbonates of Early Miocene (middle part of Asmari Formation), underlying by dolomitic carbonates of Burdigalian. From bottom to top three main types of mineralization can be distinguished in the study area: (1) layer texture resulting from replacement of algal limestone by celestite minerals with some parts showing idiomorphic crystals (geodes) along the walls of the cavities, (2) celestite occurrence as irregular massive shape interconnected small crystals and nodules, and (3) celestite mineralization associated with steeply dipping veins and open space fracture fillings, resulting from late-stage epigenetic processes. Highlightly, the ore-hosting carbonate rocks were deposited in an intertidal - supratidal protected setting with hypersaline conditions, in accordance with other celestite deposits of the Zagros Fold belt. The abundance of diagenetic crystallization rhythmites, carbonate and anhydrite inclusions as confirmed by Laser Raman spectroscopy analysis, high Sr/Ba values (average; 8726.1) and strong negative correlations between SO3 vs CaO (R2 = 0.98), SrO vs CaO (R2 = 0.96) with positive correlations between Ba vs SrO (R2 = 0.54) and SO3 vs SrO (R2 = 0.98) highlight the role of high Sr late-diagenetic brines in replacement of carbonates with celestite minerals. It seems that the inception of compressional folding during or soon after the deposition of the Asmari Formation in the carbonate platform at the margin of NW-trending basin in the foreland of the Zagros orogenic belt lead to the upward refluxing of penetrated high-Sr diagenetic brines and celestite mineralization.

New Insights into Early Cenozoic Carbon Cycling: Continental Ecosystem Response to Orbital Forcing in the Lacustrine Green River Formation (Western US) at the Conclusion of the Early Eocene Climatic Optimum

NASA Astrophysics Data System (ADS)

Musher, D.; Grogan, D. S.; Whiteside, J. H.

2010-12-01

A series of extreme warming events, known as hyperthermals, interrupted the equable climate conditions predominant during the early Cenozoic hothouse. In marine sediments, these hyperthermals are marked by prominent negative carbon isotope excursions, indicative of dramatic and abrupt changes in the global exogenic carbon pool, as well as carbonate dissolution horizons and benthic foraminiferal extinctions. Hyperthermals are well documented in the marine record, but it is less clear how patterns of global carbon cycling manifested in early Cenozoic terrestrial environments, although some studies have documented amplified excursions relative to that of the marine record. The lacustrine Eocene Green River Formation of Utah is an excellent system for studying the continental environmental context of global carbon cycle dynamics during this time. These sediments span a ~15 Myr time interval, including the entire Early Eocene Climatic Optimum (EECO) and the transition to the long-term Cenozoic cooling trend. To investigate the relationship between the continental carbon record and global carbon cycling, climate, and orbital forcing, we studied a detailed section from the P-4 core drilled in the Uinta Basin bracketing the famous “Mahogany Bed”, a petroliferous layer of oil shale recording a period of enhanced productivity and carbon burial near the end of the EECO. Our carbon isotope measurements of high molecular weight n-alkanes across this boundary suggest a stable global carbon cycle and climate regime persisting ~400 kyr at the terminal EECO. Frequency spectra of published oil yield and gamma ray data from this section reveal concentrated power at Milankovitch frequencies, permitting the assembly of a robust age model. In concert with radioisotopic age control, our orbital chronology allows for comparison of our carbon cycle record to early Eocene astronomical solutions. We show that the Mahogany Bed corresponds to strong minima in short and long eccentricity

Phosphorus retention and internal loading in the Bay of Quinte, Lake Ontario, using diagenetic modelling.

PubMed

Doan, Phuong T K; Watson, Sue B; Markovic, Stefan; Liang, Anqi; Guo, Jay; Mugalingam, Shan; Stokes, Jonathan; Morley, Andrew; Zhang, Weitao; Arhonditsis, George B; Dittrich, Maria

2018-04-24

Internal phosphorus (P) loading significantly contributes to hysteresis in ecosystem response to nutrient remediation, but the dynamics of sediment P transformations are often poorly characterized. Here, we applied a reaction-transport diagenetic model to investigate sediment P dynamics in the Bay of Quinte, a polymictic, spatially complex embayment of Lake Ontario, (Canada). We quantified spatial and temporal variability of sediment P binding forms and estimated P diffusive fluxes and sediment P retention in different parts of the bay. Our model supports the notion that diagenetic recycling of redox sensitive and organic bound P forms drive sediment P release. In the recent years, summer sediment P diffusive fluxes varied in the range of 3.2-3.6 mg P m -2  d -1 in the upper bay compared to 1.5 mg P m -2  d -1 in the middle-lower bay. Meanwhile sediment P retention ranged between 71% and 75% in the upper and middle-lower bay, respectively. The reconstruction of temporal trends of internal P loading in the past century, suggests that against the backdrop of reduced external P inputs, sediment P exerts growing control over the lake nutrient budget. Higher sediment P diffusive fluxes since mid-20th century with particular increase in the past 20 years in the shallower upper basins, emphasize limited sediment P retention potential and suggest prolonged ecosystem recovery, highlighting the importance of ongoing P control measures. Copyright © 2018 Elsevier B.V. All rights reserved.

Polygenetic Karsted Hardground Omission Surfaces in Lower Silurian Neritic Limestones: a Signature of Early Paleozoic Calcite Seas

NASA Astrophysics Data System (ADS)

James, Noel P.; Desrochers, André; Kyser, Kurt T.

2015-04-01

Exquisitely preserved and well-exposed rocky paleoshoreline omission surfaces in Lower Silurian Chicotte Formation limestones on Anticosti Island, Quebec, are interpreted to be the product of combined marine and meteoric diagenesis. The different omission features include; 1) planar erosional bedding tops, 2) scalloped erosional surfaces, 3) knobs, ridges, and swales at bedding contacts, and 4) paleoscarps. An interpretation is proposed that relates specific omission surface styles to different diagenetic-depositional processes that took place in separate terrestrial-peritidal-shallow neritic zones. Such processes were linked to fluctuations in relative sea level with specific zones of diagenesis such as; 1) karst corrosion, 2) peritidal erosion, 3) subtidal seawater flushing and cementation, and 4) shallow subtidal deposition. Most surfaces are interpreted to have been the result of initial extensive shallow-water synsedimentary lithification that were, as sea level fell, altered by exposure and subaerial corrosion, only to be buried by sediments as sea level rose again. This succession was repeated several times resulting in a suite of recurring polyphase omission surfaces through many meters of stratigraphic section. Synsedimentary cloudy marine cements are well preserved and are thus interpreted to have been calcitic originally. Aragonite components are rare and thought to have to have been dissolved just below the Silurian seafloor. Large molluscs that survived such seafloor removal were nonetheless leached and the resultant megamoulds were filled with synsedimentary calcite cement. These Silurian inner neritic-strandline omission surfaces are temporally unique. They are part of a suite of marine omission surfaces that are mostly found in early Paleozoic neritic carbonate sedimentary rocks. These karsted hardgrounds formed during a calcite-sea time of elevated marine carbonate saturation and extensive marine cement precipitation. The contemporaneous greenhouse

Testing Urey's carbonate-silicate cycle using the calcium isotopic composition of sedimentary carbonates

NASA Astrophysics Data System (ADS)

Blättler, Clara L.; Higgins, John A.

2017-12-01

Carbonate minerals constitute a major component of the sedimentary geological record and an archive of a fraction of the carbon and calcium cycled through the Earth's surface reservoirs for over three billion years. For calcium, carbonate minerals constitute the ultimate sink for almost all calcium liberated during continental and submarine weathering of silicate minerals. This study presents >500 stable isotope ratios of calcium in Precambrian carbonate sediments, both limestones and dolomites, in an attempt to characterize the isotope mass balance of the sedimentary carbonate reservoir through time. The mean of the dataset is indistinguishable from estimates of the calcium isotope ratio of bulk silicate Earth, consistent with the Urey cycle being the dominant mechanism exchanging calcium among surface reservoirs. The variability in bulk sediment calcium isotope ratios within each geological unit does not reflect changes in the global calcium cycle, but rather highlights the importance of local mineralogical and/or diagenetic effects in the carbonate record. This dataset demonstrates the potential for calcium isotope ratios to help assess these local effects, such as the former presence of aragonite, even in rocks with a history of neomorphism and recrystallization. Additionally, 29 calcium isotope measurements are presented from ODP (Ocean Drilling Program) Site 801 that contribute to the characterization of altered oceanic crust as an additional sink for calcium, and whose distinct isotopic signature places a limit on the importance of this subduction flux over Earth history.

Investigating controls on boron isotope ratios in shallow marine carbonates

NASA Astrophysics Data System (ADS)

Zhang, Shuang; Henehan, Michael J.; Hull, Pincelli M.; Reid, R. Pamela; Hardisty, Dalton S.; Hood, Ashleigh v. S.; Planavsky, Noah J.

2017-01-01

The boron isotope-pH proxy has been widely used to reconstruct past ocean pH values. In both planktic foraminifera and corals, species-specific calibrations are required in order to reconstruct absolute values of pH, due to the prevalence of so-called vital effects - physiological modification of the primary environmental signals by the calcifying organisms. Shallow marine abiotic carbonate (e.g. ooids and cements) could conceivably avoid any such calibration requirement, and therefore provide a potentially useful archive for reconstructions in deep (pre-Cenozoic) time. However, shallow marine abiotic carbonates could also be affected by local shifts in pH caused by microbial photosynthesis and respiration, something that has up to now not been fully tested. In this study, we present boron isotope measurements from shallow modern marine carbonates, from the Bahama Bank and Belize to investigate the potential of using shallow water carbonates as pH archives, and to explore the role of microbial processes in driving nominally 'abiogenic' carbonate deposition. For Bahama bank samples, our boron-based pH estimates derived from a range of carbonate types (i.e. ooids, peloids, hardground cements, carbonate mud, stromatolitic micrite and calcified filament micrite) are higher than the estimated modern mean-annual seawater pH values for this region. Furthermore, the majority (73%) of our marine carbonate-based pH estimates fall out of the range of the estimated pre-industrial seawater pH values for this region. In shallow sediment cores, we did not observe a correlation between measured pore water pH and boron-derived pH estimates, suggesting boron isotope variability is a depositional rather than early diagenetic signal. For Belize reef cements, conversely, the pH estimates are lower than likely in situ seawater pH at the time of cement formation. This study indicates the potential for complications when using shallow marine non-skeletal carbonates as marine pH archives

Invariance of the carbonate chemistry of the South China Sea from the glacial period to the Holocene and its implications to the Pacific Ocean carbonate system

NASA Astrophysics Data System (ADS)

Luo, Yiming; Kienast, Markus; Boudreau, Bernard P.

2018-06-01

Substantial and correlated changes in marine carbonate (CaCO3) content of oceanic sediments commonly accompany the transitions from cold glacial periods to warm interglacial periods. The South China Sea (SCS) is said to be ocean-dominated at depth, and its CaCO3 records should reflect and preserve the effects of changes in the carbonate chemistry of the (western) Pacific Ocean. Using published and newly acquired CaCO3 data and a model for carbonate compensation dynamics, we show that a significant change with respect to carbonate saturation is unlikely to have occurred in the SCS during the last glacial-interglacial transition. Instead, the results from a carbonate deposition model argue that the saturation state of the SCS was largely invariant; a separate diagenetic model argues that changes in sediment CaCO3 content can be explained by alterations in lithogenic input. In turn, this could indicate that the carbonate ion concentration of the (western) Pacific at depths shallower than the sill to the SCS (ca. 2,400 m) has not changed appreciably between the last glacial period and the present interglacial.

The Anarraaq Zn-Pb-Ag and barite deposit, northern Alaska: Evidence for replacement of carbonate by barite and sulfides

USGS Publications Warehouse

Kelley, K.D.; Dumoulin, Julie A.; Jennings, S.

2004-01-01

The Anarraaq deposit in northern Alaska consists of a barite body, estimated to be as much as 1 billion metric tons, and a Zn-Pb-Ag massive sulfide zone with an estimated resource of about 18 Mt at 18 percent Zn, 5.4 percent Pb, and 85 g/t Ag. The barite and sulfide minerals are hosted by the uppermost part of the Mississippian Kuna Formation (Ikalukrok unit) that consists of carbonaceous and siliceous mudstone or shale interbedded with carbonate. The amount of interbedded carbonate in the Anarraaq deposit is atypical of the district as a whole, comprising as much as one third of the section. The total thickness of the Ikalukrok unit is considerably greater in the area of the deposit (210 to almost 350 m) than to the north and south (maximum of 164 m). The mineralized zone at Anarraaq is lens shaped and has a relatively flat top and a convex base. It also ranges greatly in thickness, from a few meters to more than 100 m. Textures of some of the carbonate layers are distinctive, consisting of nodules within siliceous mudstone or layers interbedded with shale. Many of the layers contain calcitized sponge spicules or radiolarians in a carbonate matrix. Textures of barite and sulfide minerals mimic those of carbonate and provide unequivocal evidence that replacement of precursor carbonate was an important process. Barite and sulfide textures include either nodular, bladed grains of various sizes that resemble spicules (observed only with iron sulfides) or well-rounded forms that are replaced radiolarians. Mineralization at Anarraaq probably occurred in a fault-bounded Carboniferous basin during early diagenesis in the shallow subsurface. The shape and size of the mineralized body suggest that barite and sulfides replaced calcareous mass flow deposits in a submarine channel. The distribution of biogenic and/or early diagenetic silica may have served as impermeable barriers to the fluids, thereby focusing and controlling fluid flow through unreplaced carbonate layers

Carbon isotope fractionation of sapropelic organic matter during early diagenesis

USGS Publications Warehouse

Spiker, E. C.; Hatcher, P.G.

1984-01-01

Study of an algal, sapropelic sediment from Mangrove Lake, Bermuda shows that the mass balance of carbon and stable carbon isotopes in the major organic constituents is accounted for by a relatively straightforward model of selective preservation during diagenesis. The loss of 13C-enriched carbohydrates is the principal factor controlling the intermolecular mass balance of 13C in the sapropel. Results indicate that labile components are decomposed leaving as a residual concentrate in the sediment an insoluble humic substance that may be an original biochemical component of algae and associated bacteria. An overall decrease of up to about 4??? in the ?? 13C values of the organic matter is observed as a result of early diagenesis. ?? 1984.

Paleoenvironments, δ13C and δ18O signatures in the Neoproterozoic carbonates of the Comba Basin, Republic of Congo: Implications for regional correlations and Marinoan event

NASA Astrophysics Data System (ADS)

Préat, Alain; Delpomdor, Franck; Ackouala Mfere, Anna Perla; Callec, Yannick

2018-01-01

The Ediacaran Schisto-Calcaire Group is a ∼1300 m-thick succession belonging to the West Congo Supergroup in Central Africa. In the Comba Basin, it consists of three carbonate-dominated units defined as formations (SCI to SCIII) that are unconformably overlain by clastic deposits (Mpioka Group) interpreted as a molassic formation associated with the Panafrican Orogen. The underlying Upper Tillite and Cap Carbonate (SCIa) units, considered as markers of the Snowball Earth event were studied in three sections. We investigated the carbonates of the Schisto-Calcaire Group by defining new microfacies (MF1-MF7) and we performed C and O isotopic analyses in order to constraint the depositional and diagenetic events directly after the Marinoan interval. Stratigraphic variations of the stable isotopes are important in the series with lighter δ18O values (>1.5‰) than those of the Neoproterozoic ocean in the SCIc unit. According to regional stratigraphy a temperature effect can be dismissed and a freshwater surface layer is the origin of such negative δ18O values in this unit. The negative δ13C anomaly (-3.5‰ on average) of the Cap Carbonate is similarly to the δ18O values (-6.4‰ on average) in the range of the marine domain during postglacial sea level rise. The sample suite as a whole (SCII and SCIII formations) displays heavier δ18O and δ13C than those of the lower part (SCI unit) of the Schisto-Calcaire Group. The comparison with the Lower Congo (Democratic Republic of Congo) and Nyanga (Gabon) basins shows that the meteoric flushing in SCIc unit of the Schisto-Calcaire Group was regional and not local, and could be derived from a climatic evolution. Although an overall overprint is present, our isotopic relationships argue against overall diagenetic resetting of primary compositions and suggest that with careful examination combined with detailed petrographic analysis general depositional and diagenetic controls can be discerned in oxygen and carbon

Flavins in Coastal Marine Sediments: New Perspectives on Diagenetic Electron Transfer

NASA Astrophysics Data System (ADS)

Monteverde, D.; Berelson, W.; Baronas, J. J.; Sanudo-Wilhelmy, S. A.

2016-02-01

Coastal marine sediments play a critical role in the global cycling of metals and nutrients, many of which undergo diagenetic alteration. Central to these transformations are redox reactions where electron-rich organic matter is oxidized via transfer to terminal electron acceptors (NO3-, MnOx, FeOx, SO42-). The flavins (flavin adenine dinucleotide [FAD], flavin mononucleotide [FMN], and riboflavin [B2]) are microbially synthesized organic coenzymes that perform both single and double electron transfer and are known to mediate reduction of insoluble metal oxides. Culture experiments have found high rates of flavin excretion in metal-reducing Shewanella and Geobacter species, however environmental measurements of these highly labile molecules have not been previously reported. Here we present porewater measurements of FAD, FMN, and B2 from San Pedro Basin. This California Borderland basin is silled, suboxic, 900 m deep, and experiences high sedimentation. Flavin concentrations ranged from pico- (FAD: 0- 60 pM; B2: 40 - 90 pM) to nanomolar (FMN: 0.4 - 1.2 nM). The concentration cascade of FMN>B2>FAD fits well within culture experiments. Interestingly, profiles of all three flavins show a near linear increase with depth from 0-30 cm and a relatively steady concentration from 30-45 cm, supporting likely in situ production. Additionally, the flavins showed a negative correlation with dissolved Fe (R2 = 0.7 for FMN, 0.8 for FAD, and 0.9 for B2), which decreased linearly with depth from 160µM to 65µM. We discuss hypothesized mechanisms controlling flavin concentrations based on a suite of sediment geochemical parameters (dissolved Fe, Mn, TCO2, δ13C, NH3, DOM, and SO42-) as well as implications for microbial redox syntrophy. These data provide a critical link between the extensive culture-based mechanistic understanding of flavin function and the sedimentary environment. Furthermore, these results demonstrate that flavins likely serve as a significant electron transfer

Toward estimation of origin of methane at ancient seeps — Carbon isotopes of seep carbonates, lipid biomarkers, and adsorbed gas

NASA Astrophysics Data System (ADS)

Miyajima, Yusuke; Watanabe, Yumiko; Ijiri, Akira; Goto, Akiko; Jenkins, Robert; Hasegawa, Takashi; Sakai, Saburo; Matsumoto, Ryo

2017-04-01

Methane is generated mainly by microbial or thermal degradation of organic matter, and the origin of methane can be estimated based on its stable carbon isotopic signature. Seafloor seepages of methane-charged fluids have been a major source of methane to the ocean, and knowing the origin of methane at the methane seeps can provide valuable insights into the subsurface fluid circulation and biogeochemical processes. Methane seeps in the geological past are archived as authigenic methane-derived carbonate rocks, which precipitate via an alkalinity increase facilitated by microbially mediated anaerobic oxidation of methane. Here we attempted to estimate origins of methane at ancient seeps, based on several proxies preserved within the seep carbonates. We examined methane-seep carbonate rocks in the Japan Sea region, collected from lower Miocene to middle Pleistocene sediments at 11 sites on land, and also carbonate nodules collected from the seafloor off Joetsu, where thermogenic methane is seeping. Carbon isotopic compositions of the carbonates and lipid biomarkers of methane-oxidizing archaea within them were analyzed. In order to directly know original isotopic signatures of methane, we also attempted to extract adsorbed methane through acid dissolution of the powdered carbonates. Early-diagenetic carbonate phases show various δ13C values between -64.7 and -4.7‰ vs. VPDB, suggesting either biogenic or thermogenic, or both origins of methane. A lipid biomarker pentamethylicosane (PMI) extracted from the ancient carbonates has δ13C values mostly lower than -100‰ , whereas that from the modern methane-derived carbonate nodule has a higher value (-80‰ ). The δ13C values of the seeping methane (-36‰ ) and PMI in the modern Joetsu seep carbonate shows an offset of -44‰ . If this carbon isotope offset was similar at the ancient seeps, the δ13C values of PMI indicate that methane at ancient seeps in the Japan Sea region was biogenic in origin, with δ13C

Carbon dioxide warming of the early Earth

NASA Technical Reports Server (NTRS)

Arrhenius, G.

1997-01-01

Svante Arrhenius' research in atmospheric physics extended beyond the recent past and the near future states of the Earth, which today are at the center of sociopolitical attention. His plan encompassed all of the physical phenomena known at the time to relate to the formation and evolution of stars and planets. His two-volume textbook on cosmic physics is a comprehensive synopsis of the field. The inquiry into the possible cause of the ice ages and the theory of selective wavelength filter control led Arrhenius to consider the surface states of the other terrestrial planets, and of the ancient Earth before it had been modified by the emergence of life. The rapid escape of hydrogen and the equilibration with igneous rocks required that carbon in the early atmosphere prevailed mainly in oxidized form as carbon dioxide, together with other photoactive gases exerting a greenhouse effect orders of magnitude larger than in our present atmosphere. This effect, together with the ensuing chemical processes, would have set the conditions for life to evolve on our planet, seeded from spores spreading through an infinite Universe, and propelled, as Arrhenius thought, by stellar radiation pressure.

Carbon dioxide warming of the early Earth.

PubMed

Arrhenius, G

1997-02-01

Svante Arrhenius' research in atmospheric physics extended beyond the recent past and the near future states of the Earth, which today are at the center of sociopolitical attention. His plan encompassed all of the physical phenomena known at the time to relate to the formation and evolution of stars and planets. His two-volume textbook on cosmic physics is a comprehensive synopsis of the field. The inquiry into the possible cause of the ice ages and the theory of selective wavelength filter control led Arrhenius to consider the surface states of the other terrestrial planets, and of the ancient Earth before it had been modified by the emergence of life. The rapid escape of hydrogen and the equilibration with igneous rocks required that carbon in the early atmosphere prevailed mainly in oxidized form as carbon dioxide, together with other photoactive gases exerting a greenhouse effect orders of magnitude larger than in our present atmosphere. This effect, together with the ensuing chemical processes, would have set the conditions for life to evolve on our planet, seeded from spores spreading through an infinite Universe, and propelled, as Arrhenius thought, by stellar radiation pressure.

Seasonal variations in production and consumption rates of dissolved organic carbon in an organic-rich coastal sediment

NASA Astrophysics Data System (ADS)

Alperin, M. J.; Albert, D. B.; Martens, C. S.

1994-11-01

Dissolved organic carbon (DOC) concentrations in anoxic marine sediments are controlled by at least three processes: (1) production of nonvolatile dissolved compounds, such as peptides and amino acids, soluble saccharides and fatty acids, via hydrolysis of particulate organic carbon (POC). (2) conversion of these compounds to volatile fatty acids and alcohols by fermentative bacteria. (3) consumption of volatile fatty acids and alcohols by terminal bacteria, such as sulfate reducers and methanogens. We monitored seasonal changes in concentration profiles of total DOC, nonacid-volatile (NAV) DOC and acid-volatile (AV) DOC in anoxic sediment from Cape Lookout Bight, North Carolina, USA, in order to investigate the factors that control seasonal variations in rates of hydrolysis, fermentation, and terminal metabolism. During the winter months, DOC concentrations increased continuously from 0.2 mM in the bottomwater to ~4 mM at a depth of 36 cm in the sediment column. During the summer, a large DOC maximum developed between 5 and 20 cm, with peak concentrations approaching 10 mM. The mid-depth summertime maximum was driven by increases in both NAV- and AV-DOC concentrations. Net NAV-DOC reaction rates were estimated by a diagenetic model applied to NAV-DOC concentration profiles. Depth-integrated production rates of NAV-DOC increased from February through July, suggesting that net rates of POC hydrolysis during this period are controlled by temperature. Net consumption of NAV-DOC during the late summer and early fall suggests reduced gross NAV-DOC production rates, presumably due to a decline in the availability of labile POC. A distinct subsurface peak in AV-DOC concentration developed during the late spring, when the sulfate depletion depth shoaled from 25 to 10 cm. We hypothesize that the AV-DOC maximum results from a decline in consumption by sulfate-reducing bacteria (due to sulfate limitation) and a lag in the development of an active population of methanogenic

A warm or a cold early Earth? New insights from a 3-D climate-carbon model

NASA Astrophysics Data System (ADS)

Charnay, Benjamin; Le Hir, Guillaume; Fluteau, Frédéric; Forget, François; Catling, David C.

2017-09-01

Oxygen isotopes in marine cherts have been used to infer hot oceans during the Archean with temperatures between 60 °C (333 K) and 80 °C (353 K). Such climates are challenging for the early Earth warmed by the faint young Sun. The interpretation of the data has therefore been controversial. 1D climate modeling inferred that such hot climates would require very high levels of CO2 (2-6 bars). Previous carbon cycle modeling concluded that such stable hot climates were impossible and that the carbon cycle should lead to cold climates during the Hadean and the Archean. Here, we revisit the climate and carbon cycle of the early Earth at 3.8 Ga using a 3D climate-carbon model. We find that CO2 partial pressures of around 1 bar could have produced hot climates given a low land fraction and cloud feedback effects. However, such high CO2 partial pressures should not have been stable because of the weathering of terrestrial and oceanic basalts, producing an efficient stabilizing feedback. Moreover, the weathering of impact ejecta during the Late Heavy Bombardment (LHB) would have strongly reduced the CO2 partial pressure leading to cold climates and potentially snowball Earth events after large impacts. Our results therefore favor cold or temperate climates with global mean temperatures between around 8 °C (281 K) and 30 °C (303 K) and with 0.1-0.36 bar of CO2 for the late Hadean and early Archean. Finally, our model suggests that the carbon cycle was efficient for preserving clement conditions on the early Earth without necessarily requiring any other greenhouse gas or warming process.

Depositional and diagenetic processes of Qa Khanna playa, North Jordan basaltic plateau, Jordan

NASA Astrophysics Data System (ADS)

Howari, F. M.; Banat, K. M.; Abu-Salha, Y. A.

2010-09-01

The present study explored mineral occurrences and sediment characteristics of playas from northern Jordan and explained depositional and diagenetic processes as reflected from bulk chemistry and sedimentary structures. Mudcracks of different sizes and shape patterns, laminations, intersediment vesicles, and bioturbation pipes are the main sedimentary structures. Plagioclase, olivine, orthopyroxene, nepheline and other opaque minerals are all of detrital origin, and are derived from the basaltic bedrocks surrounding the studied playa. Evaporites are very rare; they are represented only by trace amounts of gypsum. The identified clay minerals in the clay fraction of the studied sediments, arranged according to their decreasing abundances are palygorskite, illite, kaolinite, smectite and chlorite. The elemental abundances were tied to clay, CaCO 3 and nearby igneous rocks. The type of clay minerals, the high pH values of the studied sediments, and the considerable incorporation of Mg and K in palygorskite and illite respectively, may strongly reflect a high evaporative and alkaline environment under arid to semi-arid conditions in an ephemeral lake of the Qa Khanna. Concentrations and distributions of both major and trace elements are essentially controlled by the clay mineralogy and the calcium carbonate content; Ca is mainly incorporated in the CaCO 3, which is either generated authigenically or by aeolian deposition. Fe and K are incorporated and fixed by illite under an evaporative and alkaline environment. Mg is incorporated in palygorskite while Mn is adsorbed on various clay minerals. Sr substitutes for Ca in the aeolian CaCO 3 and its presence in the studied sediments is independent of the prevailing conditions during the playa evolution. Rb substitutes for K in illite under the prevailing chemical conditions in the studied playa.

Warming early Mars with carbon dioxide clouds that scatter infrared radiation.

PubMed

Forget, F; Pierrehumbert, R T

1997-11-14

Geomorphic evidence that Mars was warm enough to support flowing water about 3.8 billion years ago presents a continuing enigma that cannot be explained by conventional greenhouse warming mechanisms. Model calculations show that the surface of early Mars could have been warmed through a scattering variant of the greenhouse effect, resulting from the ability of the carbon dioxide ice clouds to reflect the outgoing thermal radiation back to the surface. This process could also explain how Earth avoided an early irreversible glaciation and could extend the size of the habitable zone on extrasolar planets around stars.

Chemical Remagnetization of Jurassic Carbonates and a Primary Paleolatitude of Lower Cretaceous Volcaniclastic Rocks of the Tibetan Himalaya

NASA Astrophysics Data System (ADS)

Huang, W.; Van Hinsbergen, D. J. J.; Dekkers, M. J.; Garzanti, E.; Dupont Nivet, G.; Lippert, P. C.; Li, X.; Maffione, M.; Langereis, C. G.; Hu, X.; Guo, Z.; Kapp, P. A.

2014-12-01

Paleolatitudes for the Tibetan Himalaya Zone based on paleomagnetic inclinations provide kinematic constraints of the passive northern Indian margin and the extent of 'Greater India' before the India-Asia collision. Here, we present a paleomagnetic investigation of the Jurassic (carbonates) to Lower Cretaceous (volcaniclastic rocks) Wölong section of the Tibetan Himalaya in the Everest region. The carbonates yield positive fold tests, suggesting that the remanent magnetizations have a pre-folding origin. However, detailed paleomagnetic analyses, rock magnetic tests, end-member modeling of acquisition curves of isothermal remanent magnetization, and petrographic studies reveal that the magnetic carrier of the Jurassic carbonates is authigenic magnetite, whereas the dominant magnetic carrier of the Lower Cretaceous volcaniclastic rocks is detrital magnetite. We conclude that the Jurassic carbonates were remagnetized, whereas the Lower Cretaceous volcaniclastics retain a primary remanence. We hypothesize that remagnetization of the Jurassic carbonates was probably caused by the oxidation of early diagenetic pyrite to magnetite within the time interval at ~86-84 Ma during the latest Cretaceous Normal Superchron and earliest deposition of Cretaceous oceanic red beds in the Tibetan Himalaya. The remagnetization of the limestones prevents determining the size of 'Greater India' during Jurassic time. Instead, a paleolatitude of the Tibetan Himalaya of 23.8±2.1° S at ~86-84 Ma is suggested. This value is lower than the expected paleolatitude of India from apparent polar wander path (APWP). The volcaniclastic rocks with the primary remanence, however, yielded a Lower Cretaceous paleolatitude of Tibetan Himalaya of 55.5±3° S, fitting well with the APWP of India.

Footwall progradation in syn-rift carbonate platform-slope systems (Early Jurassic, Northern Apennines, Italy)

NASA Astrophysics Data System (ADS)

Fabbi, Simone; Santantonio, Massimo

2012-12-01

The so-called Umbria-Marche Domain of Northern Apennines represents a vast depositional system, also stretching across the Adriatic Sea subsurface, that was characterized by dominantly pelagic sedimentation through most of its Jurassic to Oligocene/Early Miocene history. The pelagic succession is underlain by Hettangian shallow-water carbonates (Calcare Massiccio Fm.), constituting a regional carbonate platform that was subjected to tectonic extension due to rifting of the Adria/African Plate in the earliest Jurassic. While tectonic subsidence of the hangingwalls drove the drowning of the platform around the Hettangian/Sinemurian boundary, the production of benthic carbonate on footwall blocks continued parallel to faulting, through a sequence of facies that was abruptly terminated by drowning and development of condensed pelagites in the early Pliensbachian. By then rifting had ceased, so that the Pliensbachian to Early Cretaceous hangingwall deposits represent a post-rift basin-fill succession onlapping the tectonically-generated escarpment margins of the highs. During the early phases of syndepositional faulting, the carbonate factories of footwall blocks were still temporarily able to fill part of the accommodation space produced by the normal faults by prograding into the incipient basins. In this paper we describe for the first time a relatively low-angle (< 10°) clinoform bed package documenting such an ephemeral phase of lateral growth of a carbonate factory. The clinoforms are sigmoidal, and form low-relief (maximum 5-7 m) bodies representing a shallow-water slope that was productive due to development of a Lithocodium-dominated factory. Continued faulting and hangingwall subsidence then decoupled the slope from the platform top, halting the growth of clinoforms and causing the platform margin to switch from accretionary to bypass mode as the pre-rift substrate became exposed along a submarine fault escarpment. The downfaulted clinoform slope was then

Climate Warming Can Increase Soil Carbon Fluxes Without Decreasing Soil Carbon Stocks in Boreal Forests

NASA Astrophysics Data System (ADS)

Ziegler, S. E.; Benner, R. H.; Billings, S. A.; Edwards, K. A.; Philben, M. J.; Zhu, X.; Laganiere, J.

2016-12-01

Ecosystem C fluxes respond positively to climate warming, however, the net impact of changing C fluxes on soil organic carbon (SOC) stocks over decadal scales remains unclear. Manipulative studies and global-scale observations have informed much of the existing knowledge of SOC responses to climate, providing insights on relatively short (e.g. days to years) and long (centuries to millennia) time scales, respectively. Natural climate gradient studies capture integrated ecosystem responses to climate on decadal time scales. Here we report the soil C reservoirs, fluxes into and out of those reservoirs, and the chemical composition of inputs and soil organic matter pools along a mesic boreal forest climate transect. The sites studied consist of similar forest composition, successional stage, and soil moisture but differ by 5.2°C mean annual temperature. Carbon fluxes through these boreal forest soils were greatest in the lowest latitude regions and indicate that enhanced C inputs can offset soil C losses with warming in these forests. Respiration rates increased by 55% and the flux of dissolved organic carbon from the organic to mineral soil horizons tripled across this climate gradient. The 2-fold increase in litterfall inputs to these soils coincided with a significant increase in the organic horizon C stock with warming, however, no significant difference in the surface mineral soil C stocks was observed. The younger mean age of the mineral soil C ( 70 versus 330 YBP) provided further evidence for the greater turnover of SOC in the warmer climate soils. In spite of these differences in mean radiocarbon age, mineral SOC exhibited chemical characteristics of highly decomposed material across all regions. In contrast with depth trends in soil OM diagenetic indices, diagenetic shifts with latitude were limited to increases in C:N and alkyl to O-alkyl ratios in the overlying organic horizons in the warmer relative to the colder regions. These data indicate that the

In situ trace metal analysis of Neoarchaean--Ordovician shallow-marine microbial-carbonate-hosted pyrites.

PubMed

Gallagher, M; Turner, E C; Kamber, B S

2015-07-01

Pre-Cambrian atmospheric and oceanic redox evolutions are expressed in the inventory of redox-sensitive trace metals in marine sedimentary rocks. Most of the currently available information was derived from deep-water sedimentary rocks (black shale/banded iron formation). Many of the studied trace metals (e.g. Mo, U, Ni and Co) are sensitive to the composition of the exposed land surface and prevailing weathering style, and their oceanic inventory ultimately depends on the terrestrial flux. The validity of claims for increased/decreased terrestrial fluxes has remained untested as far as the shallow-marine environment is concerned. Here, the first systematic study of trace metal inventories of the shallow-marine environment by analysis of microbial carbonate-hosted pyrite, from ca. 2.65-0.52 Ga, is presented. A petrographic survey revealed a first-order difference in preservation of early diagenetic pyrite. Microbial carbonates formed before the 2.4 Ga great oxygenation event (GOE) are much richer in pyrite and contain pyrite grains of greater morphological variability but lesser chemical substitution than samples deposited after the GOE. This disparity in pyrite abundance and morphology is mirrored by the qualitative degree of preservation of organic matter (largely as kerogen). Thus, it seems that in microbial carbonates, pyrite formation and preservation were related to presence and preservation of organic C. Several redox-sensitive trace metals show interpretable temporal trends supporting earlier proposals derived from deep-water sedimentary rocks. Most notably, the shallow-water pyrite confirms a rise in the oceanic Mo inventory across the pre-Cambrian-Cambrian boundary, implying the establishment of efficient deep-ocean ventilation. The carbonate-hosted pyrite also confirms the Neoarchaean and early Palaeoproterozoic ocean had higher Ni concentration, which can now more firmly be attributed to a greater proportion of magnesian volcanic rock on land rather

An integrated bio-chemostratigraphic framework for Lower Cretaceous (Barremian-Cenomanian) shallow-water carbonates of the Central Apennines (Italy)

NASA Astrophysics Data System (ADS)

Schmitt, Katharina; Heimhofer, Ulrich; Frijia, Gianluca; Huck, Stefan

2017-04-01

Shallow-water carbonate platform sections are valuable archives for the reconstruction of deep-time environmental and climatic conditions, but the biostratigraphic resolution is often rather low. Moreover, chemostratigraphic correlation with well-dated pelagic sections by means of bulk carbonate carbon-isotope stratigraphy is notoriously difficult and afflicted with large uncertainties, as shallow-water sections are particularly prone to the impact of diagenesis. In the current study, an integrated biostratigraphic-chemostratigraphic approach is applied to southern Tethyan Lower Cretaceous carbonate platform deposits (Santa Lucia, Monte La Costa sections) situated in the Central Apennines in Italy. The 500 m thick Santa Lucia section, representing an open lagoonal inner carbonate platform setting, provides a characteristic carbon- and oxygen-isotope pattern that allows for correlation with pelagic composite reference curves (Vocontian and Umbria Marche basins). Calibrated by means of foraminiferal biostratigraphy and rudist bivalve strontium-isotope stratigraphy, the section serves as local chemostratigraphic shallow-water reference for the Barremian to Cenomanian. The 250 m thick Monte La Costa section comprises predominantly coarse grained (biostromal) and often strongly cemented shelf margin deposits. Although benthic foraminifera are scarce and the carbonates evidently suffered strong diagenetic alteration, high-resolution (rudist shell) strontium-isotope stratigraphy in combination with superimposed carbon-isotope trends and biological-lithological changes (e.g., mass occurrences of Bacinella irregularis s.l) enables correlation with the Early Albian to Cenomanian portion of the Santa Lucia reference section. At both localities, chemostratigraphy indicates a major gap covering large parts of the Lower and middle Cenomanian. After having considerably improved the stratigraphic resolution of the studied sections, selected best-preserved rudist shells are going

Diet and mobility in Early Medieval Bavaria: a study of carbon and nitrogen stable isotopes.

PubMed

Hakenbeck, Susanne; McManus, Ellen; Geisler, Hans; Grupe, Gisela; O'Connell, Tamsin

2010-10-01

This study investigates patterns of mobility in Early Medieval Bavaria through a combined study of diet and associated burial practice. Carbon and nitrogen isotope ratios were analyzed in human bone samples from the Late Roman cemetery of Klettham and from the Early Medieval cemeteries of Altenerding and Straubing-Bajuwarenstrasse. For dietary comparison, samples of faunal bone from one Late Roman and three Early Medieval settlement sites were also analyzed. The results indicate that the average diet was in keeping with a landlocked environment and fairly limited availability of freshwater or marine resources. The diet appears not to have changed significantly from the Late Roman to the Early Medieval period. However, in the population of Altenerding, there were significant differences in the diet of men and women, supporting a hypothesis of greater mobility among women. Furthermore, the isotopic evidence from dietary outliers is supported by "foreign" grave goods and practices, such as artificial skull modification. These results reveal the potential of carbon and nitrogen isotope analysis for questions regarding migration and mobility. © 2010 Wiley-Liss, Inc.

Carbon dioxide sources from Alaska driven by increasing early winter respiration from Arctic tundra

PubMed Central

Lindaas, Jakob; Benmergui, Joshua; Luus, Kristina A.; Chang, Rachel Y.-W.; Daube, Bruce C.; Euskirchen, Eugénie S.; Karion, Anna; Miller, John B.; Miller, Scot M.; Parazoo, Nicholas C.; Randerson, James T.; Sweeney, Colm; Thoning, Kirk; Veraverbeke, Sander; Miller, Charles E.; Wofsy, Steven C.

2017-01-01

High-latitude ecosystems have the capacity to release large amounts of carbon dioxide (CO2) to the atmosphere in response to increasing temperatures, representing a potentially significant positive feedback within the climate system. Here, we combine aircraft and tower observations of atmospheric CO2 with remote sensing data and meteorological products to derive temporally and spatially resolved year-round CO2 fluxes across Alaska during 2012–2014. We find that tundra ecosystems were a net source of CO2 to the atmosphere annually, with especially high rates of respiration during early winter (October through December). Long-term records at Barrow, AK, suggest that CO2 emission rates from North Slope tundra have increased during the October through December period by 73% ± 11% since 1975, and are correlated with rising summer temperatures. Together, these results imply increasing early winter respiration and net annual emission of CO2 in Alaska, in response to climate warming. Our results provide evidence that the decadal-scale increase in the amplitude of the CO2 seasonal cycle may be linked with increasing biogenic emissions in the Arctic, following the growing season. Early winter respiration was not well simulated by the Earth System Models used to forecast future carbon fluxes in recent climate assessments. Therefore, these assessments may underestimate the carbon release from Arctic soils in response to a warming climate. PMID:28484001

Carbon dioxide sources from Alaska driven by increasing early winter respiration from Arctic tundra.

PubMed

Commane, Róisín; Lindaas, Jakob; Benmergui, Joshua; Luus, Kristina A; Chang, Rachel Y-W; Daube, Bruce C; Euskirchen, Eugénie S; Henderson, John M; Karion, Anna; Miller, John B; Miller, Scot M; Parazoo, Nicholas C; Randerson, James T; Sweeney, Colm; Tans, Pieter; Thoning, Kirk; Veraverbeke, Sander; Miller, Charles E; Wofsy, Steven C

2017-05-23

High-latitude ecosystems have the capacity to release large amounts of carbon dioxide (CO 2 ) to the atmosphere in response to increasing temperatures, representing a potentially significant positive feedback within the climate system. Here, we combine aircraft and tower observations of atmospheric CO 2 with remote sensing data and meteorological products to derive temporally and spatially resolved year-round CO 2 fluxes across Alaska during 2012-2014. We find that tundra ecosystems were a net source of CO 2 to the atmosphere annually, with especially high rates of respiration during early winter (October through December). Long-term records at Barrow, AK, suggest that CO 2 emission rates from North Slope tundra have increased during the October through December period by 73% ± 11% since 1975, and are correlated with rising summer temperatures. Together, these results imply increasing early winter respiration and net annual emission of CO 2 in Alaska, in response to climate warming. Our results provide evidence that the decadal-scale increase in the amplitude of the CO 2 seasonal cycle may be linked with increasing biogenic emissions in the Arctic, following the growing season. Early winter respiration was not well simulated by the Earth System Models used to forecast future carbon fluxes in recent climate assessments. Therefore, these assessments may underestimate the carbon release from Arctic soils in response to a warming climate.

Carbon dioxide sources from Alaska driven by increasing early winter respiration from Arctic tundra

NASA Astrophysics Data System (ADS)

Commane, Róisín; Lindaas, Jakob; Benmergui, Joshua; Luus, Kristina A.; Chang, Rachel Y.-W.; Daube, Bruce C.; Euskirchen, Eugénie S.; Henderson, John M.; Karion, Anna; Miller, John B.; Miller, Scot M.; Parazoo, Nicholas C.; Randerson, James T.; Sweeney, Colm; Tans, Pieter; Thoning, Kirk; Veraverbeke, Sander; Miller, Charles E.; Wofsy, Steven C.

2017-05-01

High-latitude ecosystems have the capacity to release large amounts of carbon dioxide (CO2) to the atmosphere in response to increasing temperatures, representing a potentially significant positive feedback within the climate system. Here, we combine aircraft and tower observations of atmospheric CO2 with remote sensing data and meteorological products to derive temporally and spatially resolved year-round CO2 fluxes across Alaska during 2012-2014. We find that tundra ecosystems were a net source of CO2 to the atmosphere annually, with especially high rates of respiration during early winter (October through December). Long-term records at Barrow, AK, suggest that CO2 emission rates from North Slope tundra have increased during the October through December period by 73% ± 11% since 1975, and are correlated with rising summer temperatures. Together, these results imply increasing early winter respiration and net annual emission of CO2 in Alaska, in response to climate warming. Our results provide evidence that the decadal-scale increase in the amplitude of the CO2 seasonal cycle may be linked with increasing biogenic emissions in the Arctic, following the growing season. Early winter respiration was not well simulated by the Earth System Models used to forecast future carbon fluxes in recent climate assessments. Therefore, these assessments may underestimate the carbon release from Arctic soils in response to a warming climate.

Carbon isotopic evidence for photosynthesis in Early Cambrian oceans

NASA Astrophysics Data System (ADS)

Surge, Donna M.; Savarese, Michael; Dodd, J. Robert; Lohmann, Kyger C.

1997-06-01

Were the first metazoan reefs ecologically similar to modern tropical reefs, enabling them to persist under oligotrophic conditions? We tested the hypothesis of ecological similarity by employing a geochemical approach. Petrography, cathodoluminescence, trace elements, and stable isotope analyses of primary precipitates of the Lower Cambrian Ajax Limestone, South Australia, indicate preservation of original C isotopic composition. All primary carbonate components exhibit C isotopic values similar to the composition of inorganically precipitated fibrous marine cements, suggesting that archaeocyaths and the calcimicrobe Epiphyton precipitated skeletal carbonate in equilibrium with ambient seawater in the absence of vital effects. Such data do not support the contention that archaeocyaths possessed photosymbionts. However, a +0.55‰ shift in δ13C occurs in reefs developed under shallower-water conditions relative to deeper reefs. This shift suggests the stratification of primary production in Early Cambrian oceans. The pattern is similar to that seen in the modern ocean, whereby significant photosynthesis modulates the C isotopic composition of the photic zone.

An AEM-TEM study of weathering and diagenesis, Abert Lake, Oregon: II. Diagenetic modification of the sedimentary assemblage

USGS Publications Warehouse

Banfield, J.F.; Jones, B.F.; Veblen, D.R.

1991-01-01

This paper compares the mineralogy and chemistry of clay minerals in sediments from various depths and positions in Abert Lake and surrounding playa with those of the weathered materials entering the lake in order to reveal the nature and extent of post-depositional mineralogical modification. Analytical electron microscope (AEM) data from individual clay particles reveal that each sample is comprised of a highly inhomogeneous smectite assemblage. The thin clay flakes (commonly less than 10 nm wide) display a complete range in octahedral sheet compositions from nearly dioctahedral to nearly trioctahedral. The very abundant Mg-rich lake smectites with an estimated composition K0.29(Al0.23-Mg2.16Fe0.30)Si3.80Al0.20O10(OH)2 are not formed by weathering. This confirms the importance of diagenetic Mg uptake. Lattice-fringe imaging failed to reveal distinct brucite-like or vermiculite-like layers, suggesting that interstratifications of this type are rare or absent. Siliceous coatings on clay particles (identified by silica excess in smectite analyses) seem to favor topotactic overgrowth of stevensite rather than addition of brucite-like layers to the dioctahedral nuclei. The growth of K-stevensite dilutes the Al content of the crystal, and thus the increasing diagenetic modification reduces rather than supplements its illite component. Smectite compositions within individual samples were highly variable, yet source-related characteristics such as the abundance of Fe-rich smectite were apparent. Little evidence for systematic K or Mg enrichment with depth was identified in samples from depths of down to 16 feet below the sediment-water interface. The most magnesian assemblages are associated both with weathering sources of Mg-rich smectite and playa environments subjected to repeated wetting and drying cycles. Thus, the observations suggest that clay compositions primarily reflect changes in lake levels, brine composition, and source characteristics, rather than time and

Modeling Chemical and Isotopic Variations in Lab Formed Hydrothermal Carbonates

NASA Technical Reports Server (NTRS)

Niles, P. B.; Leshin, L. A.; Golden, D. C.; Socki, R. A.; Guan, Y.; Ming, D. W.

2005-01-01

Chemical and mineralogical data (e.g. [1]) from Mars suggest that the history of liquid water on the planet was more sporadic in nature than long-lived. The non-equilibrium chemical and isotopic compositions of the carbonates preserved in the martian meteorite ALH84001 are direct evidence of ancient secondary minerals that have not undergone significant diagenesis or stabilization processes typical of long-lived aqueous systems on Earth. Thus secondary minerals and sediments on Mars may primarily record the characteristics of the aqueous environment in which they formed without being significantly overprinted by subsequent diagenetic processes during burial.

Constraining the cause of the end-Guadalupian extinction with coupled records of carbon and calcium isotopes

NASA Astrophysics Data System (ADS)

Jost, A. B.; Mundil, R.; He, B.; Brown, S. T.; Altiner, D.; Sun, Y.; DePaolo, D. J.; Payne, J.

2013-12-01

A negative δ13C excursion in carbonate sediments from Guadalupian (Middle Permian) and Lopingian (Late Permian) stratigraphic sections has been interpreted to result from a large carbon cycle disturbance during end-Guadalupian extinction event (ca. 260 Ma). However, the carbon isotope data alone are insufficient to uniquely determine the type and magnitude of perturbations to the global carbon cycle. The carbon and calcium cycles are coupled via CaCO3 burial, so changes in calcium isotopes can be used to constrain the cause of a carbon isotope excursion. In this study, we present coupled carbon and calcium isotope records from three Guadalupian-Lopingian (G/L) sections in China and Turkey. Isotope records among our studied sections are inconsistent in both their δ13C and δ44/40Ca records. Similar inconsistencies in δ13C among sections occur across previously published datasets. Sections with large (>3‰) changes in δ13C either show evidence for diagenetic alteration or do not show δ13C and δ44/40Ca changes consistent with severe volcanic degassing from Emeishan or methane clathrate destabilization. We conclude that the large isotopic changes are more likely the result of local burial conditions or diagenetic effects, rather than a large carbon cycle disturbance. Perturbations to the global carbon and calcium cycles appear to have been much smaller across the G/L transition than across the subsequent Permian-Triassic boundary. This finding is consistent with recent paleobiological data showing that the end-Guadalupian extinction was much less severe than previously believed, and was indistinguishable in magnitude from background intervals. However, selective extinction of marine animals with passive respiratory physiology indicates that the G/L extinction cannot simply be due to background extinction or sampling failure, and that it was triggered by some environmental event. Therefore, any environmental event must have been small enough to not generate large

Mineralogy of Nicobar Fan turbidites (IODP Leg 362): Himalayan provenance and diagenetic control.

NASA Astrophysics Data System (ADS)

Limonta, M.; Garzanti, E.; Ando, S.; Carter, A.; Milliken, K. L.; Pickering, K. T.

2017-12-01

In this study we use quantitative petrographic and heavy-mineral data on silt-sized and sand-sized sediments from the Nicobar Fan turbiditic depositional system to unravel their provenance and discriminate between pre-depositional and post-depositional processes controlling sediment mineralogy. Eighteen samples from the two drill sites U1480 e U1481, collected down to a depth of 1400 m during International Ocean Discovery Expedition 362, were selected for analysis. A complete section of the sedimentary section overlying oceanic basaltic basement was recovered at the U1480 drill site, whereas the U1481 drill site, located 35 km to the southeast, focused on the deeper interval of the sedimentary section overlying oceanic basement. Here we illustrate the compositional trends observed throughout the recovered succession, and compare heavy-mineral suites characterizing sediments drilled at the two U1480 and U1481 sites to check for potential differences in sediment provenance over a relatively short distance in trench settings. Diagenetic control with increasing burial depth was also specifically investigated. In Pleistocene sediments at depths of a few tens of meters only, rich heavy-mineral assemblages include mainly hornblende, epidote, and garnet, associated with apatite, clinopyroxene, tourmaline, sillimanite, kyanite, zircon, titanite, and rare staurolite and rutile, testifying to long-distance provenance from the Himalayan range via the Ganga-Brahmaputra fluvio-deltaic-turbiditic system. Heavy-mineral concentration shows a progressive decrease with burial depth, pointing to selective diagenetic dissolution of less durable detrital minerals. Clinopyroxene becomes rare below 400 m depth and was not recorded below 500 m depth, where amphibole decreases notably in relative abundance. More durable heavy minerals, including zircon, tourmaline, apatite, garnet and epidote, consequently tend to be relatively enriched with increasing age and burial depth. Petrographic and

Mesozoic (Lower Jurassic) red stromatactis limestones from the Southern Alps (Arzo, Switzerland): calcite mineral authigenesis and syneresis-type deformation

NASA Astrophysics Data System (ADS)

Neuweiler, Fritz; Bernoulli, Daniel

2005-02-01

The Broccatello lithological unit (Lower Jurassic, Hettangian to lower parts of Upper Sinemurian) near the village of Arzo (southern Alps, southern Switzerland) is a mound-shaped carbonate deposit that contains patches of red stromatactis limestone. Within the largely bioclastic Broccatello unit, the stromatactis limestone is distinguished by its early-diagenetic cavity system, a relatively fine-grained texture, and an in-situ assemblage of calcified siliceous sponges (various demosponges and hexactinellids). A complex shallow subsurface diagenetic pathway can be reconstructed from sediment petrography in combination with comparative geochemical analysis (carbon and oxygen isotopes; trace and rare earth elements, REE + Y). This pathway includes organic matter transformation, aragonite and skeletal opal dissolution, patchy calcification and lithification, sediment shrinkage, sagging and collapse, partial REE remobilization, and multiple sediment infiltration. These processes occurred under normal-marine, essentially oxic conditions and were independent from local, recurring syn-sedimentary faulting. It is concluded that the stromatactis results from a combination of calcite mineral authigenesis and syneresis-type deformation. The natural stromatactis phenomenon may thus be best explained by maturation processes of particulate polymer gels expected to form in fine-grained carbonate sediments in the shallow subsurface. Conditions favorable for the evolution of stromatactis appear to be particularly frequent during drowning of tropical or subtropical carbonate platforms.

Climate Cycling on Early Mars Caused by the Carbonate-Silicate Cycle

NASA Astrophysics Data System (ADS)

Kasting, J. F.; Batalha, N. E.; Haqq-Misra, J. D.; Kopparapu, R.

2016-12-01

For decades, scientists have tried to explain the evidence for fluvial activity on early Mars, but a consensus has yet to emerge regarding the mechanism for producing it. One hypothesis suggests early Mars was warmed by a thick greenhouse atmosphere [1]. Another suggests early Mars was generally cold but was warmed occasionally by impacts or by episodes of enhanced volcanism [2,3], with warming possibly extended by cirrus clouds [4]. These latter hypotheses struggle to produce the amounts of rainfall needed to form the martian valleys, but are consistent with inferred low rates of weathering compared to Earth. We suggest that both schools of thought are partly correct. Mars experienced dramatic climate cycles with extended periods of glaciation punctuated by warm periods lasting up to 10 Myr [5]. Cycles of repeated glaciation and deglaciation occurred because stellar insolation was low, and because CO2 outgassing could not keep pace with CO2 consumption by silicate weathering followed by deposition of carbonates. In order to deglaciate early Mars, substantial outgassing of molecular hydrogen from Mars' reduced crust and mantle was also required, as our own climate model is unable to do this without adding some greenhouse warming from H2 [6,7]. Our hypothesis can be tested by future Mars exploration that better establishes the time scale for valley formation. References: [1] Pollack JB, Kasting JF, Richardson SM, Poliakoff K. 1987. Icarus 71: 203-24 [2] Halevy I, Head JW. 2014. Nature Geoscience 7: 865-8 [3] Segura TL, Toon OB, Colaprete A, Zahnle K. 2002. Science 298: 1977-80 [4] Urata RA, Toon OB. 2013. Icarus 226: 229-50 [5] Batalha NE, Kopparapu RK, Haqq-Misra JD, Kasting JF. submitted. Climate cycling on early Mars caused by the carbonate-silicate cycle. EPSL [6] Ramirez RM, Kopparapu R, Zugger ME, Robinson TD, Freedman R, Kasting JF. 2014. Nature Geosci 7: 59-63 [7] Batalha N, Domagal-Goldman SD, Ramirez R, Kasting JF. 2015. Icarus 258: 337-49

Thallium isotope variations in seawater and hydrogenetic, diagenetic, and hydrothermal ferromanganese deposits

USGS Publications Warehouse

Rehkamper, M.; Frank, M.; Hein, J.R.; Porcelli, D.; Halliday, A.; Ingri, J.; Liebetrau, V.

2002-01-01

Results are presented for the first in-depth investigation of TI isotope variations in marine materials. The TI isotopic measurements were conducted by multiple collector-inductively coupled plasma mass spectrometry for a comprehensive suite of hydrogenetic ferromanganese crusts, diagenetic Fe-Mn nodules, hydrothermal manganese deposits and seawater samples. The natural variability of TI isotope compositions in these samples exceeds the analytical reproducibility (?? 0.05???) by more than a factor of 40. Hydrogenetic Fe-Mn crusts have ??205TI of + 10 to + 14, whereas seawater is characterized by values as low as -8 (??205TI represents the deviation of the 205TI/203TI ratio of a sample from the NIST SRM 997 TI isotope standard in parts per 104). This ~ 2??? difference in isotope composition is thought to result from the isotope fractionation that accompanies the adsorption of TI onto ferromanganese particles. An equilibrium fractionation factor of ?? ~ 1.0021 is calculated for this process. Ferromanganese nodules and hydrothermal manganese deposits have variable TI isotope compositions that range between the values obtained for seawater and hydrogenetic Fe-Mn crusts. The variability in ??205TI in diagenetic nodules appears to be caused by the adsorption of TI from pore fluids, which act as a closed-system reservoir with a TI isotope composition that is inferred to be similar to seawater. Nodules with ??205TI values similar to seawater are found if the scavenging of TI is nearly quantitative. Hydrothermal manganese deposits display a positive correlation between ??205TI and Mn/Fe. This trend is thought to be due to the derivation of TI from distinct hydrothermal sources. Deposits with low Mn/Fe ratios and low ??205TI are produced by the adsorption of TI from fluids that are sampled close to hydrothermal sources. Such fluids have low Mn/Fe ratios and relatively high temperatures, such that only minor isotope fractionation occurs during adsorption. Hydrothermal

Rethinking Controls on the Long-Term Cenozoic Carbonate Compensation Depth: Case Studies across Late Paleocene - Early Eocene Warming and Late Eocene - Early Oligocene Cooling

NASA Astrophysics Data System (ADS)

Greene, S. E.; Ridgwell, A. J.; Schmidt, D. N.; Kirtland Turner, S.; Paelike, H.; Thomas, E.

2014-12-01

The carbonate compensation depth (CCD) is the depth below which negligible calcium carbonate is preserved in marine sediments. The long-term position of the CCD is often considered to be a powerful constraint on palaeoclimate and atmospheric CO2 concentration due to the requirement that carbonate burial balance riverine weathering over long timescales. The requirement that weathering and burial be in balance is clear, but it is less certain that burial compensates for changes in weathering via shoaling or deepening of the CCD. Because most carbonate burial occurs well above the CCD , changes in weathering fluxes may be primarily accommodated by increasing or decreasing carbonate burial at shallower depths, i.e., at or near the lysocline, the depth range over which carbonate dissolution markedly increases. Indeed, recent earth system modelling studies have suggested that the position of the CCD is relatively insensitive to changes in atmospheric pCO2. Additionally, studies have questioned the nature and strength of the relationship between the CCD, carbonate saturation state in the water column, and lysocline. To test the relationship between palaeoclimate and the location of the CCD, we reconstructed the global, long-term CCD behaviour across major Cenozoic climate transitions: the late Paleocene - early Eocene long-term warming trend (study interval ~58 to 49 Ma) and the late Eocene - early Oligocene cooling and glaciation (study interval ~38 to 27 Ma). We use Earth system modelling (GENIE) to explore the links between atmospheric pCO2 and the CCD, isolating and teasing apart the roles of total dissolved inorganic carbon, temperature, circulation, and productivity in determining the CCD.

Prokaryotic algae associated with Australian proterozoic stromatolites.

NASA Technical Reports Server (NTRS)

Licari, G. R.; Cloud, P.

1972-01-01

The most favorable sites in which to study the associations between stromatolites and the algae responsible for them are places where a variety of stromatolites of possibly early diagenetic or primary silica occupy a layer of substantial thickness of little metamorphosed ancient sediments. One such place is in northwestern Queensland, Australia. Five cases of association between stromatolites and blue-green algal nannofossils were observed within a 100-m sequence of carbonate rocks in that area.

Early land use and centennial scale changes in lake-water organic carbon prior to contemporary monitoring.

PubMed

Meyer-Jacob, Carsten; Tolu, Julie; Bigler, Christian; Yang, Handong; Bindler, Richard

2015-05-26

Organic carbon concentrations have increased in surface waters across parts of Europe and North America during the past decades, but the main drivers causing this phenomenon are still debated. A lack of observations beyond the last few decades inhibits a better mechanistic understanding of this process and thus a reliable prediction of future changes. Here we present past lake-water organic carbon trends inferred from sediment records across central Sweden that allow us to assess the observed increase on a centennial to millennial time scale. Our data show the recent increase in lake-water carbon but also that this increase was preceded by a landscape-wide, long-term decrease beginning already A.D. 1450-1600. Geochemical and biological proxies reveal that these dynamics coincided with an intensification of human catchment disturbance that decreased over the past century. Catchment disturbance was driven by the expansion and later cessation of widespread summer forest grazing and farming across central Scandinavia. Our findings demonstrate that early land use strongly affected past organic carbon dynamics and suggest that the influence of historical landscape utilization on contemporary changes in lake-water carbon levels has thus far been underestimated. We propose that past changes in land use are also a strong contributing factor in ongoing organic carbon trends in other regions that underwent similar comprehensive changes due to early cultivation and grazing over centuries to millennia.

In vitro formation of Ca-oxalates and the mineral glushinskite by fungal interaction with carbonate substrates and seawater

NASA Astrophysics Data System (ADS)

Kolo, K.; Claeys, Ph.

2005-10-01

This study investigates the in vitro formation of Ca-oxalates and glushinskite through fungal interaction with carbonate substrates and seawater as a process of biologically induced metal recycling and neo-mineral formation. The study also emphasizes the role of the substrates as metal donors. In the first experiment, thin sections prepared from dolomitic rock samples of Terwagne Formation (Carboniferous, Viséan, northern France) served as substrates. The thin sections placed in Petri dishes were exposed to fungi grown from naturally existing airborne spores. In the second experiment, fungal growth and mineral formation was monitored using only standard seawater (SSW) as a substrate. Fungal growth media consisted of a high protein/carbohydrates and sugar diet with demineralized water for irrigation. Fungal growth process reached completion under uncontrolled laboratory conditions. The newly formed minerals and textural changes caused by fungal attack on the carbonate substrates were investigated using light and scanning electron microscopy (SEM-EDX), x-ray diffraction (XRD) and Raman spectroscopy. The fungal interaction and attack on the dolomitic and seawater substrates resulted in the formation of Ca-oxalates (weddellite CaC2O4·2(H2O), whewellite (CaC2O4·(H2O)) and glushinskite MgC2O4·2(H2O) associated with the destruction of the original hard substrates and their replacement by the new minerals. Both of Ca and Mg were mobilized from the experimental substrates by fungi. This metal mobilization involved a recycling of substrate metals into newly formed minerals. The biochemical and diagenetic results of the interaction strongly marked the attacked substrates with a biological fingerprint. Such fingerprints are biomarkers of primitive life. The formation of glushinskite is of specific importance that is related, besides its importance as a biomineral bearing a recycled Mg, to the possibility of its transformation through diagenetic pathway into an Mg carbonate

Investigating the Early Carbon Cycle Using Carbonaceous Inclusions and Dissolved Carbon in Detrital Zircon

NASA Astrophysics Data System (ADS)

Bell, E. A.; Boehnke, P.; Harrison, M.; Mao, W. L.

2015-12-01

Because the terrestrial rock record extends only to ~4 Ga and older materials thus far identified are limited to detrital zircons, information about volatile abundances and cycles on early Earth is limited. Carbon, for instance, plays an important role not only in the modern biosphere but also in deep recycling of materials between the crust and mantle. We are investigating the record of carbon abundance and origin in Hadean zircons from Jack Hills (W. Australia) using two main approaches. First, carbon may partition into the zircon structure at trace levels during crystallization from a magma, and better understanding of this partitioning behavior will allow for zircon's use as a monitor of magmatic carbon contents. We have measured carbon abundances in zircon from a variety of igneous rocks (gabbro; I-, A-, and S-type granitoids) via SIMS and found that although abundances are typically low (average raw 12C/30Si ~ 1x10-6), S-type granite zircons can reach a factor of 1000 over this background. Around 10% of Hadean zircons investigated show similar enrichments, consistent with other evidence for the derivation of many Jack Hills zircons from S-type granitoids and with the establishment of modern-level carbon abundances in the crust by ca. 4.2 Ga. Diamond and graphite inclusions reported in the Jack Hills zircons by previous studies proved to be contamination by polishing debris, leaving the true abundance of these materials in the population uncertain. On a second front, we have identified and investigated primary carbonaceous inclusions in these zircons. From a population of over 10,000 Jack Hills zircons, we identified one concordant 4.10±0.01 Ga zircon that contains primary graphite inclusions (so interpreted due to their enclosure in a crack-free zircon host as shown by transmission X-ray microscopy and their crystal habit). Their δ13CPDB of -24±5‰ is consistent with a biogenic origin and, in the absence of a likely inorganic mechanism to produce such a

Empirical relation between carbonate porosity and thermal maturity: an approach to regional porosity prediction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schmoker, J.W.

1984-11-01

Data indicate that porosity loss in subsurface carbonate rocks can be empirically represented by the power function, theta = a (TTI) /SUP b/ , where theta is regional porosity, TTI is Lopatin's time-temperature index of thermal maturity, the exponent, b, equals approximately -0.372, and the multiplier, a, is constant for a given data population but varies by an order of magnitude overall. Implications include the following. 1. The decrease of carbonate porosity by burial diagenesis is a maturation process depending exponentially on temperature and linearly on time. 2. The exponent, b, is essentially independent of the rock matrix, and maymore » reflect rate-limiting processes of diffusive transport. 3. The multiplying coefficient, a, incorporates the net effect on porosity of all depositional and diagenetic parameters. Within constraints, carbonate-porosity prediction appears possible on a regional measurement scale as a function of thermal maturity. Estimation of carbonate porosity at the time of hydrocarbon generation, migration, or trapping also appears possible.« less

Synchronization of the astronomical time scales in the Early Toarcian: A link between anoxia, carbon-cycle perturbation, mass extinction and volcanism

NASA Astrophysics Data System (ADS)

Ait-Itto, Fatima-Zahra; Martinez, Mathieu; Price, Gregory D.; Ait Addi, Abdellah

2018-07-01

The Late Pliensbachian-Early Toarcian is a pivotal time in the Mesozoic era, marked by pronounced carbon-isotope excursions, biotic crises and major climatic and oceanographic changes. Here we present new high-resolution carbon-isotope and magnetic-susceptibility measurements from an expanded hemipelagic Late Pliensbachian-Early Toarcian section from the Middle Atlas Basin (Morocco). Our new astronomical calibration allows the construction of an orbital time scale based on the 100-kyr eccentricity cycle. The Early Toarcian Polymorphum Zone contains 10 to 10.5 repetitions of the 100-kyr eccentricity both in the carbon-isotope and the magnetic-susceptibility data, leading to an average duration of 1.00 ± 0.08 myr. We also show that the Late Pliensbachian-Early Toarcian global carbon-cycle perturbation has an average duration of 0.24 ± 0.02 myr. These durations are comparable to previous astrochronological time scales provided for this time interval in the most complete sections of the Tethyan area, and longer than what has been provided in condensed sections. Anchoring this framework on published radiometric ages and astrochronological time scales, we estimate that the carbon-cycle perturbation of the Late Pliensbachian-Early Toarcian corresponds with the early phase of the Karoo and Chonke Aike large igneous provinces. Likewise, our new age constraints confirm that the Toarcian oceanic anoxic event is synchronous to the main phase of the Ferrar volcanic activity. Thus, these successive and short phases of the volcanic activity may have been at the origin of the successive phases of the mass extinctions observed in marine biotas in the Pliensbachian and Toarcian times.

Carbonate-evaporite cycles in the Miocene to Holocene of Abu Dhabi, United Arab Emirates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Whittle, G.L.; Alsharhan, A.S.; Takezaki, H.

1995-08-01

The coastal sabkhas of the United Arab Emirates provide a Holocene analog for the study of evaporite formation. Carbonate-evaporite sequences are common throughout geologic history and, in the Arabian Gulf region in particular, create the reservoir-seal relationship of some of the most prolific hydrocarbon reservoirs in the world. Detailed core description, thin section study and geochemical analysis of Miocene to Holocene cores from the sabkha of Abu Dhabi have been performed in order to characterize modern sabkha diagenetic patterns. Two primary lithologies, dolomite and anhydrite were identified and subdivided into lithofacies. Based on these lithofacies, deposition is interpreted to havemore » occurred in shallow open marine, lagoonal, tidal channel, tidal/algal flats and supratidal sabkha settings. The primary diagenetic effects are dolomitization, anhydritc formation and leaching. As anhydrite precipitated (in the form of gypsum), the Mg:Ca ratio increased to the point where rapid dolomitization of original limestone occurred. Leaching was pervasive, as subaerial exposure led to the formation of moldic porosity in dolomitized packstones and grainstones. Dolomitic cements in these pores, and leached zones in some of these crystals suggests that leaching continued after dolomitization. By comparing the Holocene sabkha sediments to ancient ones, insight may be gained into the extent of dolomilization both with depth and distance for in the high water mark, the zonation of the stratigraphy from upper supratidal to shallow shelf, the preservation potential of algal mats after burial, the compaction effects after shallow burial, and other diagenetic alterations.« less

Impact of stylolitization on diagenesis of a Lower Cretaceous carbonate reservoir from a giant oilfield, Abu Dhabi, United Arab Emirates

NASA Astrophysics Data System (ADS)

Paganoni, Matteo; Al Harthi, Amena; Morad, Daniel; Morad, Sadoon; Ceriani, Andrea; Mansurbeg, Howri; Al Suwaidi, Aisha; Al-Aasm, Ihsan S.; Ehrenberg, Stephen N.; Sirat, Manhal

2016-04-01

Bed-parallel stylolites are a widespread diagenetic feature in Lower Cretaceous limestone reservoirs, Abu Dhabi, United Arab Emirates (UAE). Diagenetic calcite, dolomite, kaolin and small amounts of pyrite, fluorite, anhydrite and sphalerite occur along and in the vicinity of the stylolites. Petrographic observations, negative δ18OVPDB, fluid inclusion microthermometry, and enrichment in 87Sr suggest that these cements have precipitated from hot basinal brines, which migrated along the stylolites and genetically related microfractures (tension gashes). Fluid migration was presumably related to lateral tectonic compression events related to the foreland basin formation. The low solubility of Al3 + in formation waters suggests that kaolin precipitation was linked to derivation of organic acids during organic matter maturation, probably in siliciclastic source rocks. The mass released from stylolitization was presumably re-precipitated as macro- and microcrystalline calcite cement in the host limestones. The flanks of the oilfield (water zone) display more frequent presence and higher amplitude of stylolites, lower porosity and permeability, higher homogenization temperatures and more radiogenic composition of carbonates compared to the crest (oil zone). This indicates that oil emplacement retards diagenesis. This study demonstrates that stylolitization plays a crucial role in fluid flow and diagenesis of carbonate reservoirs during basin evolution.

Altered carbon cycling and coupled changes in Early Cretaceous weathering patterns: Evidence from integrated carbon isotope and sandstone records of the western Tethys

NASA Astrophysics Data System (ADS)

Wortmann, Ulrich Georg; Herrle, Jens Olaf; Weissert, Helmut

2004-03-01

In this study we investigate if a major perturbation of the Early Cretaceous carbon cycle was accompanied by altered weathering and erosion rates. The large Aptian carbon isotope anomaly records the response of the biosphere to widespread volcanic activity and probably resulting changes in atmospheric pCO2 levels. Elevated pCO2 levels should also result in an accelerated hydrological cycle and increased silicate weathering, creating a negative feedback loop removing CO2 from the atmosphere. We propose to interpret the widespread occurrence of quartz sandstones in the Tethys-Atlantic seaway as a result of altered weathering and erosion rates in the wake of the Aptian carbon cycle excursion. We challenge the traditional notion that these are 'flysch' deposits associated with Early Cretaceous orogenic movements in the western Tethys. We propose that these sandstones were most likely part of a large conveyor belt system, acting along the Iberian and European margin of the Tethys seaway. Using chemostratigraphic correlations, we show that the activity of this system was only short-lived and coeval with changes in coastal ecology and the Aptian carbon cycle perturbations. We tentatively relate the existence of this system to a transient climate regime, characterized by fluctuating pCO2 levels.

Geochemical gradients within modern and fossil shells of Concholepas concholepas from northern Chile: an insight into U-Th systematics and diagenetic/authigenic isotopic imprints in mollusk shells

NASA Astrophysics Data System (ADS)

Labonne, Maylis; Hillaire-Marcel, Claude

2000-05-01

Seriate geochemical measurements through shells of one modern, one Holocene, and two Sangamonian Concholepas concholepas, from marine terraces of Northern Chile, were performed to document diagenetic vs. authigenic geochemical signatures, and to better interpret U-series ages on such material. Subsamples were recovered by drilling from the outer calcitic layer to the inner aragonitic layer of each of the studied shells. Unfortunately, this sampling procedure induces artifacts, notably the convertion of up to ˜20% of calcite into aragonite, and of up to ˜6% of aragonite into calcite, as well as in the epimerization of a few percent of isoleucine into D-alloisoleucine/ L-isoleucine. Negligible sampling artifacts were noticed for stable isotope and total amino acid contents. Diagenetic effects on the geochemical properties of the shells are particularly pronounced in the inner aragonitic layer and more discrete in the outer calcitic layer. The time-dependent decay of the organic matrix of the shell is illustrated by a one order of magnitude lower total amino acid content in the Sangamonian specimens by comparison with the modern shell. Conversely, the Sangamonian shells U contents increase by a similar factor and 13C- 18O enrichments as high as 2 to 3‰ seem also to occur through the same time interval possibly due to partial replacement of aragonite by gypsum. The decay of the organic matrix of the aragonitic layer of the shell is thought to play a major role with respect to U-uptake processes and stable isotope shifts. Nevertheless, asymptotic 230Th-ages (˜100 ka) in the inner U-rich layers of the Sangamonian shells, and 234U/ 238U ratios compatible with a marine origin for U, suggest U-uptake within a short diagenetic interval, when marine waters were still bathing the embedding sediment. Thus, U-series ages on fossil mollusks from such a hyper-arid environment should not differ much from the age of the corresponding marine unit deposition. However, the

High resolution ion microprobe investigation of the δ18O of carbonate cements (Jurassic, Paris Basin, France): New insights and pending questions

NASA Astrophysics Data System (ADS)

Vincent, Benoit; Brigaud, Benjamin; Emmanuel, Laurent; Loreau, Jean-Paul

2017-04-01

The scope of this work is to investigate, at a high resolution, the oxygen isotope composition (δ18Ocarb) of diagenetic products (synsedimentary and burial calcite cements) in shallow-marine carbonates. SIMS (Secondary Ion Mass Spectrometry) microprobe analyses were performed on thin sections from Oxfordian and Kimmeridgian Formations of the eastern Paris Basin and compared to data obtained on the same diagenetic products by conventional mass spectrometry (acid digestion). Hereby obtained, δ18O are similar, but the SIMS dataset displays a larger range of values. The isotopic zonation obtained by SIMS transects through sequences of cements filling pores, reveals an (expected) isotopic depletion from older stage synsedimentary calcites to younger stage blocky calcites and that follows the CL (cathodoluminescence) zonation. SIMS analyses however show that synsedimentary cements precipitated in intra-skeletal pores, have heavier δ18O than their inter-particle counterparts, with an offset of + 4‰V-PDB, despite similar petrographical characteristics. This difference is maintained in the δ18O of the first stages of blocky calcite cements, intra-skeletal blocky calcites showing heavier δ18O than the time equivalent and petrographically identical inter-particle calcites, with an offset of + 5‰V-PDB. These offsets are tentatively explained by the precipitation of cements under non-equilibrium conditions in intra-skeletal pores, where organic matter decay may have played a key role, acting notably on the pH. The occurrence of isolated micro-diagenetic environments, co-existing at the thin section scale, is tentatively proposed as an explanation to these small scale and high amplitude δ18O heterogeneities. These results may question the sampling strategy for future works. Microdrilling may miss the observed range of variation, but averaging the values may not necessarily lead to real misinterpretations if a critical selection of samples is performed, targeting

Effectiveness of potassium carbonate sesquihydrate to increase dietary cation-anion difference in early lactation cows.

PubMed

Harrison, J; White, R; Kincaid, R; Block, E; Jenkins, T; St-Pierre, N

2012-07-01

The effect of additional dietary potassium in early lactation dairy cows was evaluated with the addition of potassium carbonate sesquihydrate, which increased dietary K from 1.3 to 2.1% of dry matter (DM) from wk 3 to 12 of lactation. Cows fed potassium carbonate sesquihydrate in the form of DCAD Plus (Church & Dwight Co. Inc., Princeton, NJ) had increased DM intake, milk fat percentage and yield, energy-corrected milk, and efficiency of milk production per unit of DM intake. Milk fat of cows fed higher dietary K had a lower concentration of trans fatty acids, suggesting a role for potassium carbonate sesquihydrate in the rumen in the biohydrogenation processes converting linoleic to stearic acid. Cows fed the diet with 2.1% K had greater apparent balance of K, and no effects were noted on the concentration of blood Mg or amount of fecal Mg. The data support the feeding of greater amounts of K in the early lactation cow. Copyright © 2012 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Dioctahedral Phyllosilicates Versus Zeolites and Carbonates Versus Zeolites Competitions as Constraints to Understanding Early Mars Alteration Conditions

NASA Astrophysics Data System (ADS)

Viennet, Jean-Christophe; Bultel, Benjamin; Riu, Lucie; Werner, Stephanie C.

2017-11-01

Widespread occurrence of Fe,Mg-phyllosilicates has been observed on Noachian Martian terrains. Therefore, the study of Fe,Mg-phyllosilicate formation, in order to characterize early Martian environmental conditions, is of particular interest to the Martian community. Previous studies have shown that the investigation of Fe,Mg-smectite formation alone helps to describe early Mars environmental conditions, but there are still large uncertainties in terms of pH range, oxic/anoxic conditions, etc. Interestingly, carbonates and/or zeolites have also been observed on Noachian surfaces in association with the Fe,Mg-phyllosilicates. Consequently, the present study focuses on the dioctahedral/trioctahedral phyllosilicate/carbonate/zeolite formation as a function of various CO2 contents (100% N2, 10% CO2/90% N2, and 100% CO2), from a combined approach including closed system laboratory experiments for 3 weeks at 120°C and geochemical simulations. The experimental results show that as the CO2 content decreases, the amount of dioctahedral clay minerals decreases in favor of trioctahedral minerals. Carbonates and dioctahedral clay minerals are formed during the experiments with CO2. When Ca-zeolites are formed, no carbonates and dioctahedral minerals are observed. Geochemical simulation aided in establishing pH as a key parameter in determining mineral formation patterns. Indeed, under acidic conditions dioctahedral clay minerals and carbonate minerals are formed, while trioctahedral clay minerals are formed in basic conditions with a neutral pH value of 5.98 at 120°C. Zeolites are favored from pH ≳ 7.2. The results obtained shed new light on the importance of dioctahedral clay minerals versus zeolites and carbonates versus zeolites competitions to better define the aqueous alteration processes throughout early Mars history.

Carbonate and silicate cementation of siliciclastic sediments of the New Jersey shelf (IODP Expedition 313): relation with organic matter diagenesis and submarine groundwater discharge

NASA Astrophysics Data System (ADS)

Pierre, Catherine; Blanc-Valleron, Marie-Madeleine; Boudouma, Omar; Lofi, Johanna

2017-12-01

The New Jersey continental shelf extends 150 km off the shoreline. During IODP Expedition 313, siliciclastic deposits of late Eocene to late Pleistocene age were drilled down to 631, 669 and 755 m below seafloor at sites 27A, 28A and 29A respectively in very shallow waters (33.5 to 36 m depth). Pore water salinities display multilayered brackish-salty-brine units 10 to 170 m thick, where low-salinity water is preferentially stored in fine-grained sediments. The sharp boundaries of these buried aquifers are often marked by cemented layers a few centimetres thick. The mineralogy and scanning electron microscope observations of these layers show two phases of cementation by authigenic minerals: (1) the early carbonate cement is frequently associated with pyrite, and (2) the late silicate cement infills the residual porosity. The isotopic compositions of the carbonate cements vary widely: -2.4 < δ18O ‰ VPDB < +2.8; -15.1 < δ13C ‰ VPDB < +15.6. The δ18O values indicate that the carbonate cements precipitated with pore waters comprising variable mixtures of seawater and 18O-depleted fresh water originating from submarine groundwater discharge. The δ13C values of the carbonate cements are related to organic matter diagenesis, providing 13C-depleted dissolved inorganic carbon during bacterial sulphate reduction and anaerobic oxidation of methane, and 13C-rich dissolved inorganic carbon during methanogenesis. The diagenetic cementation processes included chemical weathering of reactive silicate minerals by the CO2-rich pore waters issued from organic matter diagenesis that released bicarbonate, cations and dissolved silica, which were further precipitated as carbonate and silicate cements. The estimated range of temperature (18±4 °C) during carbonate precipitation is consistent with carbonate cementation at moderate burial depths; however, silicate cementation occurred later during diagenesis at deeper burial depths.

Building the Next Generation of Earth Scientists: the Deep Carbon Observatory Early Career Scientist Workshops

NASA Astrophysics Data System (ADS)

Pratt, K.; Fellowes, J.; Giovannelli, D.; Stagno, V.

2016-12-01

Building a network of collaborators and colleagues is a key professional development activity for early career scientists (ECS) dealing with a challenging job market. At large conferences, young scientists often focus on interacting with senior researchers, competing for a small number of positions in leading laboratories. However, building a strong, international network amongst their peers in related disciplines is often as valuable in the long run. The Deep Carbon Observatory (DCO) began funding a series of workshops in 2014 designed to connect early career researchers within its extensive network of multidisciplinary scientists. The workshops, by design, are by and for early career scientists, thus removing any element of competition and focusing on peer-to-peer networking, collaboration, and creativity. The successful workshops, organized by committees of early career deep carbon scientists, have nucleated a lively community of like-minded individuals from around the world. Indeed, the organizers themselves often benefit greatly from the leadership experience of pulling together an international workshop on budget and on deadline. We have found that a combination of presentations from all participants in classroom sessions, professional development training such as communication and data management, and field-based relationship building and networking is a recipe for success. Small groups within the DCO ECS network have formed; publishing papers together, forging new research directions, and planning novel and ambitious field campaigns. Many DCO ECS also have come together to convene sessions at major international conferences, including the AGU Fall Meeting. Most of all, there is a broad sense of camaraderie and accessibility within the DCO ECS Community, providing the foundation for a career in the new, international, and interdisciplinary field of deep carbon science.

Combining Textural Techniques to Explore Effects of Diagenesis and Low-grade Metamorphism on Iron Mineralogy and Iron Speciation

NASA Astrophysics Data System (ADS)

Slotznick, S. P.; Webb, S.; Eiler, J. M.; Kirschvink, J. L.; Fischer, W. W.

2016-12-01

Iron chemistry and mineralogy in the sedimentary rocks provide a valuable tool for studying paleoenvironmental conditions due to the fact that iron atoms can take on either the +II or +III valence state under geological redox conditions. One method utilizing this redox chemistry is `iron speciation', a bulk chemical sequential extraction technique that maps proportions of iron species to redox conditions empirically calibrated from modern sediments. However, all Precambrian and many Phanerozoic rocks have experienced post-depositional processes; it is vital to explore their effects on iron mineralogy and speciation. We combined light and electron microscopy, magnetic microscopy, (synchrotron-based) microprobe x-ray spectroscopy, and rock magnetic measurements in order to deconvolve secondary overprints from primary phases and provide quantitative measurement of iron minerals. These techniques were applied to excellently-preserved shale and siltstone samples of the 1.4 Ga lower Belt Supergroup, Montana and Idaho, USA, spanning a metamorphic gradient from sub-biotite to garnet zone. Previously measured Silurian-Devonian shales, sandstones, and carbonates in Maine and Vermont, USA spanning from the chlorite to kyanite zone provided additional well-constrained, quantitative data for comparison and to extend our analysis. In all of the studied samples, pyrrhotite formation occurred at the sub-biotite or sub-chlorite zone. Pyrrhotite was interpreted to form from pyrite and/or other iron phases based on lithology; these reactions can affect the paleoredox proxy. Iron carbonates can also severely influence iron speciation results since they often form in anoxic pore fluids during diagenesis; textural analyses of the Belt Supergroup samples highlighted that iron-bearing carbonates were early diagenetic cements or later diagenetic overprints. The inclusion of iron from diagenetic minerals during iron speciation analyses will skew results by providing a view of pore

Sentinel Lymph Node Detection Using Carbon Nanoparticles in Patients with Early Breast Cancer

PubMed Central

Lu, Jianping; Zeng, Yi; Chen, Xia; Yan, Jun

2015-01-01

Purpose Carbon nanoparticles have a strong affinity for the lymphatic system. The purpose of this study was to evaluate the feasibility of sentinel lymph node biopsy using carbon nanoparticles in early breast cancer and to optimize the application procedure. Methods Firstly, we performed a pilot study to demonstrate the optimized condition using carbon nanoparticles for sentinel lymph nodes (SLNs) detection by investigating 36 clinically node negative breast cancer patients. In subsequent prospective study, 83 patients with clinically node negative breast cancer were included to evaluate SLNs using carbon nanoparticles. Another 83 SLNs were detected by using blue dye. SLNs detection parameters were compared between the methods. All patients irrespective of the SLNs status underwent axillary lymph node dissection for verification of axillary node status after the SLN biopsy. Results In pilot study, a 1 ml carbon nanoparticles suspension used 10–15min before surgery was associated with the best detection rate. In subsequent prospective study, with carbon nanoparticles, the identification rate, accuracy, false negative rate was 100%, 96.4%, 11.1%, respectively. The identification rate and accuracy were 88% and 95.5% with 15.8% of false negative rate using blue dye technique. The use of carbon nanoparticles suspension showed significantly superior results in identification rate (p = 0.001) and reduced false-negative results compared with blue dye technique. Conclusion Our study demonstrated feasibility and accuracy of using carbon nanoparticles for SLNs mapping in breast cancer patients. Carbon nanoparticles are useful in SLNs detection in institutions without access to radioisotope. PMID:26296136

Influence of carbon dioxide clouds on early martian climate.

PubMed

Mischna, M A; Kasting, J F; Pavlov, A; Freedman, R

2000-06-01

Recent studies have shown that clouds made of carbon dioxide ice may have warmed the surface of early Mars by reflecting not only incoming solar radiation but upwelling IR radiation as well. However, these studies have not treated scattering self-consistently in the thermal IR. Our own calculations, which treat IR scattering properly, confirm these earlier calculations but show that CO2 clouds can also cool the surface, especially if they are low and optically thick. Estimating the actual effect of CO2 clouds on early martian climate will require three-dimensional models in which cloud location, height, and optical depth, as well as surface temperature and pressure, are determined self-consistently. Our calculations further confirm that CO2 clouds should extend the outer boundary of the habitable zone around a star but that there is still a finite limit beyond which above-freezing surface temperatures cannot be maintained by a CO2-H2O atmosphere. For our own Solar System, the absolute outer edge of the habitable zone is at approximately 2.4 AU.

Analysis and application of classification methods of complex carbonate reservoirs

NASA Astrophysics Data System (ADS)

Li, Xiongyan; Qin, Ruibao; Ping, Haitao; Wei, Dan; Liu, Xiaomei

2018-06-01

There are abundant carbonate reservoirs from the Cenozoic to Mesozoic era in the Middle East. Due to variation in sedimentary environment and diagenetic process of carbonate reservoirs, several porosity types coexist in carbonate reservoirs. As a result, because of the complex lithologies and pore types as well as the impact of microfractures, the pore structure is very complicated. Therefore, it is difficult to accurately calculate the reservoir parameters. In order to accurately evaluate carbonate reservoirs, based on the pore structure evaluation of carbonate reservoirs, the classification methods of carbonate reservoirs are analyzed based on capillary pressure curves and flow units. Based on the capillary pressure curves, although the carbonate reservoirs can be classified, the relationship between porosity and permeability after classification is not ideal. On the basis of the flow units, the high-precision functional relationship between porosity and permeability after classification can be established. Therefore, the carbonate reservoirs can be quantitatively evaluated based on the classification of flow units. In the dolomite reservoirs, the average absolute error of calculated permeability decreases from 15.13 to 7.44 mD. Similarly, the average absolute error of calculated permeability of limestone reservoirs is reduced from 20.33 to 7.37 mD. Only by accurately characterizing pore structures and classifying reservoir types, reservoir parameters could be calculated accurately. Therefore, characterizing pore structures and classifying reservoir types are very important to accurate evaluation of complex carbonate reservoirs in the Middle East.

Mass transfer and carbon isotope evolution in natural water systems

USGS Publications Warehouse

Wigley, T.M.L.; Plummer, Niel; Pearson, F.J.

1978-01-01

This paper presents a theoretical treatment of the evolution of the carbon isotopes C13 and C14 in natural waters and in precipitates which derive from such waters. The effects of an arbitrary number of sources (such as dissolution of carbonate minerals and oxidation of organic material) and sinks (such as mineral precipitation, CO2 degassing and production of methane), and of equilibrium fractionation between solid, gas and aqueous phases are considered. The results are expressed as equations relating changes in isotopic composition to changes in conventional carbonate chemistry. One implication of the equations is that the isotopic composition of an aqueous phase may approach a limiting value whenever there are simultaneous inputs and outputs of carbonate. In order to unambiguously interpret isotopic data from carbonate precipitates and identify reactants and products in reacting natural waters, it is essential that isotopic changes are determined chiefly by reactant and product stoichiometry, independent of reaction path. We demonstrate that this is so by means of quantitative examples. The evolution equations are applied to: 1. (1) carbon-14 dating of groundwaters; 2. (2) interpretation of the isotopic composition of carbonate precipitates, carbonate cements and diagenetically altered carbonates; and 3. (3) the identification of chemical reaction stoichiometry. These applications are illustrated by examples which show the variation of ??C13 in solutions and in precipitates formed under a variety of conditions involving incongruent dissolution, CO2 degassing, methane production and mineral precipitation. ?? 1978.

Fluid-chemical evidence for one billion years of fluid flow through Mesoproterozoic deep-water carbonate mounds (Nanisivik zinc district, Nunavut)

NASA Astrophysics Data System (ADS)

Hahn, K. E.; Turner, E. C.; Kontak, D. J.; Fayek, M.

2018-02-01

Ancient carbonate rocks commonly contain numerous post-depositional phases (carbonate minerals; quartz) recording successive diagenetic events that can be deciphered and tied to known or inferred geological events using a multi-pronged in situ analytical protocol. The framework voids of large, deep-water microbial carbonate seep-mounds in Arctic Canada (Mesoproterozoic Ikpiarjuk Formation) contain multiple generations of synsedimentary and late cement. An in situ analytical study of the post-seafloor cements used optical and cathodoluminescence petrography, SEM-EDS analysis, fluid inclusion (FI) microthermometry and evaporate mound analysis, LA-ICP-MS analysis, and SIMS δ18O to decipher the mounds' long-term diagenetic history. The six void-filling late cements include, in paragenetic order: inclusion-rich euhedral dolomite (ED), finely crystalline clear dolomite (FCD), hematite-bearing dolomite (HD), coarsely crystalline clear dolomite (CCD), quartz (Q), replacive calcite (RC) and late calcite (LC). Based on the combined analytical results, the following fluid-flow history is defined: (1) ED precipitation by autocementation during shallow burial (fluid 1; Mesoproterozoic); (2) progressive mixing of Ca-rich hydrothermal fluid with the connate fluid, resulting in precipitation of FCD followed by HD (fluid 2; also Mesoproterozoic); (3) precipitation of hydrothermal dolomite (CCD) from high-Ca and K-rich fluids (fluid 3; possibly Mesoproterozoic, but timing unclear); (4) hydrothermal Q precipitation (fluid 4; timing unclear), and (5) RC and LC precipitation from a meteoric-derived water (fluid 5) in or since the Mesozoic. Fluids associated with FCD, HD, and CCD may have been mobilised during deposition of the upper Bylot Supergroup; this time interval was the most tectonically active episode in the region's Mesoproterozoic to Recent history. The entire history of intermittent fluid migration and cement precipitation recorded in seemingly unimportant void

New insights into the early stages of silica-controlled barium carbonate crystallisation

NASA Astrophysics Data System (ADS)

Eiblmeier, Josef; Schürmann, Ulrich; Kienle, Lorenz; Gebauer, Denis; Kunz, Werner; Kellermeier, Matthias

2014-11-01

Recent work has demonstrated that the dynamic interplay between silica and carbonate during co-precipitation can result in the self-assembly of unusual, highly complex crystal architectures with morphologies and textures resembling those typically displayed by biogenic minerals. These so-called biomorphs were shown to be composed of uniform elongated carbonate nanoparticles that are arranged according to a specific order over mesoscopic scales. In the present study, we have investigated the circumstances leading to the continuous formation and stabilisation of such well-defined nanometric building units in these inorganic systems. For this purpose, in situ potentiometric titration measurements were carried out in order to monitor and quantify the influence of silica on both the nucleation and early growth stages of barium carbonate crystallisation in alkaline media at constant pH. Complementarily, the nature and composition of particles occurring at different times in samples under various conditions were characterised ex situ by means of high-resolution electron microscopy and elemental analysis. The collected data clearly evidence that added silica affects carbonate crystallisation from the very beginning (i.e. already prior to, during, and shortly after nucleation), eventually arresting growth on the nanoscale by cementation of BaCO3 particles within a siliceous matrix. Our findings thus shed light on the fundamental processes driving bottom-up self-organisation in silica-carbonate materials and, for the first time, provide direct experimental proof that silicate species are responsible for the miniaturisation of carbonate crystals during growth of biomorphs, hence confirming previously discussed theoretical models for their formation mechanism.Recent work has demonstrated that the dynamic interplay between silica and carbonate during co-precipitation can result in the self-assembly of unusual, highly complex crystal architectures with morphologies and textures

Basanite-nephelinite suite from early Kilauea: Carbonated melts of phlogopite-garnet peridotite at Hawaii's leading magmatic edge

USGS Publications Warehouse

Sisson, T.W.; Kimura, Jun-Ichi; Coombs, M.L.

2009-01-01

A basanite-nephelinite glass suite from early submarine Kilauea defines a continuous compositional array marked by increasing concentrations of incompatible components with decreasing SiO2, MgO, and Al2O3. Like peripheral and post-shield strongly alkalic Hawaiian localities (Clague et al. in J Volcanol Geotherm Res 151:279-307, 2006; Dixon et al. in J Pet 38:911-939, 1997), the early Kilauea basanite-nephelinite glasses are interpreted as olivine fractionation products from primary magnesian alkalic liquids. For early Kilauea, these were saturated with a garnet-phlogopite-sulfide peridotite assemblage, with elevated dissolved CO2 contents responsible for the liquids' distinctly low-SiO2 concentrations. Reconstructed primitive liquids for early Kilauea and other Hawaiian strongly alkalic localities are similar to experimental 3 GPa low-degree melts of moderately carbonated garnet lherzolite, and estimated parent magma temperatures of 1,350-1,400??C (olivine-liquid geothermometry) match the ambient upper mantle geotherm shortly beneath the base of the lithosphere. The ???3 GPa source regions were too hot for stable crystalline carbonate and may have consisted of ambient upper mantle peridotite containing interstitial carbonate-silicate or carbonatitic liquid, possibly (Dixon et al. in Geochem Geophys Geosyst 9(9):Q09005, 2008), although not necessarily, from the Hawaiian mantle plume. Carbonate-enriched domains were particularly susceptible to further melting upon modest decompression during upward lithospheric flexure beneath the advancing Hawaiian Arch, or by conductive heating or upward drag by the Hawaiian mantle plume. The early Kilauea basanite-nephelinite suite has a HIMU-influenced isotopic character unlike other Hawaiian magmas (Shimizu et al. in EOS Tran Amer Geophys Union 82(47): abstr V12B-0962, 2001; Shimizu et al. in Geochim Cosmochim Acta 66(15A):710, 2002) but consistent with oceanic carbonatite involvement (Hoernle et al. in Contrib Mineral Petrol

Basanite-nephelinite suite from early Kilauea: carbonated melts of phlogopite-garnet peridotite at Hawaii's leading magmatic edge

NASA Astrophysics Data System (ADS)

Sisson, T. W.; Kimura, J.-I.; Coombs, M. L.

2009-12-01

A basanite-nephelinite glass suite from early submarine Kilauea defines a continuous compositional array marked by increasing concentrations of incompatible components with decreasing SiO2, MgO, and Al2O3. Like peripheral and post-shield strongly alkalic Hawaiian localities (Clague et al. in J Volcanol Geotherm Res 151:279-307, 2006; Dixon et al. in J Pet 38:911-939, 1997), the early Kilauea basanite-nephelinite glasses are interpreted as olivine fractionation products from primary magnesian alkalic liquids. For early Kilauea, these were saturated with a garnet-phlogopite-sulfide peridotite assemblage, with elevated dissolved CO2 contents responsible for the liquids’ distinctly low-SiO2 concentrations. Reconstructed primitive liquids for early Kilauea and other Hawaiian strongly alkalic localities are similar to experimental 3 GPa low-degree melts of moderately carbonated garnet lherzolite, and estimated parent magma temperatures of 1,350-1,400°C (olivine-liquid geothermometry) match the ambient upper mantle geotherm shortly beneath the base of the lithosphere. The ~3 GPa source regions were too hot for stable crystalline carbonate and may have consisted of ambient upper mantle peridotite containing interstitial carbonate-silicate or carbonatitic liquid, possibly (Dixon et al. in Geochem Geophys Geosyst 9(9):Q09005, 2008), although not necessarily, from the Hawaiian mantle plume. Carbonate-enriched domains were particularly susceptible to further melting upon modest decompression during upward lithospheric flexure beneath the advancing Hawaiian Arch, or by conductive heating or upward drag by the Hawaiian mantle plume. The early Kilauea basanite-nephelinite suite has a HIMU-influenced isotopic character unlike other Hawaiian magmas (Shimizu et al. in EOS Tran Amer Geophys Union 82(47): abstr V12B-0962, 2001; Shimizu et al. in Geochim Cosmochim Acta 66(15A):710, 2002) but consistent with oceanic carbonatite involvement (Hoernle et al. in Contrib Mineral Petrol

Carbon-isotope stratigraphy of Early Cretaceous (Urgonian) shoal-water deposits: Diachronous changes in carbonate-platform production in the north-western Tethys

NASA Astrophysics Data System (ADS)

Huck, S.; Heimhofer, U.; Immenhauser, A.; Weissert, H.

2013-05-01

Carbonate platforms are highly sensitive ecological systems that typically show rapid and characteristic response modes to environmental and climatic changes acting both on a regional scale and global scale. A widely accepted hypothesis proposes that the Late Barremian stepwise establishment of the Urgonian carbonate platform on the Northern Tethyan shelf was related to a gradual change from predominantly humid towards more arid greenhouse conditions. This climate change resulted in the reorganisation of the carbonate platform ecosystem from heterozoan towards photozoan-dominated assemblages and a decrease of organic-matter burial in Tethyan and Boreal basins. In order to decipher the palaeoenvironmental and climatic boundary conditions of these major changes in neritic and pelagic settings, a precise chronostratigraphy of Urgonian carbonate platform evolution is needed. Here, we provide an integrated stratigraphic framework of Lower Barremian to Lower Aptian Urgonian carbonate platform sections (Cluses, Forclaz) located at the northern rim of the Tethys (Subalpine Chains, ESE France), with special focus on sedimentological analyses and high-resolution carbon-isotope stratigraphy. A characteristic Barremian-Aptian carbon-isotope pattern permits precise platform-to-basin correlation with cyclostratigraphic and ammonite-dated pelagic and hemipelagic Tethyan sections in the Vocontian Trough (Angles/Combe-Lambert/Glaise) and Umbria Marche Basin (Gorgo a Cerbara). Similar to Helvetic shoal-water settings, the carbonate platform in the Subalpine Chains experienced a gradual transition from heterozoan- to photozoan-dominated ecosystems. This biogenic pattern points to a gradual change of the carbonate platform after the so-called "Early Barremian crisis" towards an oligotrophic rimmed platform system (Urgonian Limestone Formation). According to the chronostratigraphy of Urgonian carbonate platform evolution in the Subalpine Chains established here, the installation of a

Facies interfingering and synsedimentary tectonics on late Ladinian-early Carnian carbonate platforms (Dolomites, Italy)

NASA Astrophysics Data System (ADS)

Keim, Lorenz; Brandner, Rainer

2001-11-01

A stratigraphic model for carbonate platform evolution in the Dolomites during the late Ladinian-early Carnian is presented. New light on pre-Raibl growth of individual carbonate platforms of the western Dolomites was shed by biostratigraphic data combined with a revised lithostratigraphy. At the Schlern, Langkofel and Sella, the carbonate factory (Upper Schlern Dolomite) remained productive into the lowermost Carnian (Cordevolian = Aon Zone), and caused a levelling-out of the former steep platform-to-basin relief. In the eastern Dolomites, platforms were producing till basal Julian 2 (Austriacum Zone). At the Sella and Langkofel, the sedimentation pattern after deposition of the Upper Schlern Dolomite was strongly influenced by synsedimentary tectonics. A first phase of extensional tectonics led to local fissures, block-tilting, graben structures and breccia deposits. Composition and fabric of the reworked clasts argue for local-source sediments and short transport distances. The extensional structures are sealed by sediments of Lower Carnian age. Two facies belts (Schlernplateau beds and Dürrenstein Dolomite), which interfinger at the western side of the Sella, reflect the shallow marine environment with terrigenous-volcanoclastic input in the western Dolomites. A second generation of breccias at the Sella documents local fracturing of the Dürrenstein and Upper Schlern Dolomite. Depositional environments across the western and eastern Dolomites were largely dependent on differential subsidence. The sediments of early Carnian age on top of the Schlern platform are a few metres thick only, whereas, in the eastern Dolomite, up to 400-m-thick carbonate sediments ('Richthofen reef' and Settsass platform) were deposited. The most incomplete stratigraphic record is present at the Mendel platform in the west, where Ladinian volcanics are unconformably overlain by late Carnian 'Raibl beds'. The increase in sediment thickness towards the eastern Dolomites becomes partly

A Late Cambrian Carbon Isotope Excursion Recorded in Passive Margin Dolostones of the Central Appalachian Basin, USA.

NASA Astrophysics Data System (ADS)

Mackey, J. E.; Stewart, B. W.

2016-12-01

A Late Cambrian global positive carbon isotope excursion, known as the SPICE event [1,2] is linked to possible widespread ocean anoxia and enhanced carbon burial [3,4]. We report data from the central Appalachian Conasauga Group from the upper portion of the Middle Cambrian Maryville limestone, through the Late Cambrian Nolichucky shale and Maynardville limestone members. A geochemical, macro-, and micro-scale analyses of core material from southeastern Ohio was carried out to further constrain the timing of oceanic anoxia and trace element geochemistry relative to sediment fluxes occurring at the transition of the Middle to Late Cambrian. The section represents condensed, passive margin shale deposition and carbonate ramp development on the continental shelf of Laurentia. Carbonate sediments (primarily diagenetic dolomite) record a positive δ13C (relative to V-PDB) excursion starting in the upper Nolichucky shale member, reaching its peak (+4.0) in the overlying Maynardville limestone. At this location, there is an offset between the onlap Nolichucky shale deposition and start of the C isotope excursion; this was reported as well in a carbonate section further south of this location [2], on the other side of an extensional feature (Rome Trough) that formed a deep marine basin during Cambrian time. The condensed shale package and relatively low TOC content in our samples is likely due to the combination of a shallow, upslope basin location and isostatic influence on passive margin sedimentation. However, within the Rome Trough, the Nolichucky shale is rich in organic carbon and a recent target of hydrocarbon exploration. The data suggest a possible link between deposition of this shale and the global SPICE event. The robustness of the Late Cambrian δ13C excursion in diagenetically altered sediments and association with hydrocarbon bearing units indicates its utility as a stratigraphic indicator and as a target for exploration. Ongoing geochemical work will focus

Impact of Diagenesis on Biosignature Preservation Potential in Playa Lake Evaporites in Verde Formation, Arizona: Implications for Mars Exploration

NASA Astrophysics Data System (ADS)

Shkolyar, S.; Farmer, J. D.

2015-12-01

Major priorities for Mars science include assessing the preservation potential and impact of diagenesis on biosignature preservation in aqueous sedimentary environments. We address these priorities with field and lab studies of playa evaporites of the Verde Formation (upper Pliocene) in Arizona. Evaporites studied include bottom-nucleated halite and displacive growth gypsum in magnesite-rich mudstone. These lithotypes are potential analogs for ancient lacustrine habitable environments on Mars. This study aimed to understand organic matter preservation potential under different diagenetic histories. Methods combined outcrop-scale field observations and lab analyses, including: (1) thin-section petrography to understand diagenetic processes and paragenesis; (2) X-ray powder diffraction to obtain bulk mineralogy; (3) Raman spectroscopy to identify and place phases (and kerogenous fossil remains) within a microtextural context; (4) Total Organic Carbon (TOC) analyses to estimate weight percentages of preserved organic carbon for each subfacies endmember; and (5) electron microprobe to create 2D kerogen maps semi-quantifying kerogen preservation in each subfacies. Results revealed complex diagenetic histories for each evaporite subfacies and pathways for organic matter preservation. Secondary gypsum grew displacively within primary playa lake mudstones during early diagenesis. Mudstones then experienced cementation by Mg-carbonates. Displacive-growth gypsum was sometimes dissolved, forming crystal molds. These molds were later either infilled by secondary sulfates or recrystallized to gypsum pseudomorphs with minor phases present (i.e., glauberite). These observations helped define taphonomic models for organic matter preservation in each subfacies. This work has the potential to inform in situ target identification, sampling strategies, and data interpretations for future Mars Sample Return missions (e.g., sample caching strategies for NASA's Mars 2020 mission).

Early diagenesis and authigenic mineral formation in mobile muds of the Changjiang Estuary and adjacent shelf

NASA Astrophysics Data System (ADS)

Zhao, Bin; Yao, Peng; Bianchi, Thomas S.; Xu, Yahong; Liu, Hui; Mi, Tiezhu; Zhang, Xiao-Hua; Liu, Jiwen; Yu, Zhigang

2017-08-01

Large-river delta-front estuaries (LDEs) and their adjacent shelf margins are sites of dynamic diagenetic processes that play a significant role in coastal biogeochemical cycling. In this study, we used dissolved inorganic carbon (DIC), redox sensitive elements (Fe2 + and Mn2 +), dissolved inorganic nitrogen (DIN) nutrients (NH4+, NO3-, and NO2-), major cations and anions (K+, Ca2 +, Mg2 +, SO42 -, and Cl-) in bottom-water and sediment pore-waters, to investigate the early chemical diagenesis and authigenic mineral formation in mobile-mud deposits of the Changjiang Estuary and adjacent inner shelf of the East China Sea (ECS). Vertical profiles of DIC and NH4+ in pore-waters had similar trends at most sites, showing a significant increase with depth near the Changjiang Estuary and being relatively constant at offshore sites. Higher pore-water DIC and NH4+ concentrations were observed in nearshore sites in winter, which were likely attributed to exposure of deeper deposits by winter coastal erosion. Nitrification was observed at most sites, and AOB (ammonia-oxidizing bacteria) played a leading role in ammonia oxidation in the study areas. The nitrification-denitrification was likely important in contributing to the loss of DIN in offshore sites during summer. Large inputs of organic carbon (OC) and terrestrial materials from Changjiang River resulted in intense sulfate reduction and Fe and Mn reduction in nearshore sites. Lower C/N and C/S ratios coupled with an apparent decrease in pore-water Ca2 + and Mg2+ concentrations with depth near the Changjiang Estuary, which indicated that authigenic carbonate formation occurs in these sediments. Decreases in K+ and Mg2 + with depth reflected that reverse weathering was an important process of authigenic mineral formation in these sediments. We conclude that adsorption process, seasonal erosion-redeposition, and summer hypoxic conditions of bottom-waters may play an important role in early diagenesis processes and

The clumped isotope geothermometer in soil and paleosol carbonate

NASA Astrophysics Data System (ADS)

Quade, J.; Eiler, J.; Daëron, M.; Achyuthan, H.

2013-03-01

) from long sequences of deeply buried (⩽5 km) paleosol carbonate in the Himalayan foreland in order to evaluate potential diagenetic resetting of clumped isotope composition. We found that paleosol carbonate faithfully records plausible soil T°C(47) down to 2.5-4 km burial depth, or ˜90-125 °C. Deeper than this and above this temperature, T°C(47) in paleosol carbonate is reset to temperatures >40 °C. We observe ˜40 °C as the upper limit for T°C(47) in modern soils from soil depths >25 cm, and therefore that T°C(47) >40 °C obtained from ancient soil carbonate indicates substantially warmer climate regimes compared to the present, or non-primary temperatures produced by resetting during diagenesis. If representative, this limits the use of T°C(47) to reconstruct ancient surface temperature to modestly buried (<3-4 km) paleosol carbonates. Despite diagenetic resetting of Δ47 values, δ18O and δ13C values of the same deeply buried paleosol carbonate appear unaltered. We conclude that solid-state reordering or recrystallization of clumping of carbon and oxygen isotopes can occur in the absence of open-system exchange of paleosol carbonate with significant quantities of water or other phases.

Astronomical Constraints on the Duration of Early Jurassic Stages and Global Carbon Cycle and Climatic Perturbations

NASA Astrophysics Data System (ADS)

Ruhl, M.; Hesselbo, S. P.; Hinnov, L.; Jenkyns, H. C.; Storm, M.; Xu, W.; Riding, J. B.; Ullmann, C. V.

2015-12-01

The Early Jurassic (201.3 to 174.1 Ma) is bracketed by the end-Triassic mass extinction and global warming event, and the Toarcian-Aalenian shift to (global) icehouse conditions (McElwain et al., 1999; Hesselbo et al., 2002; Ruhl et al., 2011; Korte et al., in review). It is further marked by the early Toarcian Oceanic Anoxic Event (T-OAE), with possibly the largest exogenic carbon cycle perturbation of the Mesozoic and related perturbations in global geochemical cycles, climate and the environment, which are linked to large igneous province emplacement in the Karoo-Ferrar region (Jenkyns, 2010; Burgess et al., 2015). Furthermore, Early Jurassic continental rifting and the break-up of Pangaea and subsequent Early Jurassic opening of the Hispanic Corridor and Viking Strait respectively linked the equatorial Tethys Ocean to Eastern Panthalassa and the high-latitude Arctic Boreal realm. This initiated changes in (global) ocean currents and Earth's heat distribution and ultimately was followed by the opening of the proto-North Atlantic (Porter et al., 2013; Korte et al., in review). Here, we present high-resolution (sub-precession scale) elemental concentration data from the Mochras borehole (UK), which represents ~1300m of possibly the most complete and expanded lower Jurassic hemi-pelagic marine sedimentary archive known. We construct a floating ~9 Myr astronomical time-scale for the complete Early Jurassic Pliensbachian stage and biozones. Combined with radiometric and astrochronological constraints on early Jurassic stage boundaries, we construct a new Early Jurassic Time-Scale. With this we assess the duration and rate of change of early Jurassic global carbon cycle and climatic perturbations and we asses fundamental changes in the nature and expression of Early Jurassic long (100 - 1000 kyr) eccentricity cycles.

Marine pisolites from Upper Proterozoic carbonates of East Greenland and Spitsbergen

NASA Technical Reports Server (NTRS)

Swett, K.; Knoll, A. H.

1989-01-01

Upper Proterozoic carbonate successions from central East Greenland (the Limestone-Dolomite 'Series' of the Eleonore Bay Group) and Svalbard (the Backlundtoppen Formation of the Akademikerbreen) Group, Spitsbergen, and the Upper Russo Formation of the Raoldtoppen Group, Nordaustlandet) contain thick sequences dominated by pisolites. These rocks were generated in shallow marine environments, and the pisoids are essentially oversized ooids. A marine environment is supported by the thickness and lateral extent of the carbonates; by a sedimentary association of pisolites with stromatolites, flake-conglomerates, calcarenites, calcilutites, microphytolites, and ooids similar to that found in numerous other Proterozoic carbonate successions; by sedimentary structures, including cross-beds and megaripples that characterize the pisolitic beds; and by microorganisms that inhabit modern marine ooids of the Bahama Banks. Petrographic features and strontium abundances suggest that the pisoids were originally aragonitic, but neomorphism, silicification, calcitization, and dolomitization have extensively modified original mineralogies and fabrics. The East Greenland and Svalbard pisolitic carbonates reflect similar depositional environments and diagenetic histories, reinforcing previous bio-, litho-, and chemostratigraphic interpretations that the two sequences accumulated contiguously in a coastal zone of pisoid genesis which extended for at least 600, and probably 1000 or more, kilometres.

Marine pisolites from Upper Proterozoic carbonates of East Greenland and Spitsbergen.

PubMed

Swett, K; Knoll, A H

1989-01-01

Upper Proterozoic carbonate successions from central East Greenland (the Limestone-Dolomite 'Series' of the Eleonore Bay Group) and Svalbard (the Backlundtoppen Formation of the Akademikerbreen) Group, Spitsbergen, and the Upper Russo Formation of the Raoldtoppen Group, Nordaustlandet) contain thick sequences dominated by pisolites. These rocks were generated in shallow marine environments, and the pisoids are essentially oversized ooids. A marine environment is supported by the thickness and lateral extent of the carbonates; by a sedimentary association of pisolites with stromatolites, flake-conglomerates, calcarenites, calcilutites, microphytolites, and ooids similar to that found in numerous other Proterozoic carbonate successions; by sedimentary structures, including cross-beds and megaripples that characterize the pisolitic beds; and by microorganisms that inhabit modern marine ooids of the Bahama Banks. Petrographic features and strontium abundances suggest that the pisoids were originally aragonitic, but neomorphism, silicification, calcitization, and dolomitization have extensively modified original mineralogies and fabrics. The East Greenland and Svalbard pisolitic carbonates reflect similar depositional environments and diagenetic histories, reinforcing previous bio-, litho-, and chemostratigraphic interpretations that the two sequences accumulated contiguously in a coastal zone of pisoid genesis which extended for at least 600, and probably 1000 or more, kilometres.

Diagenetic effects on magnetic minerals in a Holocene lacustrine sediment core from Huguangyan maar lake, southeast China

NASA Astrophysics Data System (ADS)

Wu, Xudong; Wang, Yong; Bian, Liu; Shen, Ji

2016-09-01

strong Asian summer monsoon intensity during the early Holocene are accountable for intensive diagenesis in the lowermost subsection. Complete erasing of detrital magnetic input signal at certain positions of the lowermost subsection, and considerable formation of authigenic siderite indicate that palaeomagnetic records of the studied core have been significantly compromised. The studied core has relatively higher TOC content, lower detrital matter content, calmer sedimentary environments, and less DO available at its water-sediment interface than the cores retrieved at relatively shallower water depths, which all contribute to its relatively stronger diagenesis. Progressive thickening of the upper two subsections with increasing water depth is owing to progressive increase in sedimentation rate with increasing water depth, which is the key factor in determining the thickness of each diagenetic subsection of cores from HGY. It would be better that lake sediments for palaeomagnetic investigations collected at a water depth shallower than the depth of its thermocline.

Diagenetic fate of organic contaminants on the Palos Verdes Shelf, California

USGS Publications Warehouse

Eganhouse, R.P.; Pontolillo, J.; Leiker, T.J.

2000-01-01

Municipal wastes discharged through deepwater submarine outfalls since 1937 have contaminated sediments of the Palos Verdes Shelf. A site approximately 6-8 km downcurrent from the outfall system was chosen for a study of the diagenetic fate of organic contaminants in the waste-impacted sediments. Concentrations of three classes of hydrophobic organic contaminants (DDT + metabolites, polychlorinated biphenyls (PCBs), and the long-chain alkylbenzenes) were determined in sediment cores collected at the study site in 1981 and 1992. Differences between the composition of effluent from the major source of DDT (Montrose Chemical) and that found in sediments suggests that parent DDT was transformed by hydrolytic dehydrochlorination during the earliest stages of diagenesis. As a result, p,p'-DDE is the dominant DDT metabolite found in shelf sediments, comprising 60-70% of ??DDT. The p,p-DDE/p,p'-DDMU concentration ratio decreases with increasing sub-bottom depth in sediment cores, indicating that reductive dechlorination of p,p'-DDE is occurring. Approximately 9-23% of the DDE inventory in the sediments may have been converted to DDMU since DDT discharges began ca. 1953. At most, this is less than half of the decline in p,p'-DDE inventory that has been observed at the study site for the period 1981-1995. Most of the observed decrease is attributable to remobilization by processes such as sediment mixing coupled to resuspension, contaminant desorption, and current advection. Existing field data suggest that the in situ rate of DDE transformation is 102-103 times slower than rates determined in recent laboratory microcosm experiments (Quensen, J.F., Mueller, S.A., Jain, M.K., Tiedje, J.M., 1998. Reductive dechlorination of DDE to DDMU in marine sediment microcosms. Science, 280, 722-724.). This explains why the DDT composition (i.e. o,p'-, p,p'-isomers of DDE, DDD, DDT) of sediments from this site have not changed significantly since at least 1972. Congener-specific PCB

Rudist bivalve shells as palaeoenvironmental archive: assessing ecological boundary conditions of Barremian subtropical carbonate platform ecosystems

NASA Astrophysics Data System (ADS)

Huck, Stefan; Heimhofer, Ulrich

2013-04-01

Mid-Cretaceous shoal-water ecosystems have been proven to show characteristic response modes (microencruster blooms, carbonate platform drowning) to major climatic and environmental changes that finally culminated in so-called oceanic anoxic events (OAEs). During most OAEs, the widespread burial of unusual amounts of organic matter in pelagic basins caused a strong carbon-cycle perturbation, expressed as prominent positive carbon-isotope excursion. Stratigraphically, the Aptian OAE1a is marked by a well-defined carbon-isotope pattern (negative spike and subsequent positive anomaly). Judging from high-resolution chemostratigraphic (C, Sr) studies, the observed neritic response modes are diachronous in nature and certain biotic changes (orbitolinid-rich sediments, Lithocodium blooms, carbonate platform drowning) clearly predate the deposition of OAE1a black-shales. The perturbations observed in the neritic realm underline the previously quoted progressive nature of Late Barremian-Early Aptian environmental change. Considering the observed time lag between the earliest biotic perturbations and widespread oceanic anoxia, a volcanic scenario related to the release of large volumes of CO2 during the formation of the Ontong Java large igneous province seems at least likely. The aim of the current project is to reconstruct the evolution of carbonate platform ecosystems in the northern subtropical realm during the early onset of enhanced (submarine) volcanic activity. A Late Barremian carbonate platform succession (Sausset-les-Pins section), deposited on a proximal part of the Provence platform (Marseille area, SE France), has been investigated applying high-resolution chemostratigraphy and detailed sedimentological analysis. The 60-m thick section is composed of peloidal to bioclastic packstones and grainstones rich in rudist bivalves (Urgonian limestones sensu stricto) and subordinate mudstones and wackestones. In order to obtain information on the palaeoecological and

A ground-water mixing model for the origin of the Imini manganese deposit (Cretaceous) of Morocco.

USGS Publications Warehouse

Force, E.R.; Back, W.; Spiker, E. C.; Knauth, L.P.

1986-01-01

Three beds of manganese oxide ore in a 10 m-thick dolomite unit are associated with diagenetic features, and, are accordingly also diagenetic in their present aspect. Whether primary or introduced, the Mn mineralogy is attributed to reactions between fresh and saline ground-waters as the zone of mixing passed through the dolomite unit during a period of falling sea-level. The succession of diagenetic changes is: 1) precursor carbonates, 2) dolomite-janggunite, 3) hollandite-pyrolusite-chert-calcite.-G.J.N.

Stable carbon isotope fractionation in the search for life on early Mars

NASA Technical Reports Server (NTRS)

Rothschild, L. J.; Desmarais, D.

1989-01-01

The utility of measurements of C-13/C-12 ratios in organic vs inorganic deposits for searching for signs of life on early Mars is considered. It is suggested that three assumptions are necessary. First, if there was life on Mars, it caused the fractionation of carbon isotopes in analogy with past biological activity on earth. Second, the fractionation would be detectable. Third, if a fractionation would be observed, there exist no abiotic explanations for the observed fractionation pattern.

Authigenic rhodochrosite from a gas hydrate-bearing structure in Lake Baikal

NASA Astrophysics Data System (ADS)

Krylov, Alexey A.; Hachikubo, Akihiro; Minami, Hirotsugu; Pogodaeva, Tatyana V.; Zemskaya, Tamara I.; Krzhizhanovskaya, Mariya G.; Poort, Jeffrey; Khlystov, Oleg M.

2018-02-01

Early diagenetic carbonates are rare in Lake Baikal. Siderite (Fe carbonate) concretions in the sediments were discovered only recently. Here, we discuss the first finding of rhodochrosite concretions (Mn carbonate) discovered in the near-bottom sediments of the gas hydrate-bearing seepage structure St. Petersburg-2 in the deep water environment of the Central Baikal Basin. The crystal lattice of rhodochrosite contains iron and calcium substituting to manganese. Based on pore water geochemistry and of δ 13C values of rhodochrosite (- 23.3 and - 29.4‰), carbon dioxide (+ 3.8 to - 16.1‰) and methane (- 63.2 to - 67.8‰), we show that carbonate crystallization most likely occurred during microbial anaerobic oxidation of organic matter, and that part of the oxygen making up the rhodochrosite seems to be derived from the 18O-rich water released from dissociating gas hydrates.

Pink salmon ( Oncorhynchus gorbuscha) marine survival rates reflect early marine carbon source dependency

NASA Astrophysics Data System (ADS)

Kline, Thomas C., Jr.; Boldt, Jennifer L.; Farley, Edward V., Jr.; Haldorson, Lewis J.; Helle, John H.

2008-05-01

Marine survival rate (the number of adult salmon returning divided by the number of salmon fry released) of pink salmon runs propagated by Prince William Sound, Alaska (PWS) salmon hatcheries is highly variable resulting in large year-to-year run size variation, which ranged from ∼20 to ∼50 million during 1998-2004. Marine survival rate was hypothesized to be determined during their early marine life stage, a time period corresponding to the first growing season after entering the marine environment while they are still in coastal waters. Based on the predictable relationships of 13C/ 12C ratios in food webs and the existence of regional 13C/ 12C gradients in organic carbon, 13C/ 12C ratios of early marine pink salmon were measured to test whether marine survival rate was related to food web processes. Year-to-year variation in marine survival rate was inversely correlated to 13C/ 12C ratios of early marine pink salmon, but with differences among hatcheries. The weakest relationship was for pink salmon from the hatchery without historic co-variation of marine survival rate with other PWS hatcheries or wild stocks. Year-to-year variation in 13C/ 12C ratio of early marine stage pink salmon in combination with regional spatial gradients of 13C/ 12C ratio measured in zooplankton suggested that marine survival was driven by carbon subsidies of oceanic origin (i.e., oceanic zooplankton). The 2001 pink salmon cohort had 13C/ 12C ratios that were very similar to those found for PWS carbon, i.e., when oceanic subsidies were inferred to be nil, and had the lowest marine survival rate (2.6%). Conversely, the 2002 cohort had the highest marine survival (9.7%) and the lowest mean 13C/ 12C ratio. These isotope patterns are consistent with hypotheses that oceanic zooplankton subsidies benefit salmon as food subsidies, or as alternate prey for salmon predators. Oceanic subsidies are manifestations of significant exchange of material between PWS and the Gulf of Alaska. Given

A carbon isotope mass balance for an anoxic marine sediment: Isotopic signatures of diagenesis

NASA Technical Reports Server (NTRS)

Boehme, Susan E.

1993-01-01

A carbon isotope mass balance was determined for the sediments of Cape Lookout Bight, NC to constrain the carbon budgets published previously. The diffusive, ebullitive and burial fluxes of sigma CO2 and CH4, as well as the carbon isotope signatures of these fluxes, were measured. The flux-weighted isotopic signature of the remineralized carbon (-18.9 plus or minus 2.7 per mil) agreed with the isotopic composition of the remineralized organic carbon determined from the particulate organic carbon (POC) delta(C-13) profiles (-19.2 plus or minus 0.2), verifying the flux and isotopic signature estimates. The measured delta(C-13) values of the sigma CO2 and CH4 diffusive fluxes were significantly different from those calculated from porewater gradients. The differences appear to be influenced by methane oxidation at the sediment-water interface, although other potential processes cannot be excluded. The isotope mass balance provides important information concerning the locations of potential diagenetic isotope effects. Specifically, the absence of downcore change in the delta(C-13) value of the POC fraction and the identical isotopic composition of the POC and the products of remineralization indicate that no isotopic fractionation is expressed during the initial breakdown of the POC, despite its isotopically heterogeneous composition.

Sedimentology, petrography and early diagenesis of a travertine-colluvium succession from Chusang (southern Tibet)

NASA Astrophysics Data System (ADS)

Wang, Zhijun; Meyer, Michael C.; Hoffmann, Dirk L.

2016-08-01

The Chusang travertine is situated in southern Tibet at an altitude of ~ 4200 m asl. in a cold-arid, periglacial environment and is characterized by interbedding of hydrothermal carbonate with colluvium. Here we present sedimentological and petrographical data to elucidate the depositional environment and sedimentary processes responsible for hydrothermal carbonate precipitation and early diagenetic alteration as well as clastic sediment accumulation and provide initial 230Th/U ages to constrain the time-depth of this travertine-colluvium succession. Three main travertine lithofacies have been identified: 1) a dense laminated lithofacies, 2) a porous layered lithofacies and 3) an intraclastic lithofacies that results from erosion of pre-existing hot spring carbonate. The colluvium is composed of cohesive debris flow layers that derived from mass-wasting events from the adjacent hillslopes. Micro-fabric analyses suggest that dense laminated travertine forms via rapid calcite precipitation from hot spring water seasonally subjected to severe winter cooling, while porous layered travertine results from seasonal dilution of hot spring water with rain water during the summer monsoon months, which in turn stimulates biological productivity and gives rise to a porous summer layer. Early diagenesis in the form of recrystallization and extensive formation of pore cements is common in the Chusang travertine, but never eradicates the original crystal fabrics completely. The sedimentary architecture of the deposit is conditioned by (i) the gently dipping (~ 10°) pre-existing terrain on which hot spring water is discharged from multiple travertine mounds causing laterally extensive travertine sheets to precipitate, and (ii) the adjacent much steeper (up to 30°) periglacial hillslopes that are the source area of repeated debris flows that accumulate on the travertine surface. The resulting travertine-colluvium succession has a total thickness of ~ 24 m and 230Th/U dating

A terrestrial Eocene stack: tying terrestrial lake ecology to marine carbon cycling through the Early Eocene Climatic Optimum

NASA Astrophysics Data System (ADS)

Grogan, D. S.; Whiteside, J. H.; Musher, D.; Rosengard, S. Z.; Vankeuren, M. A.; Pancost, R. D.

2010-12-01

The lacustrine Green River Formation is known to span ≥15 million years through the early-middle Eocene, and recent work on radioisotopic dating has provided a framework on which to build ties to the orbitally-tuned marine Eocene record. Here we present a spliced stack of Fischer assay data from drilled cores of the Green River Formation that span both an East-West and a North-South transect of the Uinta Basin of Utah. Detailed work on two cores demonstrate that Fischer assay measurements covary with total organic carbon and bulk carbon isotopes, allowing us to use Fisher assay results as a representative carbon cycling proxy throughout the stack. We provide an age model for this core record by combining radioisotopic dates of tuff layers with frequency analysis of Fischer assay measurements. Identification of orbital frequencies tied directly to magnetochrons through radioisotopic dates allows for a direct comparison of the terrestrial to the marine Eocene record. Our analysis indicates that the marker beds used to correlate the stack cores represent periods of enhanced lake productivity and extreme carbon burial; however, unlike the hyperthermal events that are clearly marked in the marine Eocene record, the hydrocarbon-rich "Mahogany Bed" period of burial does not correspond to a clear carbon isotope excursion. This suggests that the terrestrial realm may have experienced extreme ecological responses to relatively small perturbations in the carbon cycle during the Early Eocene Climatic Optimum. To investigate the ecological responses to carbon cycle perturbations through the hydrocarbon rich beds, we analyzed a suite of microbial biomarkers, finding evidence for cyanobacteria, dinoflagellates, and potentially green sulfur bacteria. These taxa indicate fluctuating oxic/anoxic conditions in the lake during abrupt intervals of carbon burial, suggesting a lake biogeochemical regime with no modern analogues.

Disequilibrium δ18O values in microbial carbonates as a tracer of metabolic production of dissolved inorganic carbon

NASA Astrophysics Data System (ADS)

Thaler, Caroline; Millo, Christian; Ader, Magali; Chaduteau, Carine; Guyot, François; Ménez, Bénédicte

2017-02-01

both disequilibrium effects are triggered by the metabolic production of CO2, which is common in many microbially-mediated carbonation processes, leads us to propose that metabolically-induced offsets from isotopic equilibrium in microbial carbonates may be more common than previously considered. Therefore, precaution should be taken when using the oxygen isotope signature of microbial carbonates for diagenetic and paleoenvironmental reconstructions.

Major geochemical processes in the evolution of carbonate-Aquifer systems

USGS Publications Warehouse

Hanshaw, B.B.; Back, W.

1979-01-01

-reefs, where reflux dolomites may form, highly alkaline, on-shore and continental lakes, and sabkha flats; these dolomites are typically associated with evaporite minerals. However, these processes cannot account for most of the regionally extensive dolomites in the geologic record. A major environment of regional dolomitization is in the mixing zone (zone of dispersion) where profound changes in mineralogy and redistribution of porosity and permeability occur from the time of early emergence and continuing through the time when the rocks are well-developed aquifers. The reactions and processes, in response to mixing waters of differing chemical composition, include dissolution and precipitation of carbonate minerals in addition to dolomitization. An important control on permeability distribution in a mature aquifer system is the solution of dolomite with concomitant precipitation of calcite in response to gypsum dissolution (dedolomitization). Predictive models developed by mass-transfer calculations demonstrate the controlling reactions in aquifer systems through the constraints of mass balance and chemical equilibrium. An understanding of the origin, chemistry, mineralogy and environments of deposition and accumulation of carbonate minerals together with a comprehension of diagenetic processes that convert the sediments to rocks and geochemical, tectonic and hydrologic phenomena that create voids are important to hydrologists. With this knowledge, hydrologists are better able to predict porosity and permeability distribution in order to manage efficiently a carbonate-aquifer system. ?? 1979.

Constraining Δ33S signatures of Archean seawater sulfate with carbonate-associated sulfate

NASA Astrophysics Data System (ADS)

Peng, Y.; Bao, H.; Bekker, A.; Hofmann, A.

2017-12-01

Non-mass dependent sulfur isotope deviation of S-bearing phases in Archean sedimentary strata, and expressed as Δ33S, has a consistent pattern, i.e., sulfide (pyrite) predominantly bear positive Δ33S values, while Paleoarchean sulfate (barite) has negative Δ33S values. This pattern was later corroborated by observations of negative Δ33S values in Archean volcanogenic massive sulfide deposits and negative Δ33S values in early diagenetic nodular pyrite with a wide range of δ34S values, which is thought to be due to microbial sulfate reduction. These signatures have provided a set of initial conditions for a mechanistic interpretation at physical chemistry level. Unlike the younger geological times when large bodies of seawater evaporite deposits are common, to expand seawater sulfate records, carbonate-associated sulfate (CAS) was utilized as a proxy for ancient seawater sulfate. CAS extracted from the Archean carbonates carries positive Δ33S values. However, CAS could be derived from pyrite oxidation following exposure to modern oxidizing conditions and/or during laboratory extraction procedures. It is, therefore, important for us understanding context of the overall early earth atmospheric condition to empirically confirm whether Archean seawater sulfate was generally characterized by negative Δ33S signatures. Combined δ18O, Δ17O, δ34S, and Δ33S analyses of sequentially extracted water-leachable sulfate (WLS) and acid-leachable sulfate (ALS = CAS) and δ34S and Δ33S analyses of pyrite can help to identify the source of extracted sulfate. We studied drill-core samples of Archean carbonates from the 2.55 Ga Malmani and Campell Rand supgroups, South Africa. Our preliminary results show that 1) neither WLS nor ALS were extracted from samples with extremely low pyrite contents (less than 0.05 wt.%); 2) extractable WLS and ALS is present in samples with relatively high pyrite contents (more than 1 wt.%), and that δ34S and Δ33S values of WLS, ALS, and

Fluid-rock reactions in an evaporitic melange, Permian Haselgebirge, Austrian Alps

USGS Publications Warehouse

Spotl, C.; Longstaffe, F.J.; Ramseyer, K.; Kunk, Michael J.; Wiesheu, R.

1998-01-01

Tectonically isolated blocks of carbonate rocks present within the anhydritic Haselgebirge melange of the Northern Calcareous Alps record a complex history of deformation and associated deep-burial diagenetic to very low-grade metamorphic reactions. Fluids were hot (up to ~ 250 ??C) and reducing brines charged with carbon dioxide. Individual carbonate outcrops within the melange record different regimes of brine-rock reactions, ranging from pervasive dolomite recrystallization to dedolomitization. Early diagenetic features in these carbonates were almost entirely obliterated. Matrix dolomite alteration was related to thermochemical sulphate reduction (TSR) recognized by the replacement of anhydrite by calcite + pyrite ?? native sulphur. Pyrite associated with TSR is coarsely crystalline and characterized by a small sulphur isotope fractionation relative to the precursor Permian anhydrite. Carbonates associated with TSR show low Fe/Mn ratios reflecting rapid reaction of ferrous iron during sulphide precipitation. As a result, TSR-related dolomite and calcite typically show bright Mn(II)-activated cathodoluminescence in contrast to the dull cathodoluminescence of many (ferroan) carbonate cements in other deep-burial settings. In addition to carbonates and sulphides, silicates formed closely related to TSR, including quartz, K-feldspar, albite and K-mica. 40Ar/39Ar analysis of authigenic K-feldspar yielded mostly disturbed step-heating spectra which suggest variable cooling through the argon retention interval for microcline during the Late Jurassic. This timing coincides with the recently recognized subduction and closure of the Meliata-Hallstatt ocean to the south of the Northern Calcareous Alps and strongly suggests that the observed deep-burial fluid-rock reactions were related to Jurassic deformation and melange formation of these Permian evaporites.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruno, C.; Eichenseer, H.; Calatayud, P.

The poster illustrates how the recent developments in genetic stratigraphy have contributed to constrain reservoir layering and to improve prediction of reservoir quality in the oil-bearing reservoir of N`KOSSA. The mixed lithology deposits formed during Albian times. Thanks to the excellent core coverage of the reservoir (4 cored wells over the entire reservoir interval), continuous sedimentological examination and interpretation of the facies succession have been carried out. The reservoir can be subdivided into composite sequences (50 to 150 in thick) which are made up of stacked metre-scale genetic units. Three different stacking patterns of genetic units have been identified; retrogradation,more » aggradation and progradation. These patterns reflect a gradual change of depositional regimes through time. Facies variations (texture, bio-association, geometry, spatial distribution) and early diagenetic overprints can be related to each type of stacking pattern. One additional model illustrates the depositional regime corresponding to low accomodation periods which mainly record siliciclastic input and extensive carbonate diagenesis by meteoric waters The resulting four models show the overall distribution of the main depositional units, the diagenetic zonations and the resulting overall reservoir qualities. This above approach have contributed to a more detailed reservoir architecture and a better delineation of reservoir heterogeneity due to both depositional and diagenetic regimes.« less

Bio- and chemostratigraphy of the Early Aptian Oceanic Anoxic Event 1a within the mid-latitudes of northwest Europe (Germany, Lower Saxony Basin)

NASA Astrophysics Data System (ADS)

Heldt, Matthias; Mutterlose, Joerg; Berner, Uli; Erbacher, Jochen

2013-04-01

The Mid-Cretaceous period was characterised by a series of prominent anoxic events, one of these was the late Early Aptian Oceanic Anoxic Event 1a (OAE 1a). The Fischschiefer horizon is the regional sedimentary expression of this event in a small epicontinental sea in northwest Europe (Germany, Lower Saxony Basin). In the present study, two sediment cores of Lower to Upper Aptian age (Hoheneggelsen KB 9 and 40) from the Brunswick area, north Germany, have been investigated in detail with respect to their lithostratigraphy, geochemistry (CaCO3, TOC), biostratigraphy (coccoliths, nannoliths) and high-resolution chemostratigraphy (^13Ccarb and ^13Corg). Together with separately published new planktonic foraminifer data of the cores it was possible to establish a detailed time frame and to recognise the OAE 1a. The ^13C data enabled us to subdivide the deposits into isotope segments (C2-C7), which are commonly used as stratigraphic markers in coeval sediments around the world. The carbon isotope curves are compared to recently published Aptian curves from other parts of the Lower Saxony Basin, all of which record the prominent carbon isotope anomaly of the OAE 1a. A high-resolution correlation of the typical isotope trends of OAE 1a (segments C3-6) across the Lower Saxony Basin appears difficult due to an early diagenetic overprint of the primary isotope signal. These alterations can be explained by the temporary establishment of euxinic conditions the Lower Saxony Basin during OAE 1a as consequence of an interplay of different factors, such as global warming, restricted palaeogeography, increased fluvial input and intensified stable water stratification, which is supported by several lines of regional evidence.

Trace metal (Mg/Ca and Sr/Ca) analyses of single coccoliths by Secondary Ion Mass Spectrometry

NASA Astrophysics Data System (ADS)

Prentice, Katy; Jones, Tom Dunkley; Lees, Jackie; Young, Jeremy; Bown, Paul; Langer, Gerald; Fearn, Sarah; EIMF

2014-12-01

Here we present the first multi-species comparison of modern and fossil coccolith trace metal data obtained from single liths. We present both trace metal analyses (Sr, Ca, Mg and Al) and distribution maps of individual Paleogene fossil coccoliths obtained by Secondary Ion Mass Spectrometry (SIMS). We use this data to determine the effects of variable coccolith preservation and diagenetic calcite overgrowths on the recorded concentrations of strontium and magnesium in coccolith calcite. The analysis of coccoliths from deep-ocean sediments spanning the Eocene/Oligocene transition demonstrates that primary coccolith calcite is resistant to the neomorphism that is common in planktonic foraminifera from similar depositional environments. Instead, where present, diagenetic calcite forms distinct overgrowths over primary coccolith calcite rather than replacing this calcite. Diagenetic overgrowths on coccoliths are easily distinguished in SIMS analyses on the basis of relatively higher Mg and lower Sr concentrations than co-occurring primary coccolith calcite. This interpretation is confirmed by the comparable SIMS analyses of modern cultured coccoliths of Coccolithus braarudii. Further, with diagenetic calcite overgrowth being the principle source of bias in coccolith-based geochemical records, we infer that lithologies with lower carbonate content, deposited below the palaeo-lysocline, are more likely to produce geochemical records dominated by primary coccolith calcite than carbonate-rich sediments where overgrowth is ubiquitous. The preservation of primary coccolith carbonate in low-carbonate lithologies thus provides a reliable geochemical archive where planktonic foraminifera are absent or have undergone neomorphism.

The causes of covariation between C and O isotopes in the inorganic carbonate record

NASA Astrophysics Data System (ADS)

Swart, Peter; Oehlert, Amanda

2017-04-01

The δ13C values of carbonate rocks are widely used as proxies for understanding the global carbon cycle. While most workers would prefer to use δ13C values measured in oceanic sediments, during older times the only records that exist are those found in sediments deposited in epeiric seas or on continental margins and carbonate platforms. However, such records are often compromised by near surface diagenesis and therefore care must be taken to exclude altered records. One approach, which has been widely applied, has been to examine the covariation between δ13C and δ18O values, where a positive covariation has been suggested to indicate alteration. In order to test this assumption we present data from a core taken in the Bahamas that has been unequivocally subjected to both freshwater and marine diagenetic processes. Our data suggest that the majority of the zone which has been altered by freshwater shows no correlation between δ13C and δ18O values, with small intervals associated with sub-aerial exposure exhibiting inverse correlations, and only the upper partially altered portion of the core exhibiting positive relationships. The zone below the region of freshwater alteration, previously interpreted as being the mixing-zone, is characterized by a strong covariation between δ13C and δ18O values as a result of the upper portion of this zone having been affected by fresh water diagenesis compared to the lower portion. Within the marine influenced realm a variety of relationships are produced as a result of differences in sediment origin and diagenesis. For example, non-depositional surfaces, where marine diagenetic processes are maximized, are typically expressed by sharp positive correlations between δ13C and δ18O values, while changes related to different sediment sources are expressed as weak positive covariations. While the data set presented here may not be applicable in every situation, the study certainly emphasizes that care must be taken when rules

Lipidic biosignatures in diagenetically stabilized ironstones terraces of Rio Tinto, an acidic environment with analogies to Mars

NASA Astrophysics Data System (ADS)

Sánchez-García, L.; Carrizo, D.; Fernández-Remolar, D.; Parro, V.

2017-09-01

The characterization of extreme environments with analogies to Mars is important for understanding if/how life may have thrived in the Red Planet. Río Tinto in SW Spain is an extreme environment with constant acidic waters (mean pH of 2.3) and high concentration of heavy metals, which are direct consequence of the active metabolism of chemolithotrophic microorganisms thriving in the rich polymetallic sulfides present in the massive Iberian Pyritic Belt. Abundant minerals rich in ferric iron and sulfates, which result from the pyrite metabolism (e.g. jarosite, goethite, hematites, etc.) are of special interest for their potential for organics preservation [1]. Here, we investigate the occurrence and preservation of biological signatures in diagenetically stabilized ironstone deposits in Río Tinto, by using geolipidic markers.

Architecture and evolution of an Early Permian carbonate complex on a tectonically active island in east-central California

USGS Publications Warehouse

Stevens, Calvin H.; Magginetti, Robert T.; Stone, Paul

2015-01-01

The newly named Upland Valley Limestone represents a carbonate complex that developed on and adjacent to a tectonically active island in east-central California during a brief interval of Early Permian (late Artinskian) time. This lithologically unique, relatively thin limestone unit lies within a thick sequence of predominantly siliciclastic rocks and is characterized by its high concentration of crinoidal debris, pronounced lateral changes in thickness and lithofacies, and a largely endemic fusulinid fauna. Most outcrops represent a carbonate platform and debris derived from it and shed downslope, but another group of outcrops represents one or possibly more isolated carbonate buildups that developed offshore from the platform. Tectonic activity in the area occurred before, probably during, and after deposition of this short-lived carbonate complex.

Early Carboniferous (Tournasian-early Visean) global paleogeography, Paleostorm tracts, and the distribution of Waulsortian and Waulsortian-like carbonate mud mounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

King, D.T. Jr.

1990-05-01

Tournasian-early Visean mud mounds (i.e., Waulsortian and Waulsortian-like mounds) are unlike other carbonate buildups in the stratigraphic record because they lack an identifiable frame-building organism. Waulsortian mounds are comprised mainly of carbonate mud; Waulsortian-like mounds are mud-rich and contain a significant percent of skeletal grains, especially crinoids and bryozoa. This study has revealed that all of the reported Waulsortian and Waulsortian-like mounds developed in low paleolatitudes either on the southern shelf margin of the Laurussian paleocontinent or in the Laurussian interior seaway. Waulsortian and Waulsortian-like mounds are specifically not present in low-latitude regions of other paleocontinents. As Tournasian-early Visean carbonatemore » deposition was widespread in the range of 30{degree}N to 10{degree}S, the very restricted paleogeographic distribution of Waulsortian and Waulsortian-like mound locations suggests a mechanism or set of conditions that effectively limited the distribution of mud mounds. Considering the Tournasian-early Visean distribution of paleocontinents and the principles that govern the movement of modern hurricanes, tropical storms, and winter storms, the tracts of hurricanes, tropical storms, and winter storms probably crossed all main submerged paleocontinental areas except the southern Laurussian shelf margin and the Laurussian interior seaway, the two areas where mud mounds developed. The lack of storm energy in these two large areas of Laurussia provided long-term stability and thus enhanced the growth prospects of the frame-deficient Waulsortian and Waulsortian-like mud mounds. Lack of extensive periodic wave reworking and other storm-induced devastation helps to account for enigmatic features such as general mound symmetry, great size, high depositional relief (as much as 220 m), and side steepness (as steep as 50{degree}).« less

Evolution of Cupido and Coahuila carbonate platforms, early Cretaceous, northeastern Mexico

USGS Publications Warehouse

Lehmann, Christoph; Osleger, David A.; Montañez, Isabel P.; Sliter, William V.; Arnaud Vanneau, Annie; Banner, Jay L.

1999-01-01

The Cupido and Coahuila platforms of northeastern Mexico are part of the extensive carbonate platform system that rimmed the ancestral Gulf of Mexico during Barremian to Albian time. Exposures of Cupido and Coahuila lithofacies in several mountain ranges spanning an ∼80000 km2 area reveal information about platform morphology and composition, paleoenvironmental relations, and the chronology of platform evolution. New biostratigraphic data, integrated with carbon and strontium isotope stratigraphy, significantly improve chronostratigraphic relations across the region. These data substantially change previous age assignments of several formations and force a revision of the longstanding stratigraphy in the region. The revised stratigraphy and enhanced time control, combined with regional facies associations, allow the construction of cross sections, isopach maps, and time-slice paleogeographic maps that collectively document platform morphology and evolution.The orientation of the Cupido (Barremian-Aptian) shelf margin was controlled by the emergent Coahuila basement block to the northwest. The south-facing margin is a high-energy grainstone shoal, whereas the margin facing the ancestral Gulf of Mexico to the east is a discontinuous rudist-coral reef. A broad shelf lagoon developed in the lee of the Cupido margin, where as much as 660 m of cyclic peritidal deposits accumulated. During middle to late Aptian time, a major phase of flooding forced a retrograde backstep of the Cupido platform, shifting the locus of shallow-marine sedimentation northwestward toward the Coahuila block. This diachronous flooding event records both the demise of the Cupido shelf and the consequent initiation of the Coahuila ramp.The backstepped Coahuila ramp (Aptian-Albian) consisted of a shallow shoal margin separating an interior evaporitic lagoon from a low-energy, muddy deep ramp. More than 500 m of cyclic carbonates and evaporites accumulated in the evaporitic lagoon during early to

The oceanic carbon cycle implicated in the d13Ccarb and the d13Corg variations from the terminal Ediacaran to the Early Cambrian

NASA Astrophysics Data System (ADS)

Ishikawa, T.; Ueno, Y.; Komiya, T.; Shu, D.; Li, Y.; Yoshida, N.; Maruyama, S.

2009-04-01

The terminal Neoproterozoic and its transition into the Cambrian witnessed major evolutionary and geochemical changes (e.g. Knoll, 1994). Evolutionary features include extinction and subsequent radiation events (e.g. Brasier, 1994; Knoll, 1994; Knoll and Carroll, 1999; Shu 2008). Geochemical changes comprise secular variations of the global carbon cycle expressed as variations of the d13C isotope records. A representative d13C curve for inorganic carbon (d13Ccarb) across the Precambrian/Cambrian boundary (Pc/C boundary) shows the existence of large fluctuations (e.g. Kirschvink et al., 1991; Narbonne et al., 1994; Kaufman et al., 1995; Amthor et al., 2003; Maloof et al., 2005, Ishikawa et al., 2008). This indicates a significant change of the oceanic carbon cycle at that time. On the other hand, the d13C values for total organic carbon (d13Corg) have rarely been reported together with the d13Ccarb across the boundary. Therefore, the precise relation between the d13Ccarb and the d13Corg and the global carbon cycle at the Pc/C boundary are still ambiguous. This work presents a first high-resolution d13Corg chemostratigraphy of drill core samples across the Pc/C boundary in the Three Gorges area, South China. Based on the results, this work additionally proposes variations of the sizes of the oceanic carbon reservoirs by a calculation of the carbon cycle model at the Pc/C boundary. The Three Gorges section extends from the uppermost Ediacaran dolostone (Dengying Formation), through the lowermost Early Cambrian muddy limestone (Yanjiahe Formation) to the middle Early Cambrian calcareous black shale (Shuijingtuo Formation). The ^13Corg values exhibit relatively invariant values averaging at -31 permil. By comparison between the d13Ccarb and d13Corg, we recognize two different terms in this period. The first term from the Pc/C boundary to the early Nemakit-Daldynian (ND) is characterized by the decoupling of d13Corg and d13Ccarb, stable d13Corg and the significant

Geothermal prospection in the Greater Geneva Basin (Switzerland and France). Impact of diagenesis on reservoir properties of the Upper Jurassic carbonate sediments

NASA Astrophysics Data System (ADS)

Makhloufi, Yasin; Rusillon, Elme; Brentini, Maud; Clerc, Nicolas; Meyer, Michel; Samankassou, Elias

2017-04-01

Diagenesis of carbonate rocks is known to affect the petrophysical properties (porosity, permeability) of the host rock. Assessing the diagenetic history of the rock is thus essential when evaluating any reservoir exploitation project. The Canton of Geneva (Switzerland) is currently exploring the opportunities for geothermal energy exploitation in the Great Geneva Basin (GGB) sub-surface. In this context, a structural analysis of the basin (Clerc et al., 2016) associated with reservoir appraisal (Brentini et al., 2017) and rock-typing of reservoir bodies of potential interest were conducted (Rusillon et al., 2017). Other geothermal exploitation projects elsewhere (e.g. Bavaria, south Germany, Paris Basin, France) showed that dolomitized carbonate rocks have good reservoir properties and are suitable for geothermal energy production. The objectives of this work are to (1) describe and characterize the dolomitized bodies in the GGB and especially their diagenetic history and (2) quantify the reservoir properties of those bodies (porosity, permeability). Currently, our study focuses on the Upper Jurassic sedimentary bodies of the GGB. Field and well data show that the dolomitization is not ubiquitous in the GGB. Results from the petrographical analyses of the Kimmeridgian cores (Humilly-2) and of field analogues (Jura, Saleve and Vuache mountains) display complex diagenetic histories, dependent of the study sites. The paragenesis exhibits several stages of interparticular calcite cementation as well as different stages of dolomitization and/or dedolomitization. Those processes seem to follow constrained path of fluid migrations through burial, faulting or exhumation during the basin's history. These complex diagenetic histories affected the petrophysical and microstructural properties via porogenesis (conservation of initial porosity, moldic porosity) and/or poronecrosis events. The best reservoir properties appear to be recorded in patch reef and peri

Sedimentary evidence for enhanced hydrological cycling in response to rapid carbon release during the early Toarcian oceanic anoxic event

NASA Astrophysics Data System (ADS)

Izumi, Kentaro; Kemp, David B.; Itamiya, Shoma; Inui, Mutsuko

2018-01-01

A pronounced excursion in the carbon-isotope composition of biospheric carbon and coeval seawater warming during the early Toarcian (∼183 Ma) has been linked to the large-scale transfer of 12C-enriched carbon to the oceans and atmosphere. A European bias in the distribution of available data means that the precise pattern, tempo and global expression of this carbon cycle perturbation, and the associated environmental responses, remain uncertain. Here, we present a new cm-scale terrestrial-dominated carbon-isotope record through an expanded lower Toarcian section from Japan that displays a negative excursion pattern similar to marine and terrestrial carbon-isotope records documented from Europe. These new data suggest that 12C-enriched carbon was added to the biosphere in at least one rapid, millennial-scale pulse. Sedimentological analysis indicates a close association between the carbon-isotope excursion and high-energy sediment transport and enhanced fluvial discharge. Together, these data support the hypothesis that a sudden strengthening of the global hydrological cycle occurred in direct and immediate response to rapid carbon release and atmospheric warming.

Application of carbon nanoparticles in laparoscopic sentinel lymph node detection in patients with early-stage cervical cancer.

PubMed

Lu, Yan; Wei, Jin-Ying; Yao, De-Sheng; Pan, Zhong-Mian; Yao, Yao

2017-01-01

To investigate the value of carbon nanoparticles in identifying sentinel lymph nodes in early-stage cervical cancer. From January 2014 to January 2016, 40 patients with cervical cancer stage IA2-IIA, based on the International Federation of Gynecology and Obstetrics (FIGO) 2009 criteria, were included in this study. The normal cervix around the tumor was injected with a total of 1 mL of carbon nanoparticles (CNP)at 3 and 9 o'clock. All patients then underwent laparoscopic pelvic lymph node dissection and radical hysterectomy. The black-dyed sentinel lymph nodes were removed for routine pathological examination and immunohistochemical staining. Among the 40 patients, 38 patients had at least one sentinel lymph node (SLN). The detection rate was 95% (38/40). One hundred seventy-three SLNs were detected with an average of 3.9 SLNs per side. 25 positive lymph nodes, which included 21 positive SLNs, were detected in 8 (20%) patients. Sentinel lymph nodes were localized in the obturator (47.97%), internal lilac (13.87%), external lilac (26.59%), parametrial (1.16%), and common iliac (8.67%) regions. The sensitivity of the SLN detection was 100% (5/5), the accuracy was 97.37% (37/38), and the negative predictive value was 100. 0% and the false negative rate was 0%. Sentinel lymph nodes can be used to accurately predict the pathological state of pelvic lymph nodes in early cervical cancer. The detection rates and accuracy of sentinel lymph node were high. Carbon nanoparticles can be used to trace the sentinel lymph node in early cervical cancer.

The evolution of Phanerozoic seawater - Isotope paleothermometry finds consensus on Early Paleozoic warmth and constant seawater δ18O

NASA Astrophysics Data System (ADS)

Grossman, E. L.; Henkes, G. A.; Passey, B. H.; Shenton, B.; Yancey, T. E.; Perez-Huerta, A.

2015-12-01

Evolution of metazoan life is closely linked to the Phanerozoic evolution of ocean temperatures and chemistry. Oxygen isotopic evidence for early Phanerozoic paleotemperatures has been equivocal, with decreasing δ18O values with age being interpreted as warmer early oceans, decreasing seawater δ18O with age, or increasing diagenetic alteration in older samples. Here we compare an updated compilation of oxygen isotope data for carbonate and phosphate fossils and microfossils (Grossman, 2012, Geol. Time Scale, Elsevier, 195-220) with a compilation of new and existing clumped isotope data. Importantly, these data are curated based on sample preservation with special consideration given to screening techniques, and tectonic and burial history. Burial history is critical in the preservation of carbonate clumped isotope temperatures in particular, which can undergo reordering in the solid state. We use a model derived for reordering kinetics (Henkes et al., 2014, Geochim. Cosmochim. Acta 139:362-382) to screen clumped isotope data for the effects of solid-state burial alteration. With minor but significant exceptions (Late Cretaceous, Early Triassic), average δ18O values (4 m.y. window, 2 m.y. steps) for post-Devonian brachiopods, belemnites, and foraminifera, representing tropical-subtropical surface ocean conditions, yield average isotopic temperatures below 30°C (assuming a seawater δ18O value [ -1‰ VSMOW] of an "ice-free" world). In contrast, Ordovician to Devonian data show sustained temperatures of 35-40°C. Likewise, isotopic paleotemperatures from conodont apatite, known to be resistant to isotopic exchange, follow the same pattern. Clumped isotope data derived from Paleozoic brachiopod shells that experienced minimal burial (< 100 °C) and <1% reordering according to the taxon-specific clumped isotope reordering model yield typical temperatures of 25-30°C for the Carboniferous, and 35-40°C for the Ordovician-Silurian. Inserting clumped temperatures and

Organic matter mineralization and trace element post-depositional redistribution in Western Siberia thermokarst lake sediments

NASA Astrophysics Data System (ADS)

Audry, S.; Pokrovsky, O. S.; Shirokova, L. S.; Kirpotin, S. N.; Dupré, B.

2011-11-01

This study reports the very first results on high-resolution sampling of sediments and their porewaters from three thermokarst (thaw) lakes representing different stages of ecosystem development located within the Nadym-Pur interfluve of the Western Siberia plain. Up to present time, the lake sediments of this and other permafrost-affected regions remain unexplored regarding their biogeochemical behavior. The aim of this study was to (i) document the early diagenesic processes in order to assess their impact on the organic carbon stored in the underlying permafrost, and (ii) characterize the post-depositional redistribution of trace elements and their impact on the water column. The estimated organic carbon (OC) stock in thermokarst lake sediments of 14 ± 2 kg m-2 is low compared to that reported for peat soils from the same region and denotes intense organic matter (OM) mineralization. Mineralization of OM in the thermokarst lake sediments proceeds under anoxic conditions in all the three lakes. In the course of the lake development, a shift in mineralization pathways from nitrate and sulfate to Fe- and Mn-oxyhydroxides as the main terminal electron acceptors in the early diagenetic reactions was suggested. This shift was likely promoted by the diagenetic consumption of nitrate and sulfate and their gradual depletion in the water column due to progressively decreasing frozen peat lixiviation occurring at the lake's borders. Trace elements were mobilized from host phases (OM and Fe- and Mn-oxyhydroxides) and partly sequestered in the sediment in the form of authigenic Fe-sulfides. Arsenic and Sb cycling was also closely linked to that of OM and Fe- and Mn-oxyhydroxides. Shallow diagenetic enrichment of particulate Sb was observed in the less mature stages. As a result of authigenic sulfide precipitation, the sediments of the early stage of ecosystem development were a sink for water column Cu, Zn, Cd, Pb and Sb. In contrast, at all stages of ecosystem development

Organic matter mineralization and trace element post-depositional redistribution in Western Siberia thermokarst lake sediments

NASA Astrophysics Data System (ADS)

Audry, S.; Pokrovsky, O. S.; Shirokova, L. S.; Kirpotin, S. N.; Dupré, B.

2011-08-01

This study reports the very first results on high-resolution sampling of sediments and their porewaters from three thermokarst (thaw) lakes representing different stages of ecosystem development located within the Nadym-Pur interfluve of the Western Siberia plain. Up to present time, the lake sediments of this and other permafrost-affected regions remain unexplored regarding their biogeochemical behavior. The aim of this study was to (i) document the early diagenesic processes in order to assess their impact on the organic carbon stored in the underlying permafrost, and (ii) characterize the post-depositional redistribution of trace elements and their impact on the water column. The estimated organic carbon (OC) stock in thermokarst lake sediments of 14 ± 2 kg m-2 is low compared to that reported for peat soils from the same region and denotes intense organic matter (OM) mineralization. Mineralization of OM in the thermokarst lake sediments proceeds under anoxic conditions in all the three lakes. In the course of the lake development, a shift in mineralization pathways was evidenced from nitrate and sulfate to Fe- and Mn-oxyhydroxides as the main terminal electron acceptors in the early diagenetic reactions. This shift was promoted by the diagenetic consumption of nitrate and sulfate and their gradual depletion in the water column due to progressively decreasing frozen peat lixiviation occurring at the lake's borders. Trace elements were mobilized from host phases (OM and Fe- and Mn-oxyhydroxides) and partly sequestered in the sediment in the form of authigenic Fe-sulfides. Arsenic and Sb cycling was also closely linked to that of OM and Fe- and Mn-oxyhydroxides. Shallow diagenetic enrichment of particulate Sb was observed in the less mature stages. As a result of authigenic sulfide precipitation, the sediments of the early stage of ecosystem development were a sink for water column Cu, Zn, Cd, Pb and Sb. In contrast, at all stages of ecosystem development, the

Copper-nickel-rich, amalgamated ferromanganese crust-nodule deposits from Shatsky Rise, NW Pacific

USGS Publications Warehouse

Hein, J.R.; Conrad, T.A.; Frank, M.; Christl, M.; Sager, W.W.

2012-01-01

A unique set of ferromanganese crusts and nodules collected from Shatsky Rise (SR), NW Pacific, were analyzed for mineralogical and chemical compositions, and dated using Be isotopes and cobalt chronometry. The composition of these midlatitude, deep-water deposits is markedly different from northwest-equatorial Pacific (PCZ) crusts, where most studies have been conducted. Crusts and nodules on SR formed in close proximity and some nodule deposits were cemented and overgrown by crusts, forming amalgamated deposits. The deep-water SR crusts are high in Cu, Li, and Th and low in Co, Te, and Tl concentrations compared to PCZ crusts. Thorium concentrations (ppm) are especially striking with a high of 152 (mean 56), compared to PCZ crusts (mean 11). The deep-water SR crusts show a diagenetic chemical signal, but not a diagenetic mineralogy, which together constrain the redox conditions to early oxic diagenesis. Diagenetic input to crusts is rare, but unequivocal in these deep-water crusts. Copper, Ni, and Li are strongly enriched in SR deep-water deposits, but only in layers older than about 3.4 Ma. Diagenetic reactions in the sediment and dissolution of biogenic calcite in the water column are the likely sources of these metals. The highest concentrations of Li are in crust layers that formed near the calcite compensation depth. The onset of Ni, Cu, and Li enrichment in the middle Miocene and cessation at about 3.4 Ma were accompanied by changes in the deep-water environment, especially composition and flow rates of water masses, and location of the carbonate compensation depth.

Thermally Altered Silurian Cyanobacterial Mats: A Key to Earth's Oldest Fossils

NASA Astrophysics Data System (ADS)

Kazmierczak, Józef; Kremer, Barbara

2009-10-01

Diagenetic changes in thermally altered cyanobacterial mats from early Silurian black radiolarian cherts of southwestern Poland (Bardzkie Montains, Sudetes) have been studied. These early diagenetically silicified mats are composed of variously degraded remains of benthic microbes that resemble some modern chroococcalean and pleurocapsalean cyanobacteria. Two modes of degradational processes have been recognized in the studied mats: (i) early postmortem biodegradation and (ii) late diagenetic thermal or thermobaric degradation. The latter led to partial transformation of the fossilized organic remnants of cyanobacterial sheaths and capsules, which resulted in the formation of objects morphologically distant from the original microbiota but preserved features that allow for their identification as bona fide biogenic structures. Some of these thermally generated Silurian fossils are highly similar to the controversial microfossil-like carbonaceous structures described from the Early Archean Apex Chert of Australia. This similarity opens a promising way for credible recognition of remnants of cyanobacteria and similar microbiota in other thermally metamorphosed Archean sedimentary rocks

Diagenetic Microcrystalline Opal Varieties from the Monterey Formation, CA: HRTEM Study of Structures and Phase Transformation Mechanisms

NASA Technical Reports Server (NTRS)

Cady, Sherry L.; Wenk, H.-R.; DeVincenzi, Don (Technical Monitor)

1994-01-01

Microcrystalline opal varieties form as intermediary precipitates during the diagenetic transformation of biogenically precipitated non-crystalline opal (opal-A) to microquartz. With regard to the Monterey Formation of California, X-ray powder diffraction studies have shown that a decrease in the primary d-spacing of opal-CT toward that of cristobalite occurs with increasing diagenesis. The initial timing of opal-CT/quartz formation and the value of the primary opal-CT d-spacing, are influenced by the sediment. lithology. Transmission electron microscopy methods (CTEM/HRTEM) were used to investigate the structure of the diagenetic phases and establish transformation mechanisms between the varieties of microcrystalline opals in charts and porcelanites from the Monterey Formation. HRTEM images revealed that the most common fibrous varieties of microcrystalline opals contain varying amounts of structural disorder. Finite lamellar units of cristobalite-and tridymite-type. layer sequences were found to be randomly stacked in a direction perpendicular to the fiber axis. Disordered and ordered fibers were found to have coprecipitated within the same radial fiber bundles that formed within the matrix of the Most siliceous samples. HRTEM images, which reveal that the fibers within radial and lepispheric fiber bundles branch non-crystallographically, support an earlier proposal that microspheres in chert grow via a spherulitic growth mechanism. A less common variety of opal-CT was found to be characterized by non-parallel (low-angle) stacking sequences that often contain twinned lamellae. Tabular-shaped crystals of orthorhombic tridymite (PO-2) were also identified in the porcelanite samples. A shift in the primary d-spacing of opal-CT has been interpreted as an indication of solid-state ordering g toward a predominantly cristobalite structure, (opal-C). Domains of opal-C were identified as topotactically-oriented overgrowths on discrete Sections of opal-CT fibers and as

Modeling carbon-nutrient interactions during the early recovery of tundra after fire.

PubMed

Jiang, Yueyang; Rastetter, Edward B; Rocha, Adrian V; Pearce, Andrea R; Kwiatkowski, Bonnie L; Shaver, Gaius R

2015-09-01

Fire frequency has dramatically increased in the tundra of northern Alaska, USA, which has major implications for the carbon budget of the region and the functioning of these ecosystems, which support important wildlife species. We investigated the postfire succession of plant and soil carbon (C), nitrogen (N), and phosphorus (P) fluxes and stocks along a burn severity gradient in the 2007 Anaktuvuk River fire scar in northern Alaska. Modeling results indicated that the early regrowth of postfire tundra vegetation was limited primarily by its canopy photosynthetic potential, rather than nutrient availability, because of the initially low leaf area and relatively high inorganic N and P concentrations in soil. Our simulations indicated that the postfire recovery of tundra vegetation was sustained predominantly by the uptake of residual inorganic N (i.e., in the remaining ash), and the redistribution of N and P from soil organic matter to vegetation. Although residual nutrients in ash were higher in the severe burn than the moderate burn, the moderate burn recovered faster because of the higher remaining biomass and consequent photosynthetic potential. Residual nutrients in ash allowed both burn sites to recover and exceed the unburned site in both aboveground biomass and production five years after the fire. The investigation of interactions among postfire C, N, and P cycles has contributed to a mechanistic understanding of the response of tundra ecosystems to fire disturbance. Our study provided insight on how the trajectory of recovery of tundra from wildfire is regulated during early succession.

Carbon-carbon piston development

NASA Technical Reports Server (NTRS)

Gorton, Mark P.

1994-01-01

A new piston concept, made of carbon-carbon refractory-composite material, has been developed that overcomes a number of the shortcomings of aluminum pistons. Carbon-carbon material, developed in the early 1960's, is lighter in weight than aluminum, has higher strength and stiffness than aluminum and maintains these properties at temperatures over 2500 F. In addition, carbon-carbon material has a low coefficient of thermal expansion and excellent resistance to thermal shock. An effort, called the Advanced Carbon-Carbon Piston Program was started in 1986 to develop and test carbon-carbon pistons for use in spark ignition engines. The carbon-carbon pistons were designed to be replacements for existing aluminum pistons, using standard piston pin assemblies and using standard rings. Carbon-carbon pistons can potentially enable engines to be more reliable, more efficient and have greater power output. By utilizing the unique characteristics of carbon-carbon material a piston can: (1) have greater resistance to structural damage caused by overheating, lean air-fuel mixture conditions and detonation; (2) be designed to be lighter than an aluminum piston thus, reducing the reciprocating mass of an engine, and (3) be operated in a higher combustion temperature environment without failure.

Early-mid-Cretaceous evolution in Tethyan reef communities and sea level

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scott, R.W.

1988-01-01

The replacement of corals by rudists in Early Cretaceous reefal communities spanned a 30-m.y. period when sea level rose and drowned continental shelves. During this time corals formed communities in the deeper parts of reefs and rudists occupied the shallow, high-energy habitats. By Aptian time rudists dominated reefs that fringed interior shelf basins and corals formed reefs with rudists on the outer shelf margins. By late Albian coral communities had virtually disappeared, presumably because of complex environmental changes and cycles of organic productivity. Two important events of eustatic sea level rise are represented by unconformities separating carbonate depositional sequences onmore » the Arabian platform that correlate with sequence boundaries on the Gulf Coast platform. Graphic correlation techniques test the synchroneity of these events. A composite standard time scale dates these sea level rises at 115.8 Ma and 94.6 Ma; a third, intra-Albian event at 104.3 Ma is present in many places and may also be eustatic. Associated with these sea level rises were apparent changes in ocean water chemistry as evidenced by changes in isotopes and trace elements, where diagenetic effects can be discounted. During this time the climate became more humid and atmospheric CO/sub 2/ increased. The concomitant environmental changes in the oceanic conditions presumably stressed the deeper coral communities on reefs. The emergence of rudists as reef contributors had a profound effect on Late Cretaceous depositional conditions and the development of hydrocarbon reservoirs.« less

Early-mid-Cretaceous evolution in Tethyan reef communities and sea level

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scott, R.W.

1988-02-01

The replacement of corals by rudists in Early Cretaceous reefal communities spanned a 30-m.y. period when sea level rose and drowned continental shelves. During this time corals formed communities in the deeper parts of reefs and rudists occupied the shallow, high-energy habitats. By Aptian time rudists dominated reefs that fringed interior shelf basins and corals formed reefs with rudists on the outer shelf margins. By late Albian coral communities had virtually disappeared, presumably because of complex environmental changes and cycles of organic productivity. Two important events of eustatic sea level rise are represented by unconformities separating carbonate depositional sequences onmore » the Arabian platform that correlate with sequence boundaries on the Gulf Coast platform. Graphic correlation techniques test the synchroneity of these events. A composite standard time scale dates these sea level rises at 115.8 Ma and 94.6 Ma; a third, intra-Albian event at 104.3 Ma is present in many places and may also be eustatic. Associated with these sea level rises were apparent changes in ocean water chemistry as evidenced by changes in isotopes and trace elements, where diagenetic effects can be discounted. During this time the climate became more humid and atmospheric CO/sub 2/ increased. The concomitant environmental changes in the oceanic conditions presumably stressed the deeper coral communities on reefs. The emergence of rudists as reef contributors had a profound effect on Late Cretaceous depositional conditions and the development of hydrocarbon reservoirs.« less

Mineralogy and Isotopic Records of Carbonate and Silicate Cementation of the Siliciclastic Sediments of the New Jersey Shelf (IODP Expedition 313)

NASA Astrophysics Data System (ADS)

Pierre, C.; Blanc-Valleron, M. M.; Lofi, J.

2016-12-01

The New Jersey continental shelf extends up to 150 km away from the shoreline. During IODP Expedition 313 the siliciclastic deposits of late Eocene to late Pleistocene age were drilled down to 631 mbsf, 669 mbsf and 700 mbsf at the three sites 27A, 28A, 29A respectively, in very shallow water depth (33.5 to 36 m). Pore water salinities display multilayered fresh-salty-brine units 10 to 170 m thick, where freshwater is preferentially stored in fine-grained sediments (van Geldern et al 2013 ; Lofi et al 2013). The sharp boundaries of these buried aquifers are often marked by hardly cemented layers a few centimeters thick. The mineralogy and SEM observations of these layers show two phases of cementation by authigenic minerals : (1) the early carbonate cement is made of Fe-dolomite, ankerite and occasionally calcite, frequently associated with pyrite (2) the late silicate cement (silica, K-Fe-rich clay minerals, zeolites) fills in the residual porosity. The isotopic compositions of the carbonate cements vary in wide ranges : -2.4 < δ18O‰ VPDB < +2.8 ; -15.1< δ13C ‰ VPDB <+15.6. The δ18O values indicate carbonate precipitation with pore waters more or less depleted in 18O of the buried aquifers. The δ13C values of carbonate are related to organic matter diagenesis providing 13C-depleted DIC during bacterial sulphate reduction (with pyrite as a by-product of the reaction) and 13C-rich DIC during methanogenesis. The diagenetic cementation processes included chemical weathering of reactive silicate minerals by the CO2-rich pore waters issued from organic matter diagenesis that released bicarbonate, cations and dissolved silica, which were further precipitated as carbonate and silicate cements. The temperature estimated (18 ± 4°C) for the precipitation of carbonate indicates that cementation occurred at moderate burial depths, i.e. probably very soon after deposition. Lofi J et al 2013. Geosphere, 9, 4, 1009-1024 Van Geldern R et al 2013. Geosphere, 9, 1, 96-112

Fine-grained rutile in the Gulf of Maine: Diagenetic origin, source rocks, and sedimentary environment of deposition

USGS Publications Warehouse

Valentine, P.C.; Commeau, J.A.

1990-01-01

The Gulf of Maine, an embayment of the New England margin, is floored by shallow, glacially scoured basins that are partly filled with late Pleistocene and Holocene silt and clay containing 0.7 to 1.0 wt percent TiO2 chiefly in the form of silt-size rutile. Much of the rutile in the Gulf of Maine mud probably formed diagenetically in poorly cemented Carboniferous and Triassic coarse-grained sedimentary rocks of Nova Scotia and New Brunswick after the dissolution of titanium-rich detrital minerals (ilmenite, ilmenomagnetite). The diagenesis of rutile in coarse sedimentary rocks (especially arkose and graywacke) followed by erosion, segregation, and deposition (and including recycling of fine-grained rutile from shales) can serve as a model for predicting and prospecting for unconsolidated deposits of fine-grained TiO2. -from Authors

Variations of iron flux and organic carbon remineralization in a subterranean estuary caused by interannual variations in recharge

USGS Publications Warehouse

Roy, Moutusi; Martin, Jonathan B.; Cable, Jaye E.; Smith, Christopher G.

2013-01-01

We determine the inter-annual variations in diagenetic reaction rates of sedimentary iron (Fe ) in an east Florida subterranean estuary and evaluate the connection between metal fluxes and recharge to the coastal aquifer. Over the three-year study period (from 2004 to 2007), the amount of Fe-oxides reduced at the study site decreased from 192 g/yr to 153 g/yr and associated organic carbon (OC) remineralization decreased from 48 g/yr to 38 g/yr. These reductions occurred although the Fe-oxide reduction rates remained constant around 1 mg/cm2/yr. These results suggest that changes in flow rates of submarine groundwater discharge (SGD) related to changes in precipitation may be important to fluxes of the diagenetic reaction products. Rainfall at a weather station approximately 5 km from the field area decreased from 12.6 cm/month to 8.4 cm/month from 2004 to 2007. Monthly potential evapotranspiration (PET) calculated from Thornthwaite’s method indicated potential evapotranspiration cycled from about 3 cm/month in the winter to about 15 cm/month in the summer so that net annual recharge to the aquifer decreased from 40 cm in 2004 to -10 cm in 2007. Simultaneously, with the decrease in recharge of groundwater, freshwater SGD decreased by around 20% and caused the originally 25 m wide freshwater seepage face to decrease in width by about 5 m. The smaller seepage face reduced the area under which Fe-oxides were undergoing reductive dissolution. Consequently, the observed decrease in Fe flux is controlled by hydrology of the subterranean estuary. These results point out the need to better understand linkages between temporal variations in diagenetic reactions and changes in flow within subterranean estuaries in order to accurately constrain their contribution to oceanic fluxes of solutes from subterranean estuaries.

Constraining the climate and ocean pH of the early Earth with a geological carbon cycle model.

PubMed

Krissansen-Totton, Joshua; Arney, Giada N; Catling, David C

2018-04-17

The early Earth's environment is controversial. Climatic estimates range from hot to glacial, and inferred marine pH spans strongly alkaline to acidic. Better understanding of early climate and ocean chemistry would improve our knowledge of the origin of life and its coevolution with the environment. Here, we use a geological carbon cycle model with ocean chemistry to calculate self-consistent histories of climate and ocean pH. Our carbon cycle model includes an empirically justified temperature and pH dependence of seafloor weathering, allowing the relative importance of continental and seafloor weathering to be evaluated. We find that the Archean climate was likely temperate (0-50 °C) due to the combined negative feedbacks of continental and seafloor weathering. Ocean pH evolves monotonically from [Formula: see text] (2σ) at 4.0 Ga to [Formula: see text] (2σ) at the Archean-Proterozoic boundary, and to [Formula: see text] (2σ) at the Proterozoic-Phanerozoic boundary. This evolution is driven by the secular decline of pCO 2 , which in turn is a consequence of increasing solar luminosity, but is moderated by carbonate alkalinity delivered from continental and seafloor weathering. Archean seafloor weathering may have been a comparable carbon sink to continental weathering, but is less dominant than previously assumed, and would not have induced global glaciation. We show how these conclusions are robust to a wide range of scenarios for continental growth, internal heat flow evolution and outgassing history, greenhouse gas abundances, and changes in the biotic enhancement of weathering. Copyright © 2018 the Author(s). Published by PNAS.

Study of Diagenetic Features in Rudist Buildups of Cretaceous Edwards Formation Using Ground Based Hyperspectral Scanning and Terrestrial LiDAR

NASA Astrophysics Data System (ADS)

Krupnik, D.; Khan, S.; Okyay, U.; Hartzell, P. J.; Biber, K.

2015-12-01

Ground based remote sensing is a novel technique for development of digital outcrop models which can be instrumental in performing detailed qualitative and quantitative sedimentological analysis for the study of depositional environment, diagenetic processes, and hydrocarbon reservoir characterization. For this investigation, ground-based hyperspectral data collection is combined with terrestrial LiDAR to study outcrops of Late Albian rudist buildups of the Edwards formation in the Lake Georgetown Spillway in Williamson County, Texas. The Edwards formation consists of shallow water deposits of reef and associated inter-reef facies, including rudist bioherms and biostromes. It is a significant aquifer and was investigated as a hydrocarbon play in south central Texas. Hyperspectral data were used to map compositional variation in the outcrop by distinguishing spectral properties unique to each material. Lithological variation was mapped in detail to investigate the structure and composition of rudist buildups. Hyperspectral imagery was registered to a 3D model produced from the LiDAR point cloud with an accuracy of up to one pixel. Flat-topped toucasid-rich bioherm facies were distinguished from overlying toucasid-rich biostrome facies containing chert nodules, overlying sucrosic dolostones, and uppermost peloid wackestones and packstones of back-reef facies. Ground truth was established by petrographic study of samples from this area and has validated classification products of remote sensing data. Several types of porosity were observed and have been associated with increased dolomitization. This ongoing research involves integration of remotely sensed datasets to analyze geometrical and compositional properties of this carbonate formation at a finer scale than traditional methods have achieved and seeks to develop a workflow for quick and efficient ground based remote sensing-assisted outcrop studies.

The Effect of Early Diagenesis on the 238U/235U Ratio of Platform Carbonates.

NASA Astrophysics Data System (ADS)

Tissot, F.; Chen, C.; Go, B. M.; Naziemiec, M.; Healy, G.; Swart, P. K.; Dauphas, N.

2017-12-01

In the past 15 years, the so-called non-traditional stable isotopes systems (e.g., Mg, Fe, Mo, U) have emerged as powerful tracers of both high-T and low-T geochemical processes (e.g., [1]). Of particular interest for paleoredox studies is the ratio of "stable" isotopes of U (238U/235U), which has the potential to track the global extent of oceanic anoxia (e.g., [2, 3]). Indeed, in the modern ocean, U exists in two main oxidation states, soluble U6+ and insoluble U4+, and has a mean residence time of 400 kyr ([4]), much longer than the global ocean mixing time (1-2 kyr). As such the salinity-normalized ocean is homogeneous with regards to both U concentrations and isotopes (δ238USW = -0.392±0.005 ‰, [2]). The value of δ238USW at any given time is therefore the balance between U input to the ocean, mainly from rivers, and U removal, mostly into biogenic carbonates, anoxic/euxinic sediments and suboxic/hypoxic sediments (e.g., [2, 5]). Because the 238U/235U ratio of the past ocean cannot be measured directly, it has to be estimated from the measurement of the 238U/235U ratio of a sedimentary rock and assuming a constant fractionation factor. Carbonates appear as a promising record since they span most of Earth's history, and the δ238U values of modern primary carbonate precipitates and well-preserved fossil aragonitic coral up to 600 ka are indistinguishable from that of seawater (e.g., [2, 6, 7]). Yet, the effect of secondary processes on the δ238U values of non-coral carbonates, which represent the bulk of the rock record, has only been studied in a handful of shallow samples (down to 40cm, [6]) and remains poorly understood. To investigate the effect of early diagenesis on the 238U/235U ratio of carbonates on the 30kyr to 1Myr timescale, we measured δ13C, δ18O, and δ238U in samples from a 220m long drill core from the Bahamas carbonate platform. In order to separate lattice bound U from secondary U we developed a leaching protocol applicable to carbonate

Carbonate cements indicate channeled fluid flow along a zone of vertical faults at the deformation front of the Cascadia accretionary wedge (northwest U.S. coast)

NASA Astrophysics Data System (ADS)

Sample, James C.; Reid, Mary R.; Tols, Harold J.; Moore, J. Casey

1993-06-01

To understand the relation between fluid seeps and structures, sedimentary rocks were collected with the DSRV Alvin from a vertical fault zone that transects the deformation front of the Cascadia accretionary wedge. The rocks contained diagenetic carbonate cement that was precipitated from fluids expelled during accretion. Carbon, oxygen, and strontium isotope data are consistent with a fluid source at >2 km depth. Most carbon isotopes range from -1‰ to -25‰ (PDB [Peedee belemnitel] standard) consistent with a thermogenic methane source. Oxygen isotopes show extreme 18O depletions (-4‰ to -13‰ PDB) that are consistent with precipitation from fluids with temperatures as high as 100 °C. 87Sr/86Sr values of 0.70975 to 0.71279 may be due to strontium in fluids derived from clay-rich parts of the stratigraphic section. The ubiquity of carbonate precipitates and the isotope data indicate that the vertical fault zone is an efficient conduit for fluid dewatering from deep levels of the accretionary wedge.

Correlating carbon and oxygen isotope events in early to middle Miocene shallow marine carbonates in the Mediterranean region using orbitally tuned chemostratigraphy and lithostratigraphy

PubMed Central

Piller, Werner E.; Reuter, Markus; Harzhauser, Mathias

2015-01-01

Abstract During the Miocene prominent oxygen isotope events (Mi‐events) reflect major changes in glaciation, while carbonate isotope maxima (CM‐events) reflect changes in organic carbon burial, particularly during the Monterey carbon isotope excursion. However, despite their importance to the global climate history they have never been recorded in shallow marine carbonate successions. The Decontra section on the Maiella Platform (central Apennines, Italy), however, allows to resolve them for the first time in such a setting during the early to middle Miocene. The present study improves the stratigraphic resolution of parts of the Decontra section via orbital tuning of high‐resolution gamma ray (GR) and magnetic susceptibility data to the 405 kyr eccentricity metronome. The tuning allows, within the established biostratigraphic, sequence stratigraphic, and isotope stratigraphic frameworks, a precise correlation of the Decontra section with pelagic records of the Mediterranean region, as well as the global paleoclimatic record and the global sea level curve. Spectral series analyses of GR data further indicate that the 405 kyr orbital cycle is particularly well preserved during the Monterey Event. Since GR is a direct proxy for authigenic uranium precipitation during increased burial of organic carbon in the Decontra section, it follows the same long‐term orbital pacing as observed in the carbon isotope records. The 405 kyr GR beat is thus correlated with the carbon isotope maxima observed during the Monterey Event. Finally, the Mi‐events can now be recognized in the δ18O record and coincide with plankton‐rich, siliceous, or phosphatic horizons in the lithology of the section. PMID:27546980

Correlating carbon and oxygen isotope events in early to middle Miocene shallow marine carbonates in the Mediterranean region using orbitally tuned chemostratigraphy and lithostratigraphy

NASA Astrophysics Data System (ADS)

Auer, Gerald; Piller, Werner E.; Reuter, Markus; Harzhauser, Mathias

2015-04-01

During the Miocene prominent oxygen isotope events (Mi-events) reflect major changes in glaciation, while carbonate isotope maxima (CM-events) reflect changes in organic carbon burial, particularly during the Monterey carbon isotope excursion. However, despite their importance to the global climate history they have never been recorded in shallow marine carbonate successions. The Decontra section on the Maiella Platform (central Apennines, Italy), however, allows to resolve them for the first time in such a setting during the early to middle Miocene. The present study improves the stratigraphic resolution of parts of the Decontra section via orbital tuning of high-resolution gamma ray (GR) and magnetic susceptibility data to the 405 kyr eccentricity metronome. The tuning allows, within the established biostratigraphic, sequence stratigraphic, and isotope stratigraphic frameworks, a precise correlation of the Decontra section with pelagic records of the Mediterranean region, as well as the global paleoclimatic record and the global sea level curve. Spectral series analyses of GR data further indicate that the 405 kyr orbital cycle is particularly well preserved during the Monterey Event. Since GR is a direct proxy for authigenic uranium precipitation during increased burial of organic carbon in the Decontra section, it follows the same long-term orbital pacing as observed in the carbon isotope records. The 405 kyr GR beat is thus correlated with the carbon isotope maxima observed during the Monterey Event. Finally, the Mi-events can now be recognized in the δ18O record and coincide with plankton-rich, siliceous, or phosphatic horizons in the lithology of the section.

Calcium isotope evidence for suppression of carbonate dissolution in carbonate-bearing organic-rich sediments

NASA Astrophysics Data System (ADS)

Turchyn, Alexandra V.; DePaolo, Donald J.

2011-11-01

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (δ 44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of δ 44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, δ 44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the δ 44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these

Structural-Diagenetic Controls on Fracture Opening in Tight Gas Sandstone Reservoirs, Alberta Foothills

NASA Astrophysics Data System (ADS)

Ukar, Estibalitz; Eichhubl, Peter; Fall, Andras; Hooker, John

2013-04-01

In tight gas reservoirs, understanding the characteristics, orientation and distribution of natural open fractures, and how these relate to the structural and stratigraphic setting are important for exploration and production. Outcrops provide the opportunity to sample fracture characteristics that would otherwise be unknown due to the limitations of sampling by cores and well logs. However, fractures in exhumed outcrops may not be representative of fractures in the reservoir because of differences in burial and exhumation history. Appropriate outcrop analogs of producing reservoirs with comparable geologic history, structural setting, fracture networks, and diagenetic attributes are desirable but rare. The Jurassic to Lower Cretaceous Nikanassin Formation from the Alberta Foothills produces gas at commercial rates where it contains a network of open fractures. Fractures from outcrops have the same diagenetic attributes as those observed in cores <100 km away, thus offering an ideal opportunity to 1) evaluate the distribution and characteristics of opening mode fractures relative to fold cores, hinges and limbs, 2) compare the distribution and attributes of fractures in outcrop vs. core samples, 3) estimate the timing of fracture formation relative to the evolution of the fold-and-thrust belt, and 4) estimate the degradation of fracture porosity due to postkinematic cementation. Cathodoluminescence images of cemented fractures in both outcrop and core samples reveal several generations of quartz and ankerite cement that is synkinematic and postkinematic relative to fracture opening. Crack-seal textures in synkinematic quartz are ubiquitous, and well-developed cement bridges abundant. Fracture porosity may be preserved in fractures wider than ~100 microns. 1-D scanlines in outcrop and core samples indicate fractures are most abundant within small parasitic folds within larger, tight, mesoscopic folds. Fracture intensity is lower away from parasitic folds; intensity

Structural-Diagenetic Controls on Fracture Opening in Tight Gas Sandstone Reservoirs, Alberta Foothills

NASA Astrophysics Data System (ADS)

Ukar, E.; Eichhubl, P.; Fall, A.; Hooker, J. N.

2012-12-01

In tight gas reservoirs, understanding the characteristics, orientation and distribution of natural open fractures, and how these relate to the structural and stratigraphic setting are important for exploration and production. Outcrops provide the opportunity to sample fracture characteristics that would otherwise be unknown due to the limitations of sampling by cores and well logs. However, fractures in exhumed outcrops may not be representative of fractures in the reservoir because of differences in burial and exhumation history. Appropriate outcrop analogs of producing reservoirs with comparable geologic history, structural setting, fracture networks, and diagenetic attributes are desirable but rare. The Jurassic to Lower Cretaceous Nikanassin Formation from the Alberta Foothills produces gas at commercial rates where it contains a network of open fractures. Fractures from outcrops have the same diagenetic attributes as those observed in cores <100 km away, thus offering an ideal opportunity to 1) evaluate the distribution and characteristics of opening mode fractures relative to fold cores, hinges and limbs, 2) compare the distribution and attributes of fractures in outcrop vs. core samples, 3) estimate the timing of fracture formation relative to the evolution of the fold-and-thrust belt, and 4) estimate the degradation of fracture porosity due to postkinematic cementation. Cathodoluminescence images of cemented fractures in both outcrop and core samples reveal several generations of quartz and ankerite cement that is synkinematic and postkinematic relative to fracture opening. Crack-seal textures in synkinematic quartz are ubiquitous, and well-developed cement bridges abundant. Fracture porosity may be preserved in fractures wider than ~100 microns. 1-D scanlines in outcrop and core samples indicate fractures are most abundant within small parasitic folds within larger, tight, mesoscopic folds. Fracture intensity is lower away from parasitic folds; intensity

Variations of iron flux and organic carbon remineralization in a subterranean estuary caused by inter-annual variations in recharge

NASA Astrophysics Data System (ADS)

Roy, Moutusi; Martin, Jonathan B.; Cable, Jaye E.; Smith, Christopher G.

2013-02-01

We determine the inter-annual variations in diagenetic reaction rates of sedimentary iron (Fe) in an east Florida subterranean estuary and evaluate the connection between metal fluxes and recharge to the coastal aquifer. Over the three years study period (from 2004 to 2007), the amount of Fe-oxides reduced at the study site decreased from 192 to 153 g/yr and associated organic carbon (OC) remineralization decreased from 48 to 38 g/yr. These reductions occurred although the Fe-oxide reduction rates remained constant around 1 mg/cm2/yr. These results suggest that changes in flow rates of submarine groundwater discharge (SGD) related to changes in precipitation may be important to fluxes of the diagenetic reaction products. Rainfall at a weather station approximately 5 km from the field area decreased from 12.6 to 8.4 cm/month from 2004 to 2007. Monthly potential evapotranspiration (PET) calculated from Thornthwaite's method indicated potential evapotranspiration cycled from about 3 cm/month in the winter to about 15 cm/month in the summer so that net annual recharge to the aquifer decreased from 40 cm in 2004 to -10 cm in 2007. Simultaneously with the decrease in recharge of groundwater, freshwater SGD decreased by around 20% and caused the originally 25 m wide freshwater seepage face to decrease in width by about 5 m. The smaller seepage face reduced the area under which Fe-oxides were undergoing reductive dissolution. Consequently, the observed decrease in Fe flux is controlled by hydrology of the subterranean estuary. These results point out the need to better understand linkages between temporal variations in diagenetic reactions and changes in flow within subterranean estuaries in order to accurately constrain their contribution to oceanic fluxes of solutes from subterranean estuaries.

Lithofacies and Diagenetic Controls on Formation-scale Mechanical, Transport, and Sealing Behavior of Caprocks: A Case Study of the Morrow shale and Thirteen Finger Limestone, Farnsworth Unit, Texas

NASA Astrophysics Data System (ADS)

Trujillo, N. A.; Heath, J. E.; Mozley, P.; Dewers, T. A.; Cather, M.

2016-12-01

Assessment of caprock sealing behavior for secure CO2 storage is a multiscale endeavor. Sealing behavior arises from the nano-scale capillarity of pore throats, but sealing lithologies alone do not guarantee an effective seal since bypass systems, such as connected, conductive fractures can compromise the integrity of the seal. We apply pore-to-formation-scale data to characterize the multiscale caprock sealing behavior of the Morrow shale and Thirteen Finger Limestone. This work is part of the Southwest Regional Partnership on Carbon Sequestration's Phase III project at the Farnsworth Unit, Texas. The caprock formations overlie the Morrow sandstone, the target for enhanced oil recovery and injection of over one million metric tons of anthropogenically-sourced CO2. Methods include: focused ion beam-scanning electron microscopy; laser scanning confocal microscopy; electron and optical petrography; multi-stress path mechanical testing and constitutive modeling; core examinations of sedimentary structures and fractures; and a noble gas profile for formation-scale transport of the sealing lihologies and the reservoir. We develop relationships between diagenetic characteristics of lithofacies to mechanical and petrophysical measurements of the caprocks. The results are applied as part of a caprock sealing behavior performance assessment. Funding for this project is provided by the U.S. Department of Energy's National Energy Technology Laboratory through the Southwest Regional Partnership on Carbon Sequestration (SWP) under Award No. DE-FC26-05NT42591. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Early Implementation of Large Scale Carbon Dioxide Removal Projects through the Cement Industry

NASA Astrophysics Data System (ADS)

Zeman, F. S.

2014-12-01

The development of large-scale carbon dioxide reduction projects requires high purity CO2and a reactive cation source. A project seeking to provide both of these requirements will likely face cost barriers with current carbon prices. The cement industry is a suitable early implementation site for such projects by virtue of the properties of its exhaust gases and those of waste concrete. Cement plants are the second largest source of industrial CO2 emissions, globally. It is also the second largest commodity after water, has no ready substitute and is literally the foundation of society. Finally, half of the CO2 emissions originate from process reactions rather than fossil fuel combustion resulting in higher flue gas CO2concentrations. These properties, with the co-benefits of oxygen combustion, create a favorable environment for spatially suitable projects. Oxygen combustion involves substituting produced oxygen for air in a combustion reaction. The absence of gaseous N2 necessitates the recirculation of exhaust gases to maintain kiln temperatures, which increase the CO2 concentrations from 28% to 80% or more. Gas exit temperatures are also elevated (>300oC) and can reach higher temperatures if the multi stage pre-heater towers, that recover heat, are re-designed in light of FGR. A ready source of cations can be found in waste concrete, a by-product of construction and demolition activities. These wastes can be processed to remove cations and then reacted with atmospheric CO2 to produce carbonate minerals. While not carbon negative, they represent a demonstration opportunity for binding atmospheric CO2while producing a saleable product (precipitated calcium carbonate). This paper will present experimental results on PCC production from waste concrete along with modeling results for oxygen combustion at cement facilities. The results will be presented with a view to mineral sequestration process design and implementation.

A Paleomagnetic and Diagenetic Study of the Woodford Shale, Oklahoma, U.S.A.: The Timing of Hydrothermal Alteration

NASA Astrophysics Data System (ADS)

Roberts, J.; Elmore, R. D.

2017-12-01

An oriented Woodford Shale core from the Ardmore Basin near the Ouachita thrust zone (Core B) was sampled to identify diagenetic events and interpret their origin, and to test if a magnetization was present that can be used to date the altering event(s). The shale is extensively altered, exhibiting a complex paragenesis with multiple fractures and brecciated intervals. Multiple hydrothermal minerals, including biotite, magnesite, norsethite, witherite, gorceixite, potassium feldspar, sphalerite, chalcopyrite, and saddle dolomite, are present in and around fractures and in the matrix. Vitrinite and bitumen reflectance measurements indicate VRo values of 1.82% ( 230°C). Two other Woodford Shale cores (A and C) from the Anadarko Basin also contain hydrothermal minerals. Vitrinite and bitumen reflectance data reveal trends between thermal maturity and the level of hydrothermal alteration, with Core A (0.80% VRo ( 125°C) displaying the lowest alteration, and Core C ( 1.5% VRo ( 210°C) displaying intermediate alteration compared to core B. Paleomagnetic analysis of Core B reveals the presence of a characteristic remanent magnetization (ChRM) with south-southeasterly declinations and shallow inclinations that is unblocked by 450°C and is interpreted to reside in magnetite. This ChRM is interpreted to be either a chemical remanent magnetization (CRM) or a thermochemical remanent magnetization (TCRM) acquired during the Late Permian based on the pole position. The presence of specimens with the CRM/TCRM in altered rock and high thermal maturities suggests that this CRM/TCRM originated from alteration by hydrothermal fluids. These results suggest that the Woodford Shale evolved into an open diagenetic system. In addition to causing heightened thermal maturities, these hydrothermal fluids both increased porosity through dissolution and decreased porosity through precipitation of minerals. The Late Permian timing agrees with the dating of hydrothermal alteration found

Geochemistry of carbonate cements in surficial alluvial conglomerates and their paleoclimatic implications, Sultanate of Oman

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burns, S.J.; Matter, A.

1995-01-02

Early diagenetic carbonate cements are a common feature of Quaternary alluvial conglomerates in Oman. Cements are formed in the vadose and, more commonly, phreatic zones from near-surface groundwaters. In drainage areas underlain by the Semail Ophiolite, groundwaters have Mg{sup 2+}/Ca{sup 2+} ratios greater than two, and cements are often dolomite or high-magnesium calcite in addition to low-magnesium calcite. In drainage areas underlain by limestone, groundwaters have Mg{sup 2+}/Ca{sup 2+} ratios of around one or less and cement mineralogy is nearly always low-magnesium calcite. The oxygen and carbon stable isotopic ratios of the cements vary widely, from {minus}10.6{per_thousand} to +3.0{per_thousand} PDBmore » and from {minus}10.0{per_thousand} to +0.7{per_thousand} PDB, respectively. Cement {delta}{sup 18}O values principally reflect variation in rainfall {delta}{sup 18}O over a time scale of several thousand years. Rainfall and cement {delta}{sup 18}O values probably are inversely correlated with the amount of rainfall, which is related to the frequency and intensity of the Indian Ocean monsoon. Thus, cement {delta}{sup 18}O is potentially a proxy indicator of relative rainfall and monsoon activity. For each of three sampling areas, {delta}{sup 13}C is positively correlated to {delta}{sup 18}O. Cement {delta}{sup 13}C values are also related to rainfall amount because rainfall controls the plant population. Greater plant respiration of isotopically depleted CO{sub 2} to shallow groundwaters and burial of organic material in conglomerate deposits results in lower cement {delta}{sup 13}C values compared to periods of lesser plant activity.« less

Geochemistry of phosphatic-shales and associated authigenic minerals of the Miocene Monterey Formation: Implications for paragenetic evolution

NASA Astrophysics Data System (ADS)

Sandoval, A.; Loyd, S. J.

2016-12-01

The Monterey Formation is a petroleum source and reservoir rock in California that was deposited in several basins during the tectonically-active Middle Miocene. The middle carbonaceous marl member of the Monterey Formation contains intervals of phosphatic-shales that are rhythmically cemented by dolomite as layers and concretions. Diagenetic minerals can form as the result of organic matter remineralization facilitated by microbes utilizing oxygen, nitrate, iron (III), sulfate and fermentation products as electron acceptors. Precipitation of phosphate and carbonate minerals tends to occur in suboxic-anoxic sediments, generally experiencing sulfate reduction, where degradation of organic matter yields alkalinity, sulfide and phosphate ions. Here, we present sulfur and carbon geochemical data in order to better characterize the conditions that led to the precipitation of phosphorous-rich minerals (e.g., carbonate-fluorapatite (CFA)) and dolomite that occur in close stratigraphic proximity. These data include concentration of CFA-associated sulfate, carbonate associated sulfate (CAS) and the respective δ°S values. The concentration of inorganic/organic carbon and associated δC values have been determined for CFA, dolomite and the host-shale, in order to further characterize the diagenetic environment of precipitation. These data indicate that authigenesis occurred in pore waters influenced by multiple microbial reactions, including respiration and methanogenesis reactions, and ultimately highlight the complexity of the Monterey diagenetic environment.

Reactive transport and mass balance modeling of the Stimson sedimentary formation and altered fracture zones constrain diagenetic conditions at Gale crater, Mars

NASA Astrophysics Data System (ADS)

Hausrath, E. M.; Ming, D. W.; Peretyazhko, T. S.; Rampe, E. B.

2018-06-01

On a planet as cold and dry as present-day Mars, evidence of multiple aqueous episodes offers an intriguing view into very different past environments. Fluvial, lacustrine, and eolian depositional environments are being investigated by the Mars Science Laboratory Curiosity in Gale crater, Mars. Geochemical and mineralogical observations of these sedimentary rocks suggest diagenetic processes affected the sediments. Here, we analyze diagenesis of the Stimson formation eolian parent material, which caused loss of olivine and formation of magnetite. Additional, later alteration in fracture zones resulted in preferential dissolution of pyroxene and precipitation of secondary amorphous silica and Ca sulfate. The ability to compare the unaltered parent material with the reacted material allows constraints to be placed on the characteristics of the altering solutions. In this work we use a combination of a mass balance approach calculating the fraction of a mobile element lost or gained, τ, with fundamental geochemical kinetics and thermodynamics in the reactive transport code CrunchFlow to examine the characteristics of multiple stages of aqueous alteration at Gale crater, Mars. Our model results indicate that early diagenesis of the Stimson sedimentary formation is consistent with leaching of an eolian deposit by a near-neutral solution, and that formation of the altered fracture zones is consistent with a very acidic, high sulfate solution containing Ca, P and Si. These results indicate a range of past aqueous conditions occurring at Gale crater, Mars, with important implications for past martian climate and environments.

Carbon and nitrogen isotopic compositions of alkyl porphyrins from the Triassic Serpiano oil shale

NASA Technical Reports Server (NTRS)

Chicarelli, M. I.; Hayes, J. M.; Popp, B. N.; Eckardt, C. B.; Maxwell, J. R.

1993-01-01

The carbon and nitrogen isotopic compositions of seven of the most abundant alkylporphyrins from the Serpiano oil shale (marine, Triassic) were determined. For the C31 and C32 butanoporphyrins, values of delta 13CPDB and delta 15NAIR averaged -24.0% and -3.1%. In contrast, the C31 and C32 methylpropanoporphyrins, DPEP, and a C30 13-nor etioporphyrin had delta 13C and delta 15N values averaging -27.5 and -3.3%, respectively. Carbon and nitrogen isotopic values for kerogen averaged -30.8 and -0.9, whereas those for total extract averaged -31.6, and -4.0%. The butanoporphyrins apparently derive from a biological source different from that giving rise to the other porphyrins, their 13C enrichment not being related to carbon isotopic fractionation accompanying diagenetic reactions. The delta 15N values for all the porphyrins indicate that the depletion of 15N observed in the kerogen is of primary origin. Consistent with the very high abundance of hopanoids and methyl hopanoids in the aliphatic hydrocarbon fraction, it is suggested that cyanobacterial fixation of N2 may have been the main cause of 15N depletion.

The use of strontium and barium analyses for the reconstruction of the diet of the early medieval coastal population of Gdańsk (Poland): A preliminary study.

PubMed

Szostek, Krzysztof; Głab, Henryk; Pudło, Aleksandra

2009-01-01

Barium and strontium analyses yield an important perspective on temporal shifts in diet in relation to social and environmental circumstances. This research focuses on reconstructing dietary strategies of individuals in the early medieval (12-13th century) population of Gdańsk on the coast of the Baltic Sea. To describe these strategies where seafood rich in minerals was included in the diet, levels of strontium, barium, calcium and phosphorus were measured in first permanent molars of adult men and women whose remains were excavated from the churchyard in the city centre. Faunal remains from the excavation were analysed as an environmental background with respect to the content of the above-mentioned elements. The impact of diagenesis on the odontological material under study was also determined by an analysis of the soil derived from the grave and non-grave surroundings. For verification of diagenetic processes, the calcium/phosphorus index was used. Strontium, calcium, phosphorus and barium levels were determined with the spectrophotometric method using the latest generation plasma spectrophotometer Elan 6100 ICP-MS. From the results of the analysis of taphonomic parameters such as the soil pH, potential ion exchange in the grave surroundings and the Ca/P ratio, it can be inferred that diagenetic factors had little impact on the studied material. From this pilot study we can conclude that in the early Middle Ages in the Baltic Sea basin, seafood was included in the diet from early childhood and at the same time the diet contained calcium-rich milk products (also rich in minerals). The lack of sex differences may indicate the absence of a sex-specific nutritional strategy in childhood and early adolescence.

Constraining the climate and ocean pH of the early Earth with a geological carbon cycle model

PubMed Central

Krissansen-Totton, Joshua; Arney, Giada N.

2018-01-01

The early Earth’s environment is controversial. Climatic estimates range from hot to glacial, and inferred marine pH spans strongly alkaline to acidic. Better understanding of early climate and ocean chemistry would improve our knowledge of the origin of life and its coevolution with the environment. Here, we use a geological carbon cycle model with ocean chemistry to calculate self-consistent histories of climate and ocean pH. Our carbon cycle model includes an empirically justified temperature and pH dependence of seafloor weathering, allowing the relative importance of continental and seafloor weathering to be evaluated. We find that the Archean climate was likely temperate (0–50 °C) due to the combined negative feedbacks of continental and seafloor weathering. Ocean pH evolves monotonically from 6.6−0.4+0.6 (2σ) at 4.0 Ga to 7.0−0.5+0.7 (2σ) at the Archean–Proterozoic boundary, and to 7.9−0.2+0.1 (2σ) at the Proterozoic–Phanerozoic boundary. This evolution is driven by the secular decline of pCO2, which in turn is a consequence of increasing solar luminosity, but is moderated by carbonate alkalinity delivered from continental and seafloor weathering. Archean seafloor weathering may have been a comparable carbon sink to continental weathering, but is less dominant than previously assumed, and would not have induced global glaciation. We show how these conclusions are robust to a wide range of scenarios for continental growth, internal heat flow evolution and outgassing history, greenhouse gas abundances, and changes in the biotic enhancement of weathering. PMID:29610313

Constraining the climate and ocean pH of the early Earth with a geological carbon cycle model

NASA Astrophysics Data System (ADS)

Krissansen-Totton, Joshua; Arney, Giada N.; Catling, David C.

2018-04-01

The early Earth’s environment is controversial. Climatic estimates range from hot to glacial, and inferred marine pH spans strongly alkaline to acidic. Better understanding of early climate and ocean chemistry would improve our knowledge of the origin of life and its coevolution with the environment. Here, we use a geological carbon cycle model with ocean chemistry to calculate self-consistent histories of climate and ocean pH. Our carbon cycle model includes an empirically justified temperature and pH dependence of seafloor weathering, allowing the relative importance of continental and seafloor weathering to be evaluated. We find that the Archean climate was likely temperate (0–50 °C) due to the combined negative feedbacks of continental and seafloor weathering. Ocean pH evolves monotonically from 6.6‑0.4+0.6 (2σ) at 4.0 Ga to 7.0‑0.5+0.7 (2σ) at the Archean–Proterozoic boundary, and to 7.9‑0.2+0.1 (2σ) at the Proterozoic–Phanerozoic boundary. This evolution is driven by the secular decline of pCO2, which in turn is a consequence of increasing solar luminosity, but is moderated by carbonate alkalinity delivered from continental and seafloor weathering. Archean seafloor weathering may have been a comparable carbon sink to continental weathering, but is less dominant than previously assumed, and would not have induced global glaciation. We show how these conclusions are robust to a wide range of scenarios for continental growth, internal heat flow evolution and outgassing history, greenhouse gas abundances, and changes in the biotic enhancement of weathering.

The effects of early diagenesis on the chemical and stable carbon isotopic composition of wood

USGS Publications Warehouse

Spiker, E. C.; Hatcher, P.G.

1987-01-01

Studies of modern and ancient buried wood show that there is a linear correlation between carbohydrate content and the stable carbon isotope composition as carbohydrates are preferentially degraded during early diagenesis. As the carbohydrate content decreases, the ??13C value of the degraded wood decreases 1 to 2 per mil, approaching the value of the residual lignin. These results indicate that carbohydrate degradation products are lost and not incorporated into the aromatic structure as lignin is selectively preserved during early diagenesis of wood. These results also indicate that attempts to quantify terrestrial inputs to modern sedimentary organic matter based on ??13C values should consider the possibility of a 1 to 2 per mil decrease in the ??13C value of degraded wood. ?? 1987.

Brucite microbialites in living coral skeletons: Indicators of extreme microenvironments in shallow-marine settings

USGS Publications Warehouse

Nothdurft, L.D.; Webb, G.E.; Buster, N.A.; Holmes, C.W.; Sorauf, J.E.; Kloprogge, J.T.

2005-01-01

Brucite [Mg(OH)2] microbialites occur in vacated interseptal spaces of living scleractinian coral colonies (Acropora, Pocillopora, Porites) from subtidal and intertidal settings in the Great Barrier Reef, Australia, and subtidal Montastraea from the Florida Keys, United States. Brucite encrusts microbial filaments of endobionts (i.e., fungi, green algae, cyanobacteria) growing under organic biofilms; the brucite distribution is patchy both within interseptal spaces and within coralla. Although brucite is undersaturated in seawater, its precipitation was apparently induced in the corals by lowered pCO 2 and increased pH within microenvironments protected by microbial biofilms. The occurrence of brucite in shallow-marine settings highlights the importance of microenvironments in the formation and early diagenesis of marine carbonates. Significantly, the brucite precipitates discovered in microenvironments in these corals show that early diagenetic products do not necessarily reflect ambient seawater chemistry. Errors in environmental interpretation may arise where unidentified precipitates occur in microenvironments in skeletal carbonates that are subsequently utilized as geochemical seawater proxies. ?? 2005 Geological Society of America.

Elemental geochemistry and strontium-isotope stratigraphy of Cenomanian to Santonian neritic carbonates in the Zagros Basin, Iran

NASA Astrophysics Data System (ADS)

Navidtalab, Amin; Rahimpour-Bonab, Hossain; Huck, Stefan; Heimhofer, Ulrich

2016-12-01

A Neo-Tethyan upper Cenomanian-Santonian neritic carbonate ramp succession (Sarvak and Ilam formations), drilled in the Zagros Basin in southwest Iran, was investigated via detailed sedimentology, microfacies analysis, elemental geochemistry and Sr-isotope stratigraphy (SIS). The succession contains two exposure surfaces, which are known as the CT-ES and mT-ES (Cenomanian-Turonian and middle Turonian, respectively), and associated prominent negative carbon-isotope excursions that represent important regional stratigraphic marker horizons. Precise knowledge about the onset of platform exposure and the duration of the exposure-related hiatus, however, is currently lacking due to a rather low-resolved shallow-water biostratigraphic framework and a bulk carbonate carbon-isotope pattern that clearly differs from global Late Cretaceous reference curves. Therefore, the existing bio-chemostratigraphic framework was complemented by bulk carbonate strontium-isotope stratigraphy (SIS). As bulk carbonate material is in particular prone to diagenetic alteration, a careful selection of least altered samples has been carried out by means of elemental geochemistry and petrography. In contrast to what could be expected, the meteoric alteration of limestones beneath both exposure surfaces is not clearly expressed by increasing iron and manganese and coeval decreasing strontium contents. On the contrary, the impact of meteoric diagenesis is well illustrated via pronounced increases in Rb concentrations and concomitant prominent positive shifts to radiogenic strontium-isotope values, an observation that clearly reflects the decay of continentally derived 87Rb into 87Sr. Rubidium corrected strontium-isotope values place the CT-ES around the Cenomanian-Turonian boundary and point to an exposure duration of less than 0.4 Myr. This rather short-term CT-ES related hiatus is supported by petrographic evidence, which indicates a youth karstification stage of strata beneath the CT

High-resolution carbonate isotopic study of the Mural Formation (Cerro Pimas section), Sonora, México: Implications for early Albian oceanic anoxic events

NASA Astrophysics Data System (ADS)

Madhavaraju, J.; Lee, Yong Il; Scott, R. W.; González-León, C. M.; Jenkyns, H. C.; Saucedo-Samaniego, J. C.; Ramasamy, S.

2018-03-01

The 420-m thick stratigraphic section of the Mural Formation that is exposed in the Cerro Pimas area of northern Sonora, Mexico, is composed of limestone lithofacies ranging from bioclastic wackestone to boundstone, whose biota is characterized by low diversity. Prominent age-diagnostic fossils are benthic foraminifera and long-ranging calcareous algae that indicate the Aptian/Albian boundary is close to the base of the Los Coyotes Member. The carbonates of this formation have negative to positive δ13C values (-4.63 to +2.6‰) and highly depleted δ18O values that range from -12.74 to -8.34‰. The absence of correlation between δ13C and δ18O values supports a primary marine origin for the δ13C values of these limestones. The carbon-isotopic curve of the Cerro Pimas stratigraphic section has well-defined δ13C segments (C8 - C15) that compare with published curves of similar age. In the lower part of the early Albian Los Coyotes Member, the presence of OAE 1b is indicated by an increase followed by a decrease in δ13C values, suggesting correlation with the Kilian Event. The middle part of the Los Coyotes Member has a significant negative carbon-isotope excursion correlated with the globally recognizable early Albian Paquier event. Moreover, another significant negative carbon-isotope shift is observed in the upper part of the Los Coyotes Member, which can be correlated with the Leenhardt Event. The occurrence of the Kilian, Paquier and Leenhardt Events (OAE 1b cluster) in the Cerro Pimas stratigraphy confirms the global nature of these early Albian disturbances of the carbon cycle.

Deglacial climate, carbon cycle and ocean chemistry changes in response to a terrestrial carbon release

NASA Astrophysics Data System (ADS)

Simmons, C. T.; Matthews, H. D.; Mysak, L. A.

2016-02-01

Researchers have proposed that a significant portion of the post-glacial rise in atmospheric CO2 could be due to the respiration of permafrost carbon stocks that formed over the course of glaciation. In this paper, we used the University of Victoria Earth System Climate Model v. 2.9 to simulate the deglacial and interglacial carbon cycle from the last glacial maximum to the present. The model's sensitivity to mid and high latitude terrestrial carbon storage is evaluated by including a 600 Pg C carbon pool parameterized to respire in concert with decreases in ice sheet surface area. The respiration of this stored carbon during the early stages of deglaciation had a large effect on the carbon cycle in these simulations, allowing atmospheric CO2 to increase by 40 ppmv in the model, with an additional 20 ppmv increase occurring in the case of a more realistic, prescribed CO2 radiative warming. These increases occurred prior to large-scale carbon uptake due to the reestablishment of boreal forests and peatlands in the proxy record (beginning in the early Holocene). Surprisingly, the large external carbon input to the atmosphere and oceans did not increase sediment dissolution and mean ocean alkalinity relative to a control simulation without the high latitude carbon reservoir. In addition, our simulations suggest that an early deglacial terrestrial carbon release may come closer to explaining some observed deglacial changes in deep-ocean carbonate concentrations than simulations without such a release. We conclude that the respiration of glacial soil carbon stores may have been an important contributor to the deglacial CO2 rise, particularly in the early stages of deglaciation.

Differences in carbon source usage by dental plaque in children with and without early childhood caries

PubMed Central

Zhao, Yan; Zhong, Wen-Jie; Xun, Zhe; Zhang, Qian; Song, Ye-Qing; Liu, Yun-Song; Chen, Feng

2017-01-01

Early childhood caries (ECC) is a considerable pediatric and public health problem worldwide. Preceding studies have focused primarily on bacterial diversity at the taxonomic level. Although these studies have provided significant information regarding the connection between dental caries and oral microbiomes, further comprehension of this microbial community’s ecological relevance is limited. This study identified the carbon source metabolic differences in dental plaque between children with and without ECC. We compared the microbial community functional diversity in 18 caries-free subjects with 18 severe ECC patients based on sole carbon source usage using a Biolog assay. The anaerobic microbial community in the ECC patients displayed greater metabolic activity than that of the control group. Specific carbon source metabolism differed significantly between the two groups. Subjects from the two groups were well distinguished by cluster and principal component analyses based on discriminative carbon sources. Our results implied that the microbial functional diversity between the ECC patients and healthy subjects differed significantly. In addition, the Biolog assay furthered our understanding of oral microbiomes as a composite of functional abilities, thus enabling us to identify the ecologically relevant functional differences among oral microbial communities.

The impact of deep-tier burrow systems in sediment mixing and ecosystem engineering in early Cambrian carbonate settings

PubMed Central

Zhang, Li-Jun; Qi, Yong-An; Buatois, Luis A.; Mángano, M. Gabriela; Meng, Yao; Li, Da

2017-01-01

Bioturbation plays a substantial role in sediment oxygen concentration, chemical cycling, regeneration of nutrients, microbial activity, and the rate of organic matter decomposition in modern oceans. In addition, bioturbators are ecosystem engineers which promote the presence of some organisms, while precluding others. However, the impact of bioturbation in deep time remains controversial and limited sediment mixing has been indicated for early Paleozoic seas. Our understanding of the actual impact of bioturbation early in the Phanerozoic has been hampered by the lack of detailed analysis of the functional significance of specific burrow architectures. Integration of ichnologic and sedimentologic evidence from North China shows that deep-tier Thalassinoides mazes occur in lower Cambrian nearshore carbonate sediments, leading to intense disruption of the primary fabric. Comparison with modern studies suggest that some of the effects of this style of Cambrian bioturbation may have included promotion of nitrogen and ammonium fluxes across the sediment-water interface, average deepening of the redox discontinuity surface, expansion of aerobic bacteria, and increase in the rate of organic matter decomposition and the regeneration of nutrients. Our study suggests that early Cambrian sediment mixing in carbonate settings may have been more significant than assumed in previous models. PMID:28374857

Benthic Carbon Mineralization in Hadal Trenches: Insights From In Situ Determination of Benthic Oxygen Consumption

NASA Astrophysics Data System (ADS)

Luo, Min; Glud, Ronnie N.; Pan, Binbin; Wenzhöfer, Frank; Xu, Yunping; Lin, Gang; Chen, Duofu

2018-03-01

Hadal trenches have been proposed as depocenters of organic material and hot spots for organic matter mineralization. In this study, we for the first time quantified the total benthic O2 uptake in hadal trenches using in situ chamber incubations. Three trenches in the tropical Pacific were targeted and exhibited relatively high diagenetic activity given the great water depths, that is, the Mariana Trench (2.0 × 102 μmol O2 m-2 d-1, 10,853 m), the Mussau Trench (2.7 ± 0.1 × 102 μmol O2 m-2 d-1, 7,011 m), and the New Britain Trench (6.0 ± 0.1 × 102 μmol O2 m-2 d-1, 8,225 m). Combined with the analyses of total organic carbon and δ13C of total organic carbon in the sediments and previously published in situ O2 microprofiles from hadal settings, we suggest that hadal benthic carbon mineralization partly is governed by the surface production and also is linked to the distance from land. Therefore, we highlight that terrestrial organic matter can be of importance in sustaining benthic communities in some hadal settings.

An early-branching microbialite cyanobacterium forms intracellular carbonates.

PubMed

Couradeau, Estelle; Benzerara, Karim; Gérard, Emmanuelle; Moreira, David; Bernard, Sylvain; Brown, Gordon E; López-García, Purificación

2012-04-27

Cyanobacteria have affected major geochemical cycles (carbon, nitrogen, and oxygen) on Earth for billions of years. In particular, they have played a major role in the formation of calcium carbonates (i.e., calcification), which has been considered to be an extracellular process. We identified a cyanobacterium in modern microbialites in Lake Alchichica (Mexico) that forms intracellular amorphous calcium-magnesium-strontium-barium carbonate inclusions about 270 nanometers in average diameter, revealing an unexplored pathway for calcification. Phylogenetic analyses place this cyanobacterium within the deeply divergent order Gloeobacterales. The chemical composition and structure of the intracellular precipitates suggest some level of cellular control on the biomineralization process. This discovery expands the diversity of organisms capable of forming amorphous calcium carbonates.

The carbon cycle on early Earth--and on Mars?

PubMed

Grady, Monica M; Wright, Ian

2006-10-29

One of the goals of the present Martian exploration is to search for evidence of extinct (or even extant) life. This could be redefined as a search for carbon. The carbon cycle (or, more properly, cycles) on Earth is a complex interaction among three reservoirs: the atmosphere; the hydrosphere; and the lithosphere. Superimposed on this is the biosphere, and its presence influences the fixing and release of carbon in these reservoirs over different time-scales. The overall carbon balance is kept at equilibrium on the surface by a combination of tectonic processes (which bury carbon), volcanism (which releases it) and biology (which mediates it). In contrast to Earth, Mars presently has no active tectonic system; neither does it possess a significant biosphere. However, these observations might not necessarily have held in the past. By looking at how Earth's carbon cycles have changed with time, as both the Earth's tectonic structure and a more sophisticated biology have evolved, and also by constructing a carbon cycle for Mars based on the carbon chemistry of Martian meteorites, we investigate whether or not there is evidence for a Martian biosphere.

The carbon cycle on early Earth—and on Mars?

PubMed Central

Grady, Monica M; Wright, Ian

2006-01-01

One of the goals of the present Martian exploration is to search for evidence of extinct (or even extant) life. This could be redefined as a search for carbon. The carbon cycle (or, more properly, cycles) on Earth is a complex interaction among three reservoirs: the atmosphere; the hydrosphere; and the lithosphere. Superimposed on this is the biosphere, and its presence influences the fixing and release of carbon in these reservoirs over different time-scales. The overall carbon balance is kept at equilibrium on the surface by a combination of tectonic processes (which bury carbon), volcanism (which releases it) and biology (which mediates it). In contrast to Earth, Mars presently has no active tectonic system; neither does it possess a significant biosphere. However, these observations might not necessarily have held in the past. By looking at how Earth's carbon cycles have changed with time, as both the Earth's tectonic structure and a more sophisticated biology have evolved, and also by constructing a carbon cycle for Mars based on the carbon chemistry of Martian meteorites, we investigate whether or not there is evidence for a Martian biosphere. PMID:17008211

Recognition of primary and diagenetic magnetizations to determine the magnetic polarity record and timing of deposition of the moat-fill rocks of the Oligocene Creede Caldera, Colorado

USGS Publications Warehouse

Reynolds, Richard L.; Rosenbaum, Joseph G.; Sweetkind, Donald S.; Lanphere, Marvin A.; Robert, Andrew P.; Verosub, Kenneth L.

2000-01-01

postdepositional magnetite and maghemite that formed in rocks in which most or all detrital megnetic iron oxide was destroyed. Incipient oxidation of early diagenetic pyrite may have normal polarity Snowshoe Mountain Tuff (26.89 ± 0.0 Ma, 1 δ) and on the normal polarity postcaldera Fisher lava flows (as young as 26.23 ± 0.05 Ma, 1 δ) indicate that deposition of the Creede Formation spanned about 340-660 k.y. The intermittently defined normal polarity magnetization for the caldera-fill sequence, compared with different versions of the geomagnetic polarity time scale, is consistent with the shorter time span.

Early Age Carbonation Heat and Products of Tricalcium Silicate Paste Subject to Carbon Dioxide Curing.

PubMed

Li, Zhen; He, Zhen; Shao, Yixin

2018-05-04

This paper presents a study on the carbonation reaction heat and products of tricalcium silicate (C₃S) paste exposed to carbon dioxide (CO₂) for rapid curing. Reaction heat was measured using a retrofitted micro-calorimeter. The highest heat flow of a C₃S paste subject to carbonation curing was 200 times higher than that by hydration, and the cumulative heat released by carbonation was three times higher. The compressive strength of a C₃S paste carbonated for 2 h and 24 h was 27.5 MPa and 62.9 MPa, respectively. The 24-h carbonation strength had exceeded the hydration strength at 28 days. The CO₂ uptake of a C₃S paste carbonated for 2 h and 24 h was 17% and 26%, respectively. The X-ray diffraction (XRD), transmission electron microscope coupled with energy dispersive spectrometer (TEM-EDS), and 29 Si magic angle spinning⁻nuclear magnetic resonance ( 29 Si MAS-NMR) results showed that the products of a carbonated C₃S paste were amorphous silica (SiO₂) and calcite crystal. There was no trace of calcium silicate hydrate (C⁻S⁻H) or other polymorphs of calcium carbonate (CaCO₃) detected.

Bioturbating animals control the mobility of redox-sensitive trace elements in organic-rich mudstone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harazim, Dario; McIlroy, Duncan; Edwards, Nicholas P.

Bioturbating animals modify the original mineralogy, porosity, organic content, and fabric of mud, thus affecting the burial diagenetic pathways of potential hydrocarbon source, seal, and reservoir rocks. High-sensitivity, synchrotron rapid scanning X-ray fluorescence elemental mapping reveals that producers of phycosiphoniform burrows systematically partition redox-sensitive trace elements (i.e., Fe, V, Cr, Mn, Co, Ni, Cu, and As) in fine-grained siliciclastic rocks. Systematic differences in organic carbon content (total organic carbon >1.5 wt%) and quality (Δ 13C org~0.6‰) are measured between the burrow core and host sediment. The relative enrichment of redox-sensitive elements in the burrow core does not correlate with significantmore » neo-formation of early diagenetic pyrite (via trace metal pyritization), but is best explained by physical concentration of clay- and silt-sized components. A measured loss (~–15%) of the large-ionic-radius elements Sr and Ba from both burrow halo and core is most likely associated with the release of Sr and Ba to pore waters during biological ( in vivo) weathering of silt- to clay-sized lithic components and feldspar. In conclusion, this newly documented effect has significant potential to inform the interpretation of geochemical proxy and rock property data, particularly from shales, where elemental analyses are commonly employed to predict reservoir quality and support paleoenvironmental analysis.« less

Bioturbating animals control the mobility of redox-sensitive trace elements in organic-rich mudstone

DOE PAGES

Harazim, Dario; McIlroy, Duncan; Edwards, Nicholas P.; ...

2015-10-07

Bioturbating animals modify the original mineralogy, porosity, organic content, and fabric of mud, thus affecting the burial diagenetic pathways of potential hydrocarbon source, seal, and reservoir rocks. High-sensitivity, synchrotron rapid scanning X-ray fluorescence elemental mapping reveals that producers of phycosiphoniform burrows systematically partition redox-sensitive trace elements (i.e., Fe, V, Cr, Mn, Co, Ni, Cu, and As) in fine-grained siliciclastic rocks. Systematic differences in organic carbon content (total organic carbon >1.5 wt%) and quality (Δ 13C org~0.6‰) are measured between the burrow core and host sediment. The relative enrichment of redox-sensitive elements in the burrow core does not correlate with significantmore » neo-formation of early diagenetic pyrite (via trace metal pyritization), but is best explained by physical concentration of clay- and silt-sized components. A measured loss (~–15%) of the large-ionic-radius elements Sr and Ba from both burrow halo and core is most likely associated with the release of Sr and Ba to pore waters during biological ( in vivo) weathering of silt- to clay-sized lithic components and feldspar. In conclusion, this newly documented effect has significant potential to inform the interpretation of geochemical proxy and rock property data, particularly from shales, where elemental analyses are commonly employed to predict reservoir quality and support paleoenvironmental analysis.« less

Dolomitization and neomorphism of Mississippian (Visean) upper debolt formation, Blueberry field, northeastern British Columbia: Geologic, petrologic, and chemical evidence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Durocher, S.; Al-Aasm, I.S.

1997-06-01

Petrographic, chemical, and isotopic studies of the Mississippian (Visean) upper Debolt Formation in the Blueberry field, British Columbia, Canada, reveal that dolomitization was the result of several diagenetic events and that neomorphic alteration of these dolomites significantly modified their original chemical signatures. These studies also demonstrate how tectonics play an important role in controlling and modifying reservoir dolomites in the area. Petrographic investigations have documented two early dolomite phases, (1) early matrix dolomite and (2) pervasive dolomite, and two later generations, (3) coarse cement and (4) pseudomorphic replacement of crinoids. Early matrix dolomite occurs as small (average 25 {mu}m) subhedralmore » to euhedral crystals that replace the matrix of carbonate mudstones, wackestones, and packstones. Petrographic evidence suggests that early matrix dolomite had a relatively early, precompaction origin, possibly from marine fluids. However, geochemical evidence indicates that later fluids have altered their original geochemical signatures. Pervasive dolomite, which forms the reservoir intercrystalline porosity, occurs with planar-s and planar-e textures. Planar-s crystals typically have a dirty appearance and exhibit homogeneous dull brown/red cathodoluminescence colors. Planar-e crystals may appear with a cloudy core and a clear rim, and under cathodoluminescence display an irregular dull brown/red core and a thin, bright red rim. Due to the spatial distribution pattern of pervasive dolomite with respect to the overlying unconformity surface, its paleogeographic distribution and close temporal relationship with meteoric diagenetic events, pervasive dolomite formed from a mixture of seawater and meteoric fluids. However, alteration of their primary chemistry by later fluids is indicated by their depleted {delta}{sup 18}O values and radiogenic {sup 87}Sr/{sup 86}Sr ratios.« less

Effect of Harvest Residue Management on Tree Productivity and Carbon Pools during Early Stand Development in a Loblolly Pine Plantation

Treesearch

Chris A. Maier; Kurt H. Johnsen; Phillip Dougherty; Daniel McInnis; Pete Anderson; Steve Patterson

2012-01-01

Soil incorporation of postharvest forest floor or logging residues during site preparation increased mineral soil carbon (C) and nitrogen (N) concentration and had a differential effect on early stand growth in a clonal loblolly pine (Pinus taeda L.) plantation. Incorporating 25 Mg ha

Carbonate factories: A conundrum in sedimentary geology

NASA Astrophysics Data System (ADS)

Pomar, L.; Hallock, P.

2008-03-01

Describing, characterizing and interpreting the nearly infinite variety of carbonate rocks are conundrums - intricate and difficult problems having only conjectural answers - that have occupied geologists for more than two centuries. Depositional features including components, rock textures, lithofacies, platform types and architecture, all vary in space and time, as do the results of diagenetic processes on those primary features. Approaches to the study of carbonate rocks have become progressively more analytical. One focus has evolved from efforts to build reference models for specific Phanerozoic windows to scrutinize the effect of climate and long-term oscillations of the ocean-atmosphere system in influencing the mineralogy of carbonate components. This paper adds to the ongoing lively debates by attempting to understand changes in the predominant types of carbonate-producing organisms during the Mesozoic-Cenozoic, while striving to minimize the uniformitarian bias. Our approach integrates estimates of changes in Ca 2+ concentration in seawater and atmospheric CO 2, with biological evolution and ecological requirements of characteristic carbonate-producing marine communities. The underlying rationale for our approach is the fact that CO 2 is basic to both carbonates and organic matter, and that photosynthesis is a fundamental biological process responsible for both primary production of organic matter and providing chemical environments that promote calcification. Gross photosynthesis and hypercalcification are dependent largely upon sunlight, while net primary production and, e.g., subsequent burial of organic matter typically requires sources of new nutrients (N, P and trace elements). Our approach plausibly explains the changing character of carbonate production as an evolving response to changing environmental conditions driven by the geotectonic cycle, while identifying uncertainties that deserve further research. With metazoan consumer diversity reduced

Early Age Carbonation Heat and Products of Tricalcium Silicate Paste Subject to Carbon Dioxide Curing

PubMed Central

Li, Zhen; He, Zhen; Shao, Yixin

2018-01-01

This paper presents a study on the carbonation reaction heat and products of tricalcium silicate (C3S) paste exposed to carbon dioxide (CO2) for rapid curing. Reaction heat was measured using a retrofitted micro-calorimeter. The highest heat flow of a C3S paste subject to carbonation curing was 200 times higher than that by hydration, and the cumulative heat released by carbonation was three times higher. The compressive strength of a C3S paste carbonated for 2 h and 24 h was 27.5 MPa and 62.9 MPa, respectively. The 24-h carbonation strength had exceeded the hydration strength at 28 days. The CO2 uptake of a C3S paste carbonated for 2 h and 24 h was 17% and 26%, respectively. The X-ray diffraction (XRD), transmission electron microscope coupled with energy dispersive spectrometer (TEM-EDS), and 29Si magic angle spinning–nuclear magnetic resonance (29Si MAS-NMR) results showed that the products of a carbonated C3S paste were amorphous silica (SiO2) and calcite crystal. There was no trace of calcium silicate hydrate (C–S–H) or other polymorphs of calcium carbonate (CaCO3) detected. PMID:29734681

Constraining the thermal history of the North American Midcontinent Rift System using carbonate clumped isotopes and organic thermal maturity indices

USGS Publications Warehouse

Gallagher, Timothy M.; Sheldon, Nathan D.; Mauk, Jeffrey L.; Petersen, Sierra V.; Gueneli, Nur; Brocks, Jochen J.

2017-01-01

The Midcontinent Rift System (MRS) is a Late Mesoproterozoic (∼1.1 Ga) sequence of volcanic and sedimentary rocks exposed in the Lake Superior Region of North America. The MRS continues to be the focus of much research due to its economic mineral deposits as well as its archive of Precambrian life and tectonic processes. In order to constrain the post-depositional thermal history of the MRS, samples were analyzed for carbonate clumped isotope composition and organic thermal maturity. Clumped isotope values from sedimentary/early-diagenetic samples were partially reset during burial to temperatures between 68 and 75 °C. Solid-state reordering models indicate that maximum burial temperatures of 125–155 °C would reset the clumped isotope values to the observed temperature range prior to the onset of regional cooling and uplift. Clumped isotope results from late-stage veins in the White Pine Mine encompass a greater temperature range (49–116 °C), indicative of spatially variable hydrothermal activity and vein emplacement after burial temperatures fell below 100 °C during regional cooling and uplift. Clumped isotope and organic thermal maturity data do not indicate significant spatial differences in thermal history along the MRS. Observed variability in bulk organic matter composition and biomarker indices are therefore more likely a result of shifts in primary productivity or early-degradation processes. These results demonstrate that the MRS experienced a spatially consistent, relatively mild thermal history (125–155 °C) and is therefore a valuable archive for understanding the Late Mesoproterozoic environment.

Pyrolytic indices of diagenetic transformation of lignin as biogeochemical proxies for soil organic matter quality and C storage potential

NASA Astrophysics Data System (ADS)

Jiménez-González, Marco A.; Almendros, Gonzalo; Álvarez, Ana M.; Jiménez-Morillo, Nicasio T.; González-Vila, Francisco J.

2017-04-01

The environmental factors involved in soil organic carbon sequestration remain unclear. The functional relationships between the macromolecular structure of the soil organic matter (SOM) and its resilience has been a constant in classical biogeochemical models. Other more recent hypotheses have postulated that preservation by soil minerals may play a chief role in the accumulation of stable SOM forms. However, additional experimental data are required to demonstrate a cause-to-effect relationship between preservation and stabilization. Some authors might consider that models neglecting the role of macromolecular structure are swapping cause and effect i.e., that SOM structurally flexible, weakly condensed and having 'open' structures is the one with high potential to interact with the soil mineral matrix, leading to stable microaggregates. In this study up to 35 topsoil samples (0-5 cm) were collected from different Spanish soils with contrasted values of organic C (the dependent variable), geological substrate and vegetation type. A wide array of uni- and multivariate chemometric models were applied to independent variables consisting of total abundances of the major aromatic compounds, i.e., alkylbenzenes and methoxyphenols released from whole soil samples using pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS). These two families of compounds were selected since they are classically considered to inform on the degree of microbial reworking of lignins, which is an important precursor of the aromatic moiety of the SOM. A series of pyrolytic surrogate indices (aiming to express SOM diagenetic transformation in relation to the original biogenic molecular composition) were especially successful in forecasting SOC, viz: a) ratio between alkylbenzenes and methoxyphenols, b) ratio between short-chain (C0-C4) and long-chain (>C4) alkylbenzenes, c) ratio between methoxyphenols and short-chain alkylbenzenes, and d) ratios between methoxyphenols with different side

Hydrochemical variations in selected geothermal groundwater and carbonated springs in Korea: a baseline study for early detection of CO2 leakage.

PubMed

Choi, Hanna; Piao, Jize; Woo, Nam C; Cho, Heuynam

2017-02-01

A baseline hydrochemistry of the above zone aquifer was examined for the potential of CO 2 early detection monitoring. Among the major ionic components and stable isotope ratios of oxygen, hydrogen, and carbon, components with a relative standard deviation (RSD) of <10 % for the seasonal variation were selected as relatively stable. These components were tested for sensitivity to the introduction of 0.1 mol/L CO 2 (g) using the PHREEQC simulation results. If the relatively stable components were sensitive to the introduction of CO 2 , then they could be used as indicators of CO 2 leakage into the above zone. As an analog to the zone above CO 2 storage formation, we sampled deep groundwater, including geothermal groundwater from well depths of 400-700 m below the ground surface (bgs) and carbonated springs with a high CO 2 content in Korea. Under the natural conditions of inland geothermal groundwater, pH, electrical conductivity (EC), bicarbonate (HCO 3 ), δ 18 O, δ 2 H, and δ 13 C were relatively stable as well as sensitive to the introduction of CO 2 (g), thus showing good potential as monitoring parameters for early detection of CO 2 leakage. In carbonated springs, the parameters identified were pH, δ 18 O, and δ 2 H. Baseline hydrochemistry monitoring could provide information on parameters useful for detecting anomalies caused by CO 2 leakage as measures for early warning.

Origin of sulfide and phosphate deposits in Upper Proterozoic carbonate strata, Irece basin, Bahia, Brazil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kyle, J.R.; Misi, A.

1991-03-01

Carbonate strata of the Una Group represent late Proterozoic platform sedimentation in the Irece basin of north-central Brazil. Stratabound sulfide- and phosphate-rich units occur within a 50-m thick tidal flat sequence of dolomitic limestone and cherty dolomite. Three types of primary phosphate concentrations are present: columnar stromatolitic, laminar stromatolitic, and intraclastic. Resedimented phosphate clasts and phosphatic units interbedded with non phosphatic dolomites suggest early diagenetic replacement of algal carbonate units. Local stratabound Zn-Pb-Ag sulfide concentrations at the Tres Irmas prospect occur within silty dolomite with shallow water sedimentary structures and local disturbed laminae, synsedimentary faults, and breccias. Sulfide minerals includemore » pyrite, sphalerite, galena, marcasite, jordanite, tetrahedrite, and covellite. Pyrite crystal aggregates commonly show bladed forms. Nodular aggregates of length-slow quartz are locally associated with sulfides. Sulfur isotope analyses indicate relatively uniform heavy {delta}{sup 34}S values. Barite shows a {delta}{sup 34}S range from +25.2 to +29.6{per thousand}, CDT. Pyrite and sphalerite representative of a variety of textural types have a {delta}{sup 34}S range of +20.2 to +22.6{per thousand}. Late Proterozoic evaporite sulfates show a wide range of {delta}{sup 34} S values from about +10 to +28{per thousand}. Thus, the {delta}{sup 34}S values for Irece barite could reflect original seawater sulfate values. However, the relatively heavy {delta}{sup 34}S values of the associated sulfides suggests that the original seawater sulfate was modified by bacterial sulfate reduction processes in shallow sea floor sediments. Textural and {delta}{sup 34}S evidence suggests that a later stage of metallic mineralization scavenged sulfur from preexisting sulfides or from direct reduction of evaporitic sulfate minerals.« less

In search of early life: Carbonate veins in Archean metamorphic rocks as potential hosts of biomarkers

NASA Astrophysics Data System (ADS)

Peters, Carl A.; Piazolo, Sandra; Webb, Gregory E.; Dutkiewicz, Adriana; George, Simon C.

2016-11-01

The detection of early life signatures using hydrocarbon biomarkers in Precambrian rocks struggles with contamination issues, unspecific biomarkers and the lack of suitable sedimentary rocks due to extensive thermal overprints. Importantly, host rocks must not have been exposed to temperatures above 250 °C as at these temperatures biomarkers are destroyed. Here we show that Archean sedimentary rocks from the Jeerinah Formation (2.63 billion yrs) and Carawine Dolomite (2.55 billion yrs) of the Pilbara Craton (Western Australia) drilled by the Agouron Institute in 2012, which previously were suggested to be suitable for biomarker studies, were metamorphosed to the greenschist facies. This is higher than previously reported. Both the mineral assemblages (carbonate, quartz, Fe-chlorite, muscovite, microcline, rutile, and pyrite with absence of illite) and chlorite geothermometry suggest that the rocks were exposed to temperatures higher than 300 °C and probably ∼400 °C, consistent with greenschist-facies metamorphism. This facies leads to the destruction of any biomarkers and explains why the extraction of hydrocarbon biomarkers from pristine drill cores has not been successful. However, we show that the rocks are cut by younger formation-specific carbonate veins containing primary oil-bearing fluid inclusions and solid bitumens. Type 1 veins in the Carawine Dolomite consist of dolomite, quartz and solid bitumen, whereas type 2 veins in the Jeerinah Formation consist of calcite. Within the veins fluid inclusion homogenisation temperatures and calcite twinning geothermometry indicate maximum temperatures of ∼200 °C for type 1 veins and ∼180 °C for type 2 veins. Type 1 veins have typical isotopic values for reprecipitated Archean sea-water carbonates, with δ13CVPDB ranging from - 3 ‰ to 0‰ and δ18OVPDB ranging from - 13 ‰ to - 7 ‰, while type 2 veins have isotopic values that are similar to hydrothermal carbonates, with δ13CVPDB ranging from - 18 �

Diagenetic palaeotemperatures from aqueous fluid inclusions: re- equilibration of inclusions in carbonate cements by burial heating.

USGS Publications Warehouse

Burruss, R.C.

1987-01-01

Calculations based on the observed behaviour of inclusions in fluorite under external confining P allows prediction of the T and depths of burial necessary to initiate re-equilibration of aqueous inclusions in the common size range 40-4 mu m. Heating of 20-60oC over the initial trapping T may cause errors of 10-20oC in the homogenization T. This suggests that re-equilibration may cause aqueous inclusions in carbonates to yield a poor record of their low-T history, but a useful record of the maximum T experienced by the host rock. Previous work suggests that inclusions containing petroleum fluids will be less susceptible to re-equilibration.This and the following six abstracts represent papers presented at a joint meeting of the Applied Mineralogy Group of the Mineralogical Society and the Petroleum Group of the Geological Society held in Newcastle upon Tyne in April 1986.-R.A.H.

The carbon-isotopic composition of Proterozoic carbonates: Riphean successions from northwestern Siberia (Anabar Massif, Turukhansk Uplift)

NASA Technical Reports Server (NTRS)

Knoll, A. H.; Kaufman, A. J.; Semikhatov, M. A.

1995-01-01

Thick carbonate-dominated successions in northwestern Siberia document secular variations in the C-isotopic composition of seawater through Mesoproterozoic and early Neoproterozoic (Early to early Late Riphean) time. Mesoproterozoic dolomites of the Billyakh Group, Anabar Massif, have delta 13C values that fall between 0 and -1.9 permil versus PDB, with values in the upper part of the succession (Yusmastakh Formation) consistently higher than those of the lower (Ust'-Il'ya and Kotuikan formations). Consistent with available biostratigraphic and radiometric data, delta 13C values for Billyakh carbonates compare closely with those characterizing early Mesoproterozoic carbonates (about 1600-1200 Ma) worldwide. In contrast, late Mesoproterozoic to early Neoproterozoic limestones and dolomites in the Turukhansk Uplift exhibit moderate levels of secular variation. Only the lowermost carbonates in the Turukhansk succession (Linok Formation) have delta 13C values that approximate Billyakh values. Higher in the Turukhansk succession, delta 13C values vary from -2.7 to +4.6 permil (with outliers as low as -5.0 permil interpreted as diagentically altered). Again, consistent with paleontological and radiometric data, these values compare well with isotopic values from 1200 to 850 Ma successions elsewhere. Five sections measured in different parts of the Turukhansk basin show nearly identical patterns of variation, confirming that carbonate delta 13C correlates primarily with time and not facies. The Siberian sections illustrate the potential of integrated biostratigraphic and chemostratigraphic data in the intra- and interbasinal correlation of Mesoproterozoic and early Neoproterozoic rocks.

Accretion and differentiation of carbon in the early Earth.

PubMed

Tingle, T N

1998-05-15

The abundance of C in carbonaceous and ordinary chondrites decreases exponentially with increasing shock pressure as inferred from the petrologic shock classification of Scott et al. [Scott, E.R.D., Keil, K., Stoffler, D., 1992. Shock metamorphism of carbonaceous chondrites. Geochim. Cosmochim. Acta 56, 4281-4293] and Stoffler et al. [Stoffler, D., Keil, K., Scott, E.R.D., 1991. Shock metamorphism of ordinary chondrites. Geochim. Cosmochim. Acta 55, 3845-3867]. This confirms the experimental results of Tyburczy et al. [Tyburczy, J.A., Frisch, B., Ahrens, T.J., 1986. Shock-induced volatile loss from a carbonaceous chondrite: implications for planetary accretion. Earth Planet. Sci. Lett. 80, 201-207] on shock-induced devolatization of the Murchison meteorite showing that carbonaceous chondrites appear to be completely devolatilized at impact velocities greater than 2 km s-1. Both of these results suggest that C incorporation would have been most efficient in the early stages of accretion, and that the primordial C content of the Earth was between 10(24) and 10(25) g C (1-10% efficiency of incorporation). This estimate agrees well with the value of 3-7 x 10(24) g C based on the atmospheric abundance of 36Ar and the chondritic C/36Ar (Marty and Jambon, 1987). Several observations suggest that C likely was incorporated into the Earth's core during accretion. (1) Graphite and carbides are commonly present in iron meteorites, and those iron meteorites with Widmanstatten patterns reflecting the slowest cooling rates (mostly Group I and IIIb) contain the highest C abundances. The C abundance-cooling rate correlation is consistent with dissolution of C into Fe-Ni liquids that segregated to form the cores of the iron meteorite parent bodies. (2) The carbon isotopic composition of graphite in iron meteorites exhibits a uniform value of -5% [Deines, P., Wickman, F.E. 1973. The isotopic composition of 'graphitic' carbon from iron meteorites and some remarks on the troilitic

Active hematite concretion formation in modern acid saline lake sediments, Lake Brown, Western Australia

NASA Astrophysics Data System (ADS)

Bowen, Brenda Beitler; Benison, K. C.; Oboh-Ikuenobe, F. E.; Story, S.; Mormile, M. R.

2008-04-01

Concretions can provide valuable records of diagenesis and fluid-sediment interactions, however, reconstruction of ancient concretion-forming conditions can be difficult. Observation of modern hematite concretion growth in a natural sedimentary setting provides a rare glimpse of conditions at the time of formation. Spheroidal hematite-cemented concretions are actively precipitating in shallow subsurface sediments at Lake Brown in Western Australia. Lake Brown is a hypersaline (total dissolved solids up to 23%) and acidic (pH ˜ 4) ephemeral lake. The concretion host sediments were deposited between ˜ 1 and 3 ka, based on dating of stratigraphically higher and lower beds. These age constraints indicate that the diagenetic concretions formed < 3 ka, and field observations suggest that some are currently forming. These modern concretions from Lake Brown provide an example of very early diagenetic formation in acid and saline conditions that may be analogous to past conditions on Mars. Previously, the hematite concretions in the Burns formation on Mars have been interpreted as late stage diagenetic products, requiring long geologic time scales and multiple fluid flow events to form. In contrast, the Lake Brown concretions support the possibility of similar syndepositional to very early diagenetic concretion precipitation on Mars.

Compositions, ages, and diagenetic histories of the carbonate, sulfide, oxide, and phosphatic concretions at Gay Head, Massachusetts

USGS Publications Warehouse

Poppe, L.J.; Commeau, R.F.; O'Leary, Dennis W.

1988-01-01

The calcite/ankerite concretions were formed in a hot, seasonally arid, caliche-prone environment of early Raritan age; the pyrite, marcasite, and siderite concretions precipitated in sediments deposited in low-energy, marshy, estuarine environments of late Raritan age. The phosphate concretions formed in a middle to inner shelf environment. The goethite and lepidocrocite concretions are secondary oxidation or alteration products of the prexistent Cretaceous concretions that were excavated during the Pleistocene and incorporated into the glacial drift. -from Authors

Origin and timing of Dauphiné twins in quartz cement in fractured sandstones from diagenetic environments: Insight from fluid inclusions

NASA Astrophysics Data System (ADS)

Fall, András; Ukar, Estibalitz; Laubach, Stephen E.

2016-09-01

Electron backscattered diffraction techniques (EBSD) show that Dauphiné twins in quartz are widespread in many tectonometamorphic environments. Our study documents that under diagenetic temperatures (< 200 °C) and burial depths < 5 km Dauphiné twins are common in isolated fracture quartz deposits spanning between fracture walls (i.e., quartz bridges) in low-porosity quartz-cemented sandstones. Using examples from East Texas and Colorado cores, we show that twins are associated with crack-seal microstructure and fluid inclusions. Fracture wall-parallel and wall-normal inclusion trails contain coexisting aqueous and hydrocarbon gas inclusions, so homogenization temperatures of aqueous inclusions record true trapping temperatures. Inclusions in alignments normal to fracture walls are large and irregularly shaped compared to those aligned parallel to walls, but both show similar liquid-to-vapor ratios. Stacking transmitted light images with scanning electron microscope cathodoluminescence (SEM-CL) and EBSD images demonstrates that Dauphiné twin boundaries are localized along wall-normal inclusion trails. Trapping temperatures for wall-normal inclusion trails are usually higher than those aligned parallel to the fracture wall. Wall-normal fluid inclusion assemblage temperatures typically match the highest temperatures of wall-parallel assemblages trapped during sequential widening, but not necessarily the most recent. In context of burial histories for these samples, this temperature pattern implies that wall-normal assemblages form at discrete times during or after crack-seal fracture widening. Localization in isolated, potentially high-stress quartz deposits in fractures is compatible with a mechanical origin for these Dauphiné twins. Punctuated temperature values and discrepant sizes and shapes of inclusions in wall-normal trails implies that twinning is a by-product of the formation of the wall-normal inclusion assemblages. The association of Dauphiné twins

Isotope Biogeochemistry of Sulfur in a Cold-Water Carbonate Mound (IODP Site 1317)

NASA Astrophysics Data System (ADS)

Ferdelman, T. G.; Boettcher, M. E.

2007-12-01

To establish a depositional model for cold-water carbonate mounds, Challenger Mound and adjacent continental slope sites were drilled during IODP Expedition 307 in May 2005. Although a role for methane seepage and subsequent anaerobic oxidation was discounted both as a hard-round substrate for mound initiation and as a principal source of carbonate within the mound succession, interstitial water profiles of sulfate, alkalinity, Mg, and Sr indicated a tight coupling between carbonate diagenesis and mircrobial sulfate reduction. The reaction of sulfide with siliciclastic iron-bearing minerals to form pyrite was proposed to account for enhanced diagenetic carbonate precipitation (Ferdelman et al., 2006; Proc. IODP, vol. 307; doi:10.2204/iodp.proc.307.2006). To characterize these geomicrobial sulfur transformations in the carbonate mound sediments, the inorganic and stable isotope geochemical compositions of pore water sulfate and solid phase reduced sulfur compounds were performed. Acid-volatile sulfur (AVS) and pyrite del 34S compositions were usually similar and exhibited an increasing trend of from -40 per mil near surface to -20 per mil at the mound base at 132 mbsf. However, several excursions to more 34S sulfur enriched pyrite to values >0 per mil were observed in the deeper sections of the mound sequence. These excursions may be linked transitory changes in the depth of the methane-sulfate transition zone during mound build-up. The oxygen isotopic composition of residual dissolved sulfate indicates intracellular isotope exchange processes within the cells of SRBs, leading to increasing equilibration between extracellular pore water and sulfate.

Identification of novel sulfur-containing steroids in sediments and petroleum: probable incorporation of sulfur into δ 5,7-sterols during early diagenesis

NASA Astrophysics Data System (ADS)

Sinninghe Damsté, Jaap S.; Schouten, Stefan; de Leeuw, Jan W.; van Duin, Adri C. T.; Geenevasen, Jan A. J.

1999-01-01

A novel sulfur-containing sterane, 4α,7α-epithio-5β-cholestane, has been identified in a sediment extract from the Miocene Northern Apennines marl (Italy) after its isolation by column chromatography and high pressure liquid chromatography. The compound has been characterised by GC-MS and mild Nickel boride desulfurisation and one and two-dimensional 1H NMR techniques. C 27-C 29 homologs have been detected in sediment extracts of three different formations and in one petroleum sample. These sulfur-containing steroids are probably formed by an intramolecular reaction of inorganic sulfides with early diagenetic products of Δ 5,7-sterols.

Response of carbon isotopic compositions of Early-Middle Permian coals in North China to palaeo-climate change

NASA Astrophysics Data System (ADS)

Ding, Dianshi; Liu, Guijian; Sun, Xiaohui; Sun, Ruoyu

2018-01-01

To investigate the magnitude to which the carbon isotopic ratio (δ13C) varies in coals in response to their contemporary terrestrial environment, the Early-Middle Permian Huainan coals (including coals from the Shanxi Formation, Lower Shihezi Formation and Upper Shihezi Formation) in North China were systematically sampled. A 2.5‰ variation range of δ13C values (-25.15‰ to -22.65‰) was observed in Huainan coals, with an average value of -24.06‰. As coal diagenesis exerts little influence on carbon isotope fractionation, δ13C values in coals were mainly imparted by those of coal-forming flora assemblages which were linked to the contemporary climate. The δ13C values in coals from the Shanxi and Lower Shihezi Formations are variable, reflecting unstable climatic oscillations. Heavy carbon isotope is enriched in coals of the Capitanian Upper Shihezi Formation, implying a shift to high positive δ13C values of coeval atmospheric CO2. Notably, our study provides evidence of the Kamura event in the terrestrial environment for the first time.

Plasma-Enabled Carbon Nanostructures for Early Diagnosis of Neurodegenerative Diseases

PubMed Central

Pineda, Shafique; Han, Zhao Jun; Ostrikov, Kostya (Ken)

2014-01-01

Carbon nanostructures (CNs) are amongst the most promising biorecognition nanomaterials due to their unprecedented optical, electrical and structural properties. As such, CNs may be harnessed to tackle the detrimental public health and socio-economic adversities associated with neurodegenerative diseases (NDs). In particular, CNs may be tailored for a specific determination of biomarkers indicative of NDs. However, the realization of such a biosensor represents a significant technological challenge in the uniform fabrication of CNs with outstanding qualities in order to facilitate a highly-sensitive detection of biomarkers suspended in complex biological environments. Notably, the versatility of plasma-based techniques for the synthesis and surface modification of CNs may be embraced to optimize the biorecognition performance and capabilities. This review surveys the recent advances in CN-based biosensors, and highlights the benefits of plasma-processing techniques to enable, enhance, and tailor the performance and optimize the fabrication of CNs, towards the construction of biosensors with unparalleled performance for the early diagnosis of NDs, via a plethora of energy-efficient, environmentally-benign, and inexpensive approaches. PMID:28788112

Solid-state 13C NMR studies of a large fossil gymnosperm from the Yallourn Open Cut, Latrobe Valley, Australia

USGS Publications Warehouse

Bates, A.L.; Hatcher, P.G.

1989-01-01

A series of samples taken from the cross section of a 3-m-diameter fossilized gymnospermous log (Araucariaceae) in the Yallourn Seam of the Australian brown coals was examined by solid state 13C nuclear magnetic resonance to delineate chemical changes related to the combined processes of peatification and coalification. The results show that cellulosic materials were degraded and lost on the periphery of the log, however, the degree of such degradation in the central core is substantially less. The lignin is uniformly altered by coalification reactions to a macromolecular substance displaying decreased aryl ether linkages but significantly greater amounts of carbon linkages compared to modern lignin. Changes in the methoxyl carbon contents of lignin in cross section reveal demethylation reactions, but these do not appear to be related to degree of carbon linking. Both the degredation of cellulosic materials and demethylation of lignin appear to be early diagenetic processes occurring during peatification independently of the coalification reactions. ?? 1989.

Climate change and carbon-cycling during the latest Cretaceous-Early Paleogene; a new 13.5 million year-long, orbital-resolution, stable isotope record from the South Atlantic

NASA Astrophysics Data System (ADS)

Barnet, J.; Littler, K.; Kroon, D.; Leng, M. J.; Westerhold, T.; Roehl, U.; Zachos, J. C.

2017-12-01

The "greenhouse" world of the latest Cretaceous-Early Paleogene ( 70-34 Ma) was characterised by multi-million year variability in climate and the carbon-cycle. Throughout this interval the pervasive imprint of orbital-cyclicity, particularly eccentricity and precession, is visible in elemental and stable isotope data obtained from multiple deep-sea sites. Periodic "hyperthermal" events, occurring largely in-step with these orbital cycles, have proved particularly enigmatic, and may be the closest, albeit imperfect, analogues for anthropogenic climate change. This project utilises CaCO3-rich marine sediments recovered from ODP Site 1262 at a paleo-depth of 3600 m on the Walvis Ridge, South Atlantic, of late Maastrichtian-mid Paleocene age ( 67-60 Ma). We have derived high-resolution (2.5-4 kyr) carbon and oxygen isotope data from the epifaunal benthic foraminifera species Nuttallides truempyi. Combining the new record with the existing Late Paleocene-Early Eocene record generated from the same site by Littler et al. (2014), yields a single-site reference curve detailing 13.5 million years of orbital cyclicity in paleoclimate and carbon cycle from the latest Cretaceous to near the peak warmth of the Early Paleogene greenhouse. Spectral analysis of this new combined dataset allows us to identify long (405-kyr) eccentricity, short (100-kyr) eccentricity, and precession (19-23-kyr) as the principle forcing mechanisms governing pacing of the background climate and carbon-cycle during this time period, with a comparatively weak obliquity (41-kyr) signal. Cross-spectral analysis suggests that changes in climate lead the carbon cycle throughout most of the record, emphasising the role of the release of temperature-sensitive carbon stores as a positive feedback to an initial warming induced by changes in orbital configuration. The expression of comparatively understudied Early Paleocene events, including the Dan-C2 Event, Latest Danian Event, and Danian/Selandian Transition

Biogeochemical processes controlling authigenic carbonate formation within the sediment column from the Okinawa Trough

NASA Astrophysics Data System (ADS)

Li, Jiwei; Peng, Xiaotong; Bai, Shijie; Chen, Zhiyan; Van Nostrand, Joy D.

2018-02-01

Authigenic carbonates are one type of conspicuous manifestation in seep environments that can provide long-term archives of past seepage activity and methane cycling in the oceans. Comprehensive investigations of the microbial community functional structure and their roles in the process of carbonate formation are, however, lacking. In this study, the mineralogical, geochemical, and microbial functional composition were examined in seep carbonate deposits collected from the west slope of the northern section of the Okinawa Trough (OT). The aim of this work was to explore the correspondence between the mineralogical phases and microbial metabolism during carbonate deposit formation. The mineralogical analyses indicated that authigenic carbonate minerals (aragonite, magnesium-rich calcite, dolomite, ankerite and siderite) and iron-bearing minerals (limonite, chlorite, and biotite) were present in these carbonate samples. The carbon and oxygen isotopic values of the carbonate samples varied between -51.1‰ to -4.7‰ and -4.8‰ to 3.7‰, respectively. A negative linear correlation between carbon and oxygen isotopic compositions was found, indicating a mixture of methane-derived diagenetic (low δ13C/high 18O) carbonates and detrital origin (high δ13C/low 18O) carbonates at the OT. GeoChip analyses suggested that various metabolic activities of microorganisms, including methanogenesis, methane oxidation, sulfite oxidation, sulfate reduction, and metal biotransformations, all occurred during the formation process. On the basis of these findings, the following model for the methane cycle and seep carbonate deposit formation in the sediment column at the OT is proposed: (1) in the upper oxidizing zone, aerobic methane oxidation was the main way of methane consumption; (2) in the sulfate methane transition zone, sulfate-dependent AOM (anaerobic oxidation of methane) consumes methane, and authigenic minerals such as aragonite, magnesium-calcite, and sulfide minerals

Origin and Timing of Dauphiné Twins Using Fluid Inclusions in Quartz-Cement Fractures in Sandstones from Diagenetic Environments

NASA Astrophysics Data System (ADS)

Fall, A.; Ukar, E.; Laubach, S.

2016-12-01

Dauphiné twins in quartz are widespread in many tectonometamorphic environments. Under diagenetic temperatures (<200°C) and burial depths less than 5 km Dauphiné twins are also common in isolated fracture quartz deposits spanning between fracture walls in low-porosity quartz-cemented sandstones. The twin boundaries coincide with fracture wall-normal fluid inclusion trails. The association of Dauphiné twins and fluid inclusion trails from which temperature and possibly timing can be inferred provides a way to research mechanism and timing of twinning, and potentially the magnitude of paleostrain and stress in some diagenetic settings. Using examples from East Texas and Colorado cores, we show that twins are associated with crack-seal microstructure and fluid inclusions. Fracture wall-parallel and wall-normal inclusion trails contain coexisting aqueous and hydrocarbon gas inclusions, so homogenization temperatures of aqueous inclusions, ranging from 130°C to 159°C in the East Texas Basin, and from 162°C to 176°C in the Piceance Basin, record true trapping temperatures. Inclusions in wall-normal trails are large and irregularly shaped compared to those in wall-parallel trails, but both show similar liquid-to-vapor ratios. Trapping temperatures for wall-normal inclusion trails are usually higher than those in the wall-parallel trails. Wall-normal fluid inclusion assemblage temperatures typically match the highest temperatures of wall-parallel assemblages trapped during sequential widening, but not necessarily the most recent. In context of burial histories for these samples, this temperature pattern implies that wall-normal assemblages form at discrete times during or after crack-seal fracture widening. Stacking transmitted light images with scanning electron microscope cathodoluminescence (SEM-CL) and electron backscattered diffraction (EBSD) images demonstrates that the twin boundaries are localized along wall-normal inclusion trails. Localization in isolated

New insights on the age of the post-Urgonian marly cover of the Apt region (Vaucluse, SE France) and its implications on the demise of the North Provence carbonate platform

NASA Astrophysics Data System (ADS)

Frau, Camille; Pictet, Antoine; Spangenberg, Jorge E.; Masse, Jean-Pierre; Tendil, Anthony J.-B.; Lanteaume, Cyprien

2017-08-01

Our contribution presents an integrated litho-, bio- and chemostratigraphic study of the best-preserved outcrops of the post-Urgonian marly cover (A1 unit) of the North Provence carbonate platform. The study of the rich ammonite fauna from the Apt-Gargas area (SE Vaucluse) confirms that the A1 unit is older than previously assumed and dated to the upper (but non-uppermost) part of the lower Aptian Deshayesites forbesi Zone of the Mediterranean standard zonation. This interval is assigned to the lower part of the Roloboceras hambrovi Subzone as defined in the present contribution which is time equivalent to the spreading of the OAE 1a. Microfossil occurrences previously documented in the A1 unit are consistent with our ammonite-age calibration. Unfortunately, the curves of the carbon and oxygen stable isotopes exhibit a correlative signal probably caused by an early diagenetic overprint which questions the previous use of the C-isotope signal for precise chronostratigraphic correlation with respect to the OAE 1a excursion. The top of the A1 unit is marked by a burrowed firmground locally infilled and capped by glauconite-rich sandy marls which grade into the blue-grey muddy marls of the overlying A2 unit. The hiatus associated to this discontinuity is equivalent to the culmination of the OAE 1a, including the uppermost D. forbesi Zone (= upper R. hambrovi Subzone as herein defined) and the lower D. deshayesi Zone. The revised calibration of the post-Urgonian marl implies that the ammonite-age calibration of the North Provence carbonate platform should be revised and questions the timing and driving mechanisms of its stepwise demise.

Evaluating the Mn/Ca Ratio of Foraminiferal Calcite Determined by Flow-Through ICP-MS as a Proxy for Terrigenous Input, Upwelling, and Carbon Rain Rate

NASA Astrophysics Data System (ADS)

Klinkhammer, G. P.; Mix, A. C.; Benway, H. M.; Haley, B. A.

2004-12-01

The Mn/Ca ratio of the biogenic calcite preserved in deep-sea sediments has potential as a tracer of terrestrial input, upwelling, and carbon rain rate over geologic time scales. The basis for this potential lies in features of the Mn cycle in the oceans, which are well known. Manganese is a biogeochemically reactive element, but has a lower affinity for dissolved oxygen and organic matter than iron, making it more stable over short time scales, and less affected by speciation. Depth profiles of Mn in oligotrophic ocean waters show a sharp contrast between low concentrations in deep water (0.20 nM) and relatively high concentrations in the mixed layer (2-5 nM). Mn oxides are stable in high oxygen environments but reduced in the suboxic conditions found in the oxygen minimum zone (OMZ). This behavior makes the intermediate water to surface water concentration ratio of Mn sensitive to the intensity of the OMZ, an artifact of the carbon rain rate, and dust/river input. In sediments, suboxic dissolution is balanced by the formation of carbonate making Mn highly reactive during early diagenesis. These features of the Mn cycle in seawater make the Mn/Ca ratio of foraminifera an attractive paleoproxy, but only if the primary signature can be recovered after diagenetic alteration. Recently our laboratory developed a flow-through extraction system that gives us fresh insight into this problem by making it possible to separate mineral phases associated with the foraminiferal fraction by differences in their solubilities. This paper examines foraminiferal Mn/Ca ratios in core tops and down core records from the eastern equatorial Pacific determined with this new technique. We access the potential of flow-through Mn/Ca by comparing its record to those of Mg/Ca and stable isotopes.

Depositional environments and cyclicity of the Early Ordovician carbonate ramp in the western Tarim Basin (NW China)

NASA Astrophysics Data System (ADS)

Guo, Chuan; Chen, Daizhao; Song, Yafang; Zhou, Xiqiang; Ding, Yi; Zhang, Gongjing

2018-06-01

During the Early Ordovician, the Tarim Basin (NW China) was mainly occupied by an extensive shallow-water carbonate platform, on which a carbonate ramp system was developed in the Bachu-Keping area of the western part of the basin. Three well-exposed typical outcrop sections of the Lower Ordovician Penglaiba Formation were investigated in order to identify the depositional facies and to clarify origins of meter-scale cycles and depositional sequences, thereby the platform evolution. Thirteen lithofacies are identified and further grouped into three depositional facies (associations): peritidal, restricted and open-marine subtidal facies. These lithofacies are vertically stacked into meter-scale, shallowing-upward peritidal and subtidal cycles. The peritidal cycles are mainly distributed in the lower and uppermost parts of the Penglaiba Formation deposited in the inner-middle ramp, and commonly start with shallow subtidal to intertidal facies followed by inter- to supratidal facies. In contrast, the subtidal cycles occur throughout the formation mostly in the middle-outer ramp and are dominated by shallow to relatively deep (i.e., intermediate) subtidal facies. The dominance of asymmetrical and incomplete cycles suggests a dominant control of Earth's orbital forcing on the cyclic deposition on the platform. On the basis of vertical facies and cycle stacking patterns, and accommodation changes illustrated by the Fischer plots from all studied sections, five third-order depositional sequences are recognized in the Penglaiba Formation. Individual sequences comprise a lower transgressive part and an upper regressive one. In shallow-water depositional environments, the transgressive packages are dominated by thicker-than-average subtidal cycles, indicating an increase in accommodation space, whereas regressive parts are mainly represented by thinner-than-average peritidal and subtidal cycles, denoting a decrease in accommodation space. In contrast, in intermediate to

Cool episode and platform demise in the Early Aptian: New insights on the links between climate and carbonate production

NASA Astrophysics Data System (ADS)

Bonin, Aurélie; Pucéat, Emmanuelle; Vennin, Emmanuelle; Mattioli, Emanuela; Aurell, Marcos; Joachimski, Michael; Barbarin, Nicolas; Laffont, Rémi

2016-01-01

The Early Aptian encountered several crises in neritic and pelagic carbonate production, major perturbations in the carbon cycle, and an oceanic anoxic event (OAE1a). Yet the causal links between these perturbations and climate changes remain poorly understood, partly because temperature records spanning the Early Aptian interval are still scant. We present new δ18O data from well-preserved bivalves from a carbonate platform of the Galve subbasin (Spain) that document a major cooling event postdating most of OAE1a. Our data show that cooling postdates the global platform demise and cannot have triggered this event that occurred during the warmest interval. The warmest temperatures coincide with the time equivalent of OAE1a and with platform biotic assemblages dominated by microbialites at Aliaga as well as on other Tethyan platforms. Coral-dominated assemblages then replace microbialites during the subsequent cooling. Nannoconids are absent during most of the time equivalent of the OAE1a, probably related to the well-known crisis affecting this group. Yet they present a transient recovery in the upper part of this interval with an increase in both size and abundance during the cool interval portion that postdates OAE1a. An evolution toward cooler and drier climatic conditions may have induced the regional change from microbial to coral assemblages as well as nannoconids size and abundance increase by limiting continent-derived input of nutrients.

Seep carbonates and chemosynthetic coral communities in the Early Paleocene alpine accretionary wedge: evidences from the Bocco Shale (Internal Liguride ophiolitic sequence, Northern Apennine, Italy)

NASA Astrophysics Data System (ADS)

Pandolfi, Luca; Boschi, Chiara; Luvisi, Edoardo; Alessandro, Ellero; Marroni, Michele; Meneghini, Francesca

2014-05-01

In Northern Apennines, the Internal Liguride units are characterized by an ophiolite sequence that represents the stratigraphic base of a Late Jurassic-Early Paleocene sedimentary cover. The Bocco Shale represents the youngest deposit recognized in the sedimentary cover of the ophiolite sequence, sedimented just before the inception of subduction-related deformation history. The Bocco Shale has been interpreted as a fossil example of deposits related to the frontal tectonic erosion of the alpine accretionary wedge slope. The frontal tectonic erosion resulted in a large removal of material from the accretionary wedge front reworked as debris flows and slide deposits sedimented on the lower plate above the trench deposits. These trench-slope deposits may have been successively deformed and metamorphosed during the following accretion processes. The frontal tectonic erosion can be envisaged as a common process during the convergence-related evolution of the Ligure-Piemontese oceanic basin in the Late Cretaceous-Early Tertiary time span. In the uppermost Internal Liguride tectonic unit (Portello Unit of Pandolfi and Marroni. 1997), that crops-out in Trebbia Valley, several isolated blocks of authigenic carbonates, unidentificated corals and intrabasinal carbonatic arenites have been recognized inside the fine-grained sediments that dominate the Early Paleocene Lavagnola Fm. (cfr. Bocco Shale Auctt.). The preliminary data on stable isotopes from blocks of authigenic carbonates (up to 1 m thick and 3 m across) and associated corals archive a methane signatures in their depleted carbon isotope pattern (up to δ13C -30‰ PDB) and suggest the presence of chemosynthetic paleocommunities. The seep-carbonates recognized at the top of Internal Liguride succession (cfr. Bocco Shale Auctt.) occur predominantly as blocks in very thick mudstone-dominated deposits and probably developed in an environment dominated by the expulsion of large volume of cold methane-bearing fluids

The effects of diagenesis and dolomitization on Ca and Mg isotopes in marine platform carbonates: Implications for the geochemical cycles of Ca and Mg

NASA Astrophysics Data System (ADS)

Fantle, Matthew S.; Higgins, John

2014-10-01

The Ca, Mg, O, and C isotopic and trace elemental compositions of marine limestones and dolostones from ODP Site 1196A, which range in depth (∼58 to 627 mbsf) and in depositional age (∼5 and 23 Ma), are presented. The objectives of the study are to explore the potential for non-traditional isotope systems to fingerprint diagenesis, to quantify the extent to which geochemical proxies are altered during diagenesis, and to investigate the importance of diagenesis within the global Ca and Mg geochemical cycles. The data suggest that Ca, which has a relatively high solid to fluid mass ratio, can be isotopically altered during diagenesis. In addition, the alteration of Ca correlates with the alteration of Mg in such a way that both can serve as useful tools for deciphering diagenesis in ancient rocks. Bulk carbonate δ44Ca values vary between 0.60 and 1.31‰ (SRM-915a scale); the average limestone δ44Ca is 0.97 ± 0.24‰ (1SD), identical within error to the average dolostone (1.03 ± 0.15 1SD ‰). Magnesium isotopic compositions (δ26Mg, DSM-3 scale) range between -2.59‰ and -3.91‰, and limestones (-3.60 ± 0.25‰) and dolostones (-2.68 ± 0.07‰) are isotopically distinct. Carbon isotopic compositions (δ13C, PDB scale) vary between 0.86‰ and 2.47‰, with average limestone (1.96 ± 0.31‰) marginally offset relative to average dolostone (1.68 ± 0.57‰). The oxygen isotopic compositions (δ18O, PDB scale) of limestones (-1.22 ± 0.94‰) are substantially lower than the dolostones measured (2.72 ± 1.07‰). The isotopic data from 1196A suggest distinct and coherent trends in isotopic and elemental compositions that are interpreted in terms of diagenetic trajectories. Numerical modeling supports the contention that such trends can be interpreted as diagenetic, and suggests that the appropriate distribution coefficient (KMg) associated with limestone diagenesis is ∼1 to 5 × 10-3, distinctly lower than those values (>0.015) reported in laboratory

The Geologic Signature of Anaerobic Oxidation of Methane (Invited)

NASA Astrophysics Data System (ADS)

Ussler, W.; Paull, C. K.

2010-12-01

authigenic carbonates may be appear in the geologic record. Based on the stochiometry of the AOM reaction [CH4 + SO4= → HCO3- + HS-], HCO3- and HS- should occur in a 1:1 molar ratio in sediment pore water. Methane-derived carbonates are common in methane-rich sediments and methane venting areas, however the corresponding amount of HS- precipitated as iron monosulfides (FeS) is not. The prediction, based on their molecular weights and densities, is that the volume ratio of authigenic carbonate to FeS should be 2:1. However, in anoxic Black Sea sediments, where a high degree of preservation would be expected, the authigenic carbonate to FeS ratio is ~50:1. Massive accumulations of FeS associated with authigenic carbonates have not been observed. There are a number of fates for the HS- produced by AOM: (1) HS- is oxidized in situ adding sulfate back to the pore water pool; (2) HS- selectively diffuses (relative to HCO3-) towards the seafloor and is oxidized in the benthic water column; or (3) FeS precipitates, but is oxidized when authigenic carbonates are exhumed leaving a vuggy texture. None of these explanations are entirely satisfactory for the early diagenetic loss of HS- from sediments, but strongly suggest that massive accumulations of FeS derived from AOM will not be found in the geologic record.

Sulphurisation of homohopanoids: Effects on carbon number distribution, speciation, and 22 S/22 R epimer ratios

NASA Astrophysics Data System (ADS)

Köster, Jürgen; Van Kaam-Peters, Heidy M. E.; Koopmans, Martin P.; De Leeuw, Jan W.; Sinninghe Damsté, Jaap S.

1997-06-01

Sulphurisation has been recognised as the most important diagenetic pathway acting on hopanoids in the organic-rich limestones, marlstone, and dolomite investigated. The qualitative and quantitative analysis of free and S-bound hopanoid moieties revealed that the incorporation of sulphur has a major impact on the carbon number distribution, the speciation and on the 22 S/(22S+22 R) ratio of the hopanoids. C 35 carbon skeletons are preferentially preserved by sulphur incorporation at the end of the side chain. Hopanoid sulphides, with the sulphur atom attached to one carbon atom of ring D or E and to one carbon atom of the side chain (condensed-type), are predominantly formed from precursors with a partially degraded side chain. In all samples the degree of sulphurisation of hopanoids increases with increasing carbon number. The carbon skeleton speciation changes with maturation in favour of hopanoid thiophenes, which are evidently the most stable hopanoid sulphur compounds, and hopanes. Hopanes are mainly formed via a sulphurisation/desulphurisation pathway and increase in concentration with maturity. Their original carbon number distribution is strongly shifted towards the lower homologues. With increasing maturity only a slight dominance of the C 35 members emerges. The most abundant series of condensed-type hopanoid sulphides have a 22R homohopane carbon skeleton that is not isomerised during maturation. The generation of hopanes from these condensed-type hopanoid sulphides during maturation leads to 22 S/(22S+22 R) ratios which increase with carbon number (e.g., from about 0.2 for C 31 to 0.5 for C 35 homologues). Data acquired from the sedimentary rock samples are supported by those obtained from artificial maturation experiments of a limestone by hydrous pyrolysis at different temperatures. The data show that generally accepted molecular maturation parameters have to be applied with caution.

Geochemistry of Early Frasnian (Late Devonian) pyrite-ammonoid level in the Kostomłoty Basin, Poland, and a new proxy parameter for assessing the relative amount of syngenetic and diagenetic pyrite

NASA Astrophysics Data System (ADS)

Pisarzowska, Agnieszka; Berner, Zsolt A.; Racki, Grzegorz

2014-07-01

Pyrite geochemistry (isotope and trace element composition, degree of pyritization, S/Corg ratio) was used in context of selected lithogeochemical parameters (major and trace elements, including sulphur, organic carbon, and δ13C of carbonate carbon) to constrain fluctuations in depositional conditions during the Early to Middle Frasnian carbon isotopic perturbation (punctata Event) in the Kostomłoty Basin, Poland. Based on the ratio between the sum of oxyanionic elements and transition metals in pyrite, a new proxy parameter (index of syngenetic pyrite, ISYP) is proposed for assessing the relative amount of syngenetic pyrite in a sample. The distribution of the ISYP along the Kostomłoty - Małe Górki section (upper Szydłówek to the basal Kostomłoty beds) is in concert with conclusions inferred from paleoecologic data and other geochemical parameters (degree of pyritization, S/Corg, δ34Spyrite). According to these, the lower segment of the Szydłówek Beds was deposited in a normally oxygenated environment, but undergoing increasing primary productivity in surface water, as indicated by an increase in δ13Ccarb and in Cu/Zr ratio in bulk rock, which triggered the periodic deposition of sediments slightly enriched in organic matter, notably within the pyrite-ammonoid level (= Goniatite Level). Fluctuating, but in general high S/Corg ratios, DOPR values and ISYP values suggest that during this time - against the background of a generally dysoxic environment - shorter or longer lasting episodes of more restricted (anoxic and possibly even euxinic) bottom water conditions developed. Low sedimentation rates enabled a continuous and practically unlimited supply of sulphate during bacterial sulphate reduction (BSR), which in turn led to a strong depletion of pyrite sulphur in 34S in this interval (constantly around -29‰). In contrast, below and above the Goniatite Level, higher δ34S values (up to + 3‰), are compatible with closed system conditions and higher

Planktic foraminiferal response to early Eocene carbon cycle perturbations in the southeast Atlantic Ocean (ODP Site 1263)

NASA Astrophysics Data System (ADS)

Luciani, Valeria; D'Onofrio, Roberta; Dickens, Gerald R.; Wade, Bridget S.

2017-11-01

At low latitude locations in the northern hemisphere, striking changes in the relative abundances and diversity of the two dominant planktic foraminifera genera, Morozovella and Acarinina, are known to have occurred close to the Early Eocene Climatic Optimum (EECO; 49-53 Ma). Lower Eocene carbonate-rich sediments at Ocean Drilling Program (ODP) Site 1263 were deposited on a bathymetric high (Walvis Ridge) at 40° S, and afford an opportunity to examine such planktic foraminiferal assemblage changes in a temperate southern hemisphere setting. We present here quantified counts of early Eocene planktic foraminiferal assemblages from Hole 1263B, along with bulk sediment stable isotope analyses and proxy measurements for carbonate dissolution. The bulk sediment δ13C record at Site 1263 resembles similar records generated elsewhere, such that known and inferred hyperthermal events can be readily identified. Although some carbonate dissolution has occurred, the well-preserved planktic foraminiferal assemblages mostly represent primary changes in environmental conditions. Our results document the permanent decrease in Morozovella abundance and increase in Acarinina abundance at the beginning of the EECO, although this switch occurred 165 kyr after that at low-latitude northern hemisphere locations. This suggests that unfavourable environmental conditions for morozovellids at the start of the EECO, such as sustained passage of a temperature threshold or other changes in surface waters, occurred at lower latitudes first. The remarkable turnover from Morozovella to Acarinina was widely geographically widespread, although the causal mechanism remains elusive. In addition, at Site 1263, we document the virtual disappearance within the EECO of the biserial chiloguembelinids, commonly considered as inhabiting intermediate water depths, and a reduction in abundance of the thermocline-dwelling subbotinids. We interpret these changes as signals of subsurface water properties

Complex resistivity spectra in relation to multiscale pore geometry in carbonates and mixed-siliciclastic rocks

NASA Astrophysics Data System (ADS)

Norbisrath, Jan Henrik

Carbonate rocks are known to have complex and heterogeneous pore structures, which result from their biogenic origin and strong affinity for diagenetic processes that change their pore structure after burial. The combination of sheer endless variations of precursor biogenic material, depositional environments, and diagenetic effects results in rocks that are interesting to study but intricate to understand. Many schemes to categorize the diversity of carbonate rocks are in use today; most are based on the macropore structure and qualitative thin-section analysis. Many studies, however, acknowledge that micropores have a significant influence on the macroscopic petrophysical rock properties, which are essential to determine reservoir quality. Micropores are, by definition, smaller than the thickness of a thin-section (< 30 microm) and hence cannot be quantified with conventional methods. For their analysis, scanning electron microscopy (SEM) is the logical next step. The challenge is that mechanical polishing methods produce excessive surface roughness at micron scale; the resulting surfaces are not suited for quantification of micropores. Advances in broad-ion-beam (BIB) milling enable preparation of nanometer-precision 2D sections that are suited for quantitative analysis with the SEM. To accomplish the objective of accurate quantification of carbonate micropores, part one of this dissertation employs the BIB-SEM technique on a variety of carbonate rock samples and finds four major carbonate microporosity types: (1) small intercrystalline, (2) large inter-crystalline, (3) intercement, and (4) micromoldic. Each microporosity type shows a distinct capacity to conduct electrical charge, which largely controls the magnitude and range of cementation factors (m) in rocks with such microporosity type. The BIB-SEM method is also used on a dataset of mixed carbonate-siliciclastic (mudrock) samples with high kerogen and pyrite content. Results show that the nanopore

A study of ignition of metal impregnated carbons: the influence of oxygen content in the activated carbon matrix.

PubMed

van der Merwe, M M; Bandosz, T J

2005-02-01

A study of the reason for the early ignition of coconut-based impregnated carbon in comparison with the peat-based impregnated carbon was conducted. The surface features of carbons were evaluated using various physicochemical methods. The metal analysis of the initial carbon indicated that the content of potassium was higher in the coconut-based carbon. The surface functional group analysis revealed the presence of similar surface species; however, the peat-based carbon was more acidic in its chemical nature. Since the oxygen content was higher in the peat-based carbon, the early ignition of the coconut-based material was attributed to its higher affinity to chemisorb oxygen, which leads to exothermic effects. This conclusion was confirmed by performing oxidation of coconut-based carbon prior to impregnation. This process increased the ignition temperature for Cu/Cr impregnated coconut-based material from 186 to 289 degrees C and for the Cu/Zn/Mo impregnated carbon from 235 to 324 degrees C.

Availability of free oxygen in deep bottom water of some Archean-Early Paleoproterozoic ocean basins as derived from iron formation facies analyses

NASA Astrophysics Data System (ADS)

Beukes, N. J.; Smith, A.

2013-12-01

Archean to Early Paleoproterozoic ocean basins are commonly, although not exclusively, depicted as rather static systems; either permanently stratified with shallow mixed oxygenated water overlying anoxic deep water or with a totally anoxic water column. The anoxic water columns are considered enriched in dissolved ferrous iron derived from hydrothermal plume activity. These sourced deposition of iron formations through precipitation of mainly ferrihydrite via reaction with free oxygen in the stratified model or anaerobic iron oxidizing photoautotrophs in the anoxic model. However, both these models face a simple basic problem if detailed facies reconstructions of deepwater microbanded iron formations (MIFs) are considered. In such MIFs it is common that the deepest water and most distal facies is hematite rich followed shoreward by magnetite, iron silicate and siderite facies iron formation. Examples of such facies relations are known from jaspilitic iron formation of the ~3,2 Ga Fig Tree Group (Barberton Mountainland), ~ 2,95 Ga iron formations of the Witwatersrand-Mozaan basin and the ~2,5 Ga Kuruman Iron Formation, Transvaal Supergroup, South Africa. Facies relations of these MIFs with associated siliciclastics or carbonates also indicate that the upper water columns of the basins, down to below wave base, were depleted in iron favoring anoxic-oxic stratification rather than total anoxia. In the MIFs it can be shown that hematite in the distal facies represents the earliest formed diagenetic mineral; most likely crystallized from primary ferrihydrite. The problem is one of how ferrihydrite could have been preserved on the ocean floor if it was in direct contact with reducing ferrous deep bottom water. Rather dissolved ferrous iron would have reacted with ferrihydrite to form diagenetic magnetite. This dilemma is resolved if in the area of deepwater hematite MIF deposition, the anoxic ferrous iron enriched plume was detached from the basin floor due to buoyancy

Paragenesis of the Morgan Creek Limestone, Late Cambrian, central Texas: Constraints on the formation of glauconite

NASA Astrophysics Data System (ADS)

Chafetz, Henry S.

2007-06-01

Deposition of the Morgan Creek Limestone, a member of the Cambrian Wilberns Formation, began a few meters above a disconformable surface and displays abundant indicators of accumulation in shallow marine to tidal flat environments. These indicators include: intercalation of a lithologic variety of thin beds (e.g. biosparites, biomicrites, oosparites, intrasparites), which display rapid vertical and lateral lithologic changes, numerous stromatolitic horizons, channels filled with graded oosparites and intrasparites that cut through micrite accumulations, and finely laminated (non-burrowed) siltstones. Glauconite is a ubiquitous minor constituent throughout in the form of pellets, replaced skeletal material and mica books, and, most informatively, as an authigenic precipitate in the form of fibroradiating rims on carbonate allochems and siliciclastic grains. Fibroradiating glauconite rims were disrupted and pushed away from the pelmatozoan nuclei on which they precipitated. Combined sedimentological and paragenetic constraints indicate that the glauconite was the earliest diagenetic event to affect these sediments and occurred essentially at the sediment-water interface within these relatively high-energy, shallow marine deposits. Precipitation of glauconite was closely followed by precipitation of carbonate cement as well as dissolution of aragonitic constituents. Later diagenetic processes included selective dolomitization and silicification. In modern seas glauconite is reported to form at and below mid-shelf water depths. Thus, the constraints pertaining to the origin of modern glauconite are not valid for Late Cambrian deposits and probably are also not applicable for Late Cretaceous through Early Paleogene glauconites.

Evidence for only minor contributions from bacteria to sedimentary organic carbon

NASA Technical Reports Server (NTRS)

Hartgers, W. A.; Sinninghe Damste, J. S.; Requejo, A. G.; Allan, J.; Hayes, J. M.; de Leeuw, J. W.

1994-01-01

Because their molecular signatures are often prominent in extracts of sediments, bacteria are thought to be important contributors to petroleum source beds. It has been shown recently, however, that abundances of biomarkers do not always reflect relative contributions to sedimentary organic carbon (Corg). The contribution of photosynthetic green sulphur bacteria to sediments can be assessed effectively because the diagenetic products of distinctive carotenoids from these organisms occur widely and their biomass is isotopically labelled, being enriched in 13C. We show here that, although sediments and oils from the Western Canada and Williston basins contain prominent biomarkers of photosynthetic bacteria, the absence of 13C enrichment in the total Corg requires that the bacterial contribution is in fact minimal. Although the importance of bacterial reworking of sedimentary debris cannot be doubted, we argue that our findings, when considered in conjunction with those from other settings, suggest that bacterial biomass may commonly represent only a minor component of total Corg in carbonaceous rocks.

Are glendonites reliable indicators of cold conditions? Evidence from the Lower Cretaceous of Spitsbergen

NASA Astrophysics Data System (ADS)

Vickers, Madeleine; Price, Gregory; Watkinson, Matthew; Jerrett, Rhodri

2017-04-01

Glendonites are pseudomorphs after the mineral ikaite, and have been found in marine sediments throughout geological time. Ikaite is a metastable, hydrated form of calcium carbonate, which is only stable under specific conditions: between -2 and +5 °C, and with high alkalinity and phosphate concentrations. Glendonites are often associated with cold climates due to the strong temperature control on ikaite growth, and the coincidence in the geological record with episodes of global cooling. Glendonites are found in the Lower Cretaceous succession in Spitsbergen. During the Early Cretaceous, Spitsbergen was at a palaeolatitude of 60°N, and was part of a shallow epicontinental sea that formed during the Mesozoic as Atlantic rifting propagated northwards. Though the Early Cretaceous was generally characterised by greenhouse climate conditions, episodic cold snaps occurred during the Valanginian (the "Weissert Event") and during Aptian-Albian. Using high resolution carbon-isotope stratigraphy, we show that the first occurrences of glendonites are in the upper Lower Hauterivian and in the very upper Upper Hauterivian, stratigraphically higher than the Valanginian cooling event. Glendonites are also found in horizons in the Upper Aptian, coincident with the Aptian-Albian cold snap. Petrological analysis of the glendonite structure reveals differences between the Hauterivian and Aptian glendonites, with evidence for multiple diagenetic phases of growth in the Hauterivian glendonites, suggesting oscillating chemical conditions. This evidence suggests that local environmental conditions may have a stronger control on glendonite formation and preservation than global climate. We present a new model for ikaite growth and slow transformation to glendonite in marine sediments, which points to a more complex suite of diagenetic transformations than previously modelled. Furthermore, we critically assess whether such pseudomorphs after marine sedimentary ikaite may be indicators

Thallium isotope evidence for a permanent increase in marine organic carbon export in the early Eocene

USGS Publications Warehouse

Nielsen, S.G.; Mar-Gerrison, S.; Gannoun, A.; LaRowe, D.; Klemm, V.; Halliday, A.N.; Burton, K.W.; Hein, J.R.

2009-01-01

The first high resolution thallium (Tl) isotope records in two ferromanganese crusts (Fe-Mn crusts), CD29 and D11 from the Pacific Ocean are presented. The crusts record pronounced but systematic changes in 205Tl/203Tl that are unlikely to reflect diagenetic overprinting or changes in isotope fractionation between seawater and Fe-Mn crusts. It appears more likely that the Fe-Mn crusts track the Tl isotope composition of seawater over time. The present-day oceanic residence time of Tl is estimated to be about 20,000??yr, such that the isotopic composition should reflect ocean-wide events. New and published Os isotope data are used to construct age models for these crusts that are consistent with each other and significantly different from previous age models. Application of these age models reveals that the Tl isotope composition of seawater changed systematically between ~ 55??Ma and ~ 45??Ma. Using a simple box model it is shown that the present day Tl isotope composition of seawater depends almost exclusively on the ratio between the two principal output fluxes of marine Tl. These fluxes are the rate of removal of Tl from seawater via scavenging by authigenic Fe-Mn oxyhydroxide precipitation and the uptake rate of Tl during low temperature alteration of oceanic crust. It is highly unlikely that the latter has changed greatly. Therefore, assuming that the marine Tl budget has also not changed significantly during the Cenozoic, the low 205Tl/203Tl during the Paleocene is best explained by a more than four-fold higher sequestration of Tl by Fe-Mn oxyhydroxides compared with at the present day. The calculated Cenozoic Tl isotopic seawater curve displays a striking similarity to that of S, providing evidence that both systems may have responded to the same change in the marine environment. A plausible explanation is a marked and permanent increase in organic carbon export from ~ 55??Ma to ~ 45??Ma, which led to higher pyrite burial rates and a significantly reduced

Compositional variations and differential diagenesis in Miocene turbidites from the western coast of Mallorca (Balearic Islands, Spain)

NASA Astrophysics Data System (ADS)

Felder, Sonja; Westphal, Hildegard; Munnecke, Axel; Mateu Vicens, Guillem

2010-05-01

Compositional variations and differential diagenesis in Miocene turbidites from the western coast of Mallorca (Balearic Islands, Spain) Sonja Felder (1), Hildegard Westphal (1), Axel Munnecke (2), Guillem Mateu Vicens (1,3) (1) MARUM and Department of Geosciences, Universität Bremen, Leobener Straße, 28359 Bremen, Germany (2) GeoZentrum Nordbayern, Universität Erlangen-Nürnberg, Loewenichstr. 28, 91054 Erlangen, Germany (3) Dipartimento di Scienze della Terra, Università di Roma "La Sapienza", Ple Aldo 7 Moro, 5. I-00185 Roma, Italy Cyclic alternations of limestone and marl beds crop out along the western coast of the Island of Mallorca. This Miocene succession is traditionally interpreted to represent more weathering-resistant turbidites interlayered by softer hemipelagic background sediment. However, the cementation patterns that dominate the appearance of the outcrop do not always consistently follow sedimentary layering; locally the cemented beds are systematically oblique to the sedimentary layers. Compositional studies demonstrate that differences in non-carbonate fraction, carbonate concentration and fossil content (e.g. foraminiferal assemblages) trace sedimentary bedding, regardless the diagenetic style. Limestone versus marl lithology, in contrast, is defined by the diagenetic style, tight cementation by calcite cements in the limestones versus low porosity and compaction in the marls. The reason for this striking pattern of diagenetic bedding cross-cutting sedimentary layers is assumed to be related to tectonic fracturing, opening pathways for diagenetic fluids. This example cautions the straight-forward interpretation of limestone-marl alternations as direct witnesses of environmental or climatic variations.

Influence of AOM on iron-sulfur-carbon systematics in marine sediment: A study from Krishna-Godavari basin, Bay of Bengal

NASA Astrophysics Data System (ADS)

Carvalho, M. A.

2017-12-01

Sedimentary diagenetic processes play key role in global sulfur-iron-carbon cycle. Microbially driven organoclastic sulfate reduction and anaerobic oxidation of methane (AOM) pathways are responsible for sulfate reduction in marine sediments. Concomitant H2S production and iron sulfide precipitation lead to Fe-sulfide burial in the sediments. Intra/intermolecular organic bound sulfur is also another major sink of global sulfur burial. In the present study, we have investigated the sulfidisation process in a core from Krishna-Godavari (K-G) basin, Bay of Bengal. K-G basin is well known for gas hydrate deposits and methane enrichment within 100-120 mbsf. Previous work from K-G basin has shown tell-tale evidence of paleo episodic- methane expulsion events and formation of authigenic carbonate crust at or above the sea floor1. Our study was carried out on a core MD-161-15 (water depth of 983 m and Lat. =16° 00.5700' N;Long. = 82° 03.4502' E) recovered on board R/V Marion Dufrense). The pyrite content in the core (measured as chromium reducible sulfur: CRS) range from 0.003 to 1.1 wt%. The reactive content (FeTR = FeOx + FeD + FeCRS) range from 0.9 to 3.5 wt%, where FeOX, FeD and FeCRS represents oxalate extractable (magnetite), buffered dithionite extractable (ferrihydrite, lepidocrocite, goethite, hematite) and boiling CrCl2 (in 6N HCl) extractable (Pyrite: FeS2) iron respectively. The δ34SCRS range from -49 to +16.7 ‰ VCDT and show good positive correlation with FeTR. Presence of highly 13C depleted authigenic carbonate in the sediments within 1600-3000 mbsf indicate influence of AOM and possible methane seepage2. The δ34SCRS profile show marked 34S depletion trend within the top 1012 mbsf. Below this depth, δ34SCRS values show steadily increasing trend superimposed by zones of sharp enrichment/ depletion of 34S. The 34S enrichment trend may attributed to late diagenetic pyritization from 34S enriched H2S produced from residual pore water sulfate via AOM

Influence of a major exposure surface on the development of microporous micritic limestones - Example of the Upper Mishrif Formation (Cenomanian) of the Middle East

NASA Astrophysics Data System (ADS)

Deville de Periere, M.; Durlet, C.; Vennin, E.; Caline, B.; Boichard, R.; Meyer, A.

2017-05-01

Microporous platform top limestones of the Cenomanian Mishrif Formation (offshore Qatar) were studied in order to investigate the diagenetic processes associated with the top-Mishrif subaerial unconformity and its influence on the development of microporosity in underlying carbonates. Petrographical and stable isotope results indicate that complex diagenetic changes occurred during subaerial exposure of the Mishrif Formation, including pervasive dissolution and meteoric cementation, as well as neomorphism of the micritic matrix. Micrites at the top of the Mishrif Formation are coarse (i.e. > 2 μm), sub-rounded and very dull luminescent under cathodoluminescence. In this uppermost part of the studied interval, the limestone matrix first underwent dissolution of unstable grains in the vadose zone, with subsequent precipitation of low-magnesium calcite (LMC) overgrowths within an oxidising phreatic setting. This process explains the poor luminescence of the micrite crystals and their relatively coarse crystallometry which results in the present day in relatively good reservoir properties. δ13C ratios within the microporous limestones are negative (up to - 4‰ V-PDB) due to the incorporation of isotopically light carbon derived from palaeosols which developed during exposure. By contrast, fine (i.e. < 2 μm), polyhedral and bright luminescent micritic matrix with higher δ13C values (up to + 4‰ V-PDB) and lower permeability are dominant within the underlying carbonate interval. These fine micrites are likely to be the product of early neomorphic recrystallisation in the lowermost part of the palaeo-aquifer associated with the Top-Mishrif Unconformity, and were precipitated from meteoric or mixed dysoxic waters which were slightly supersaturated with respect to calcite.

Isotopic evidence for organic matter oxidation by manganese reduction in the formation of stratiform manganese carbonate ore

USGS Publications Warehouse

Okita, P.M.; Maynard, J.B.; Spiker, E. C.; Force, E.R.

1988-01-01

Unlike other marine-sedimentary manganese ore deposits, which are largely composed of manganese oxides, the primary ore at Molango (Hidalgo State, Mexico) is exclusively manganese carbonate (rhodochrosite, Mn-calcite, kutnahorite). Stable isotope studies of the carbonates from Molango provide critical new information relevant to the controversy over syngenetic and diagenetic models of stratiform manganese deposit formation. Negative ??13C values for carbonates from mineralized zones at Molango are strongly correlated with manganese content both on a whole rock scale and by mineral species. Whole rock ??13C data fall into three groups: high-grade ore = -16.4 to -11.5%.; manganese-rich, sub-ore-grade = -5.2 to 0%.; and unmineralized carbonates = 0 to +2.5%. (PDB). ??18O data show considerable overlap in values among the three groups: +4.8 to -2.8, -5.4 to -0.3%., and -7.4 to +6.2 (PDB), respectively. Isotopic data for individual co-existing minerals suggest a similar separation of ??13C values: ??13C values from calcite range from -1.1 to +0.7%. (PDB), whereas values from rhodochrosite are very negative, -12.9 to -5.5%., and values from kutnahorite or Mn-calcite are intermediate between calcite and rhodochrosite. 13C data are interpreted to indicate that calcite (i.e. unmineralized carbonate) formed from a normal marine carbon reservoir. However, 13C data for the manganese-bearing carbonates suggest a mixed seawater and organic source of carbon. The presence of only trace amounts of pyrite suggests sulfate reduction may have played a minor part in oxidizing organic matter. It is possible that manganese reduction was the predominant reaction that oxidized organic matter and that it released organic-derived CO2 to produce negative ??13C values and manganese carbonate mineralization. ?? 1988.

CHARACTERIZATION OF SANDSTONE RESERVOIRS FOR ENHANCED OIL RECOVERY: THE PERMIAN UPPER MINNELUSA FORMATION, POWDER RIVER BASIN, WYOMING.

USGS Publications Warehouse

Schenk, C.J.; Schmoker, J.W.; Scheffler, J.M.

1986-01-01

Upper Minnelusa sandstones form a complex group of reservoirs because of variations in regional setting, sedimentology, and diagenetic alteration. Structural lineaments separate the reservoirs into northern and southern zones. Production in the north is from a single pay sand, and in the south from multi-pay sands due to differential erosion on top of the Upper Minnelusa. The intercalation of eolian dune, interdune, and sabkha sandstones with marine sandstones, carbonates, and anhydrites results in significant reservoir heterogeneity. Diagenetic alterations further enhance heterogeneity, because the degree of cementation and dissolution is partly facies-related.

Carbonate Platform Development and Stromatolite Morphogenesis: Constraints on Environmental and Biological Evolution

NASA Technical Reports Server (NTRS)

Grotzinger, John P.

2002-01-01

Work this past year has focused on the globally significant events of faunal turnover, tectonic reorganization, and biogeochemical change that closely coincided with the Precambrian-Cambrian boundary in the Sultanate oilman. Higher temporal and chronostratigraphic resolution are required in order to answer this question. Stratigraphic sections must contain fossils, volcanic rocks, and abundant carbonates with little or no diagenetic overprint. The Ara Group of the South Oman Salt Basin presents such a succession - with carbonate rocks tightly enclosed in a protective envelope of impermeable halite, these rocks have likely never exchanged with younger fluids. Our work has had two thrusts. The first pertains to the geochemistry of the Athel Formation, a deep water deposit formed at the Precambrian-Cambrian boundary which contains unique records of ocean anoxia for that time interval. This unit is important because it will enable tighter focus on the links which existed between global biogeochemical events and episodes of faunal extinction and radiation. The second direction involves a comparison of terminal Proterozoic thrombolites between Oman (subsurface) and Namibia (outcrop). These thrombolites are important not only as significant deposits of ancient microbial communities, but because they formed the key substrate for growth of the oldest calcified metazoans - Cloudina and Namacalathus.

Self-healing of early age cracks in cement-based materials by mineralization of carbonic anhydrase microorganism

PubMed Central

Qian, Chunxiang; Chen, Huaicheng; Ren, Lifu; Luo, Mian

2015-01-01

This research investigated the self-healing potential of early age cracks in cement-based materials incorporating the bacteria which can produce carbonic anhydrase. Cement-based materials specimens were pre-cracked at the age of 7, 14, 28, 60 days to study the repair ability influenced by cracking time, the width of cracks were between 0.1 and 1.0 mm to study the healing rate influenced by width of cracks. The experimental results indicated that the bacteria showed excellent repairing ability to small cracks formed at early age of 7 days, cracks below 0.4 mm was almost completely closed. The repair effect reduced with the increasing of cracking age. Cracks width influenced self-healing effectiveness significantly. The transportation of CO2and Ca2+ controlled the self-healing process. The computer simulation analyses revealed the self-healing process and mechanism of microbiologically precipitation induced by bacteria and the depth of precipitated CaCO3 could be predicted base on valid Ca2+. PMID:26583014

Geochemistry of carbon and sulfur in the 2.7 Ga stromatolitic carbonate and shale (ABDP#10 core) from Meentheena, Western Australia

NASA Astrophysics Data System (ADS)

Tomiuka, T.; Yamaguchi, K. E.

2014-12-01

Earth's surface environments about 2.7 Ga ago likely experienced drastic changes such as rapid continental growth, negative excursion of organic carbon isotopes, and positive excursion of mass-independently fractionated sulfur isotopes. Discovery of biomarkers indicating cyanobacteria, although questionable, was also claimed. The coeval shallow ocean could have contained appreciable amount of molecular O2 produced by cyanobacteria, but it has been unknown whether deep sea was oxygenated by ocean circulation. In order to unravel the shallow water environment, we obtained modern-weathering-free 2.7 Ga drilcore samples of stromatolitic carbonate and shale by Archean Biosphere Drilling Project (ABDP#10 core) in Meentheena, NE Western Australia. The purpose of this study is to extract information regarding the surface ocean chemistry by abundance (of various species) and corresponding stable isotope compositions of carbon and sulfur. Based on mass balance calculation, we obtained a much reduced fraction of organic carbon to total carbon (forg) to be 0.11 (c.f., Phanerozoic average is 0.2), suggesting that aerobic and/or anaerobic decomposition of organic matter was vigorous. The very low δ13Corg values suggest carbon recycling involving methanogenesis by methanogen (e.g., 2CH2O → CH4 + CO2) accompanied by large isotope fractionation. Generated CH4 was oxidized by methylotroph to CO2, which was reused to form organic matter by biochemical processes such as photosynthesis. Either O2 or SO42- was required to facilitate CH4 oxidation, suggesting availability of oxidized species in the 2.7 Ga shallow sea environment. Abundance of Spy with near zero δ34Spy values suggest syndepositional and/or diagenetic formation of bacteriogenic pyrite utilizing sulfate formed by oxidation of mantle-derived sulfur (δ34S ≈ 0‰). A plot of Spy vs. Corg abundance shows a trend falling between a Phanerozoic normal marine trend (Spy/Corg = 0.36) and a freshwater trend (Spy << Corg

Examining the diagenetic alteration of human bone material from a range of archaeological burial sites using nuclear microscopy

NASA Astrophysics Data System (ADS)

Elliott, T. A.; Grime, G. W.

1993-05-01

The inorganic analysis of archaeological bone material can potentially provide a wealth of information about the chronology, diet and palaeoenvironment of past populations: for example, strontium and uranium levels are used in palaeodietary and dating studies, respectively. However, the extent to which the chemical composition of bone is subject to diagenetic change during burial is open to controversy due, in part, to differences in analytical technique, bone types and burial conditions. To investigate this problem, archaeological human bone material from a number of different geological environments including Pompeii and a 12th century British ecclesiastical site, together with material from two seawater burials (The "Mary Rose" and a 6th century Mediterranean wreck) have been studied using the nuclear microprobe facility at the University of Oxford. Results using microbeam PIXE show that bone is subject to contamination from a wide range of trace elements depending on the burial conditions. Elemental maps are presented to demonstrate the distribution of trace element accumulation under different burial conditions, and the significance of this work to future trace element studies is discussed.

Distinguishing Terrestrial Organic Carbon in Marginal Sediments of East China Sea and Northern South China Sea

NASA Astrophysics Data System (ADS)

Kandasamy, Selvaraj; Lin, Baozhi; Wang, Huawei; Liu, Qianqian; Liu, Zhifei; Lou, Jiann-Yuh; Chen, Chen-Tung Arthur; Mayer, Lawrence M.

2016-04-01

Knowledge about the sources, transport pathways and behavior of terrestrial organic carbon in continental margins adjoining to large rivers has improved in recent decades, but uncertainties and complications still exist with human-influenced coastal regions in densely populated wet tropics and subtropics. In these regions, the monsoon and other episodic weather events exert strong climatic control on mineral and particulate organic matter delivery to the marginal seas. Here we investigate elemental (TOC, TN and bromine-Br) and stable carbon isotopic (δ13C) compositions of organic matter (OM) in surface sediments and short cores collected from active (SW Taiwan) and passive margin (East China Sea) settings to understand the sources of OM that buried in these settings. We used sedimentary bromine to total organic carbon (Br/TOC) ratios to apportion terrigenous from marine organic matter, and find that Br/TOC may serve as an additional, reliable proxy for sedimentary provenance in both settings. Variations in Br/TOC are consistent with other provenance indicators in responding to short-lived terrigenous inputs. Because diagenetic alteration of Br is insignificant on shorter time scales, applying Br/TOC ratios as a proxy to identify organic matter source along with carbon isotope mixing models may provide additional constraints on the quantity and transformation of terrigenous organics in continental margins. We apply this combination of approaches to land-derived organic matter in different depositional environments of East Asian marginal seas.

Early diagenesis of travertine deposits from the Tibetan Plateau - implications for 230Th/234U dating and palaeoenvironmental reconstruction

NASA Astrophysics Data System (ADS)

Wang, Zhijun; Meyer, Michael; Hoffmann, Dirk; Spötl, Christoph; Aldenderfer, Mark; Sanders, Diethard

2014-05-01

Travertine is calcium carbonate precipitated from hydrothermal springs. These terrestrial carbonate deposits can be used as high-resolution archives for reconstructing palaeoclimatic and palaeoenvironmental change and are also suitable for uranium-series disequilibrium (230Th/234U) dating. In many instances such spring deposits are associated with archaeological remains (e.g. stone artifacts and other traces of prehistoric human activity) and are therefore of interest for palaeoclimatologists and archaeologists alike. However, travertines are often affected by early diagenesis that can impact on the closed-system U-series behavior and on their geochemical signature. Hence, careful evaluation of the travertine microfabrics is required before these types of hot spring deposits can be accurately dated and used for paleoenviromental reconstruction. The Tibetan plateau hosts numerous hydrothermal spring deposits that occur along neotectonic faults. In this study, samples were collected from two archaeological travertine sites, i.e. Chusang and Tirthapuri, located in southern and western Tibet, respectively. Microscopic analysis of thin sections reveals a wide variety of crystal fabrics, including micrite, microspar and sparite, the latter can be composed of columnar or mosaic crystals, respectively. Areas where dendritic crystals are preserved are identified in our micrographs as well. Many of the Chusang and Tirthapuri travertine samples are porous. Drusy sparite is rimming most of the pore walls and a complex succession of secondary calcite phases precipitated in these pore spaces as well. The different generations of pore cement comprise micrite and sparite that can be laminated or fibrous in character and show sometimes evidence of an aragonite precursor. Detrital material like quartz, feldspar and other grains as well as humic and fulvic acids have been washed into the travertine pores too. Based on our microscopic analysis a complex growth history can be

Quantifying early 17th century changes in Chesapeake Bay estuarine carbon dynamics from James River, VA oyster geochemistry

NASA Astrophysics Data System (ADS)

Grimm, B. L.; Spero, H. J.; Harding, J. M.

2012-12-01

The first successful European colonization of North America occurred in 1607 following the arrival of English settlers at Jamestown, Virginia. Within a few decades, land use changes and clear-cutting farming practices dramatically altered the terrestrial landscape and removed the overlying canopy and stabilizing root network of the previously-dominant hardwood forests. The Eastern oyster, Crassostrea virginica, has inhabited the Chesapeake Bay since the end of the last deglaciation. During the start of the Jamestown Colony, an extensive drought (1606-1612) shifted James River salinity zones upriver, expanding the available oyster habitat to the vicinity of Jamestown. This allowed the colonists to collect and eat oysters from areas near the colony down to the river's entry into the bay, and later discard the shells in wells and trash pits that have recently been excavated. The oysters' calcium carbonate shells discovered in these deposits act as multi-year stationary recorders preserving the local environmental chemistry throughout their life until collection. Here we present δ13C, δ18O, and radiocarbon data from historical oyster shell hinge transects that encompass the time period between ~1609 and the early 1700s. Samples include shells from the 1609 Jamestown freshwater well and five additional sites, as well as modern shells collected in 2006. Because shell δ13C and radiocarbon (14C) reflect James River δ13CDIC, it is possible to document carbon source changes during this period of land use change. Our preliminary data suggest a decrease in ambient δ13CDIC of approximately 2‰ between just prior to 1609 conditions and the modern estuary. This is most likely due to an increase in isotopically light organic carbon loading into the river as water moves more rapidly through the terrestrial system. Radiocarbon reservoir ages will also be presented to better constrain carbon flow through the system during this period of disturbance. δ18O measurements from the

Lithological and Petrographic Analyses of Carbonates and Sandstones From the Southern Gulf of Mexico

NASA Astrophysics Data System (ADS)

Garcia-Avendaño, A.; Urrutia-Fucugauchi, J.

2012-04-01

We present results of sedimentological and petrological studies of drill cores from the Bay of Campeche in the southern Gulf of Mexico. Based on reports on drill cores obtained from oil exploratory wells in the Cantarell Complex located 80 kilometres offshore in the Bay of Campeche and studies related to regional geology composite simplified stratigraphic columns for offshore Campeche region have been constructed up to depths of approximately 5000 m. The stratigraphic column is formed by a thick sediment sequence of Middle Jurassic age (evaporites, Callovian), Late Jurassic (terrigenous, calcareous clays and calcareous layers), Lower Cretaceous (carbonates), Upper Cretaceous-Paleogene (calcareous breccias), Paleogene-Neogene (terrigenous-carbonates intercalations) and Quaternary (terrigenous). The core samples studied come from wells in the Sihil and Akal fields in Cantarell. Analysis of reports on lithological descriptions indicates that these wells sample dolomitized sedimentary breccias from the Upper Cretaceous-Paleocene and fine-grained sandstones from the Late Jurassic Tithonian, respectively. Based on results of petrographic studies, the texture, cementing material and porosity of the units have been documented. The thin sections for carbonates were classified based on their texture according to Dunham (1962) for carbonate rocks, classified according to their components using the ternary diagrams of Folk (1974). Percentages refer to the data presented in tables, which were obtained by point-counting technique (with a total 250). Photomicrographs of scanning electron microscope (SEM) provide magnification for easy documentation of crystalline arrangements and description of micro-porous for different types of carbonates such as dolomite, in addition to the morphology of authigenic clays. Results of these studies and previous works in the area permit characterization of diagenetic processes of the carbonate sediments in the Campeche Bay, and provide

Earth's early atmosphere as seen from carbon and nitrogen isotopic analysis of Archean sediments

NASA Technical Reports Server (NTRS)

Gibson, E. K., Jr.; Carr, L. P.; Gilmour, I.; Pillinger, C. T.

1986-01-01

The origin and evolution of the Earth's early atmosphere has long been a topic of great interest but determination of actual compositions over geologic time is a difficult problem. However, recent systematic studies of stromatolite deposits (Precambrian Paleobiology Research Group) has extended our knowledge of Archean ecosystems. It has been shown that many stromatolite deposits have undergone negligible alteration since their time of formation. The discovery of primary fluid inclusions within unaltered 3.5 b.y. old Archiean sediments and the observation that the 3.3 b.y. old Barberton cherts have remained closed to argon loss and have not been subjected to thermal metamorphism suggests that an opportunity exists for the direct measurement of the volatile constituents present at their time of formation. Of primary interest to this study was the possibility that the stromatolites and other Archean sediments might retain a vestige of the atmosphere and thus afford an indication of the variations in carbon dioxide and nitrogen isotopic compositions with time. A suite of essentially unaltered Archean stromatolites and the cherts of different ages and geologic sites have been analyzed for their trapped carbon dioxide and nitrogen compositions by the stepped combustion extraction tech nique utilizing static mass spectrometers for the isotope measurements.

Stable carbon isotopes: possible clues to early life on Mars.

PubMed

Schidlowski, M

1992-01-01

Organic and inorganic carbon in terrestrial near-surface environments are characterized by a marked difference in their 13C/12C ratios which can be traced back in the Earth's sedimentary record over almost 4 billion years. There is no doubt that the bias in favour of 12C displayed by biogenic matter derives, for the most part, from the isotope-selecting properties of the carbon-fixing enzyme (ribulose-1,5-bisphosphate carboxylase) that is operative in the principal photosynthetic pathway and promotes most of the carbon transfer from the non-living to the living realm. Postulating a universality of biological principles in analogy to the proven universality of the laws of physics and chemistry, we may expect enzymatic reactions in exobiological systems to be beset with B similar kinetic fractionation effects. Hence, the retrieval from the oldest Martian sediments of isotopic fractionations between reduced and oxidized (carbonate) carbon may substantially constrain current conjectures on the possible existence of former life on Mars.

Major early Eocene carbon cycle perturbations and changes in planktic foraminiferal assemblages from the southeast Atlantic Ocean (ODP Site 1263)

NASA Astrophysics Data System (ADS)

Luciani, Valeria; D'Onofrio, Roberta; Dickens, Gerald Roy; Wade, Bridget

2017-04-01

On a paleoclimatic perspective the early Paleogene represents one of the most interesting and dynamic intervals of the Earth's history. Present record indicates that the Earth climate system reached its Cenozoic maximum peak of global warming and probably of pCO2 during the early Eocene climatic optimum (EECO, 49-53 Ma). Superimposed to the general trend, our planet experienced short-term ( 40-200 kyr) repeated peaks in global temperatures and major changes in the carbon cycle, known as hyperthermals. Great scientific interest has been focused on the early Paleogene hyperthermal events, given the assumed similarity with the current climatic scenario. Less attention has been dedicated to the EECO long lasting perturbation of extraordinary warming thus many characters of this interval still remain largely unconstrained, especially as for the biotic response. We present here results on early Eocene planktic foraminiferal analysis from the southeast Atlantic Ocean Drilling Program (ODP) Site 1263 (Walvis Ridge, Leg 208) to explore possible relationship between changes in assemblages and carbon cycle perturbation. The time interval is of particular interest for an abrupt switch occurred at low-latitude of the northern hemisphere between two important calcifiers of the tropical-subtropical early Paleogene oceans, the genera Morozovella and Acarinina at the carbon isotopic excursion known as J event, at the EECO onset. Precisely, the relative abundance of Morozovella permanently decreased by at least half, along with a progressive decrease in the number of species. Concomitantly, Acarinina almost doubled its abundance and diversified. Site 1263 was located during the early Eocene at a latitude of 40° south therefore representing a temperate setting of southern hemisphere not yet explored for planktic foraminiferal changes. We document a permanent decrease in Morozovella abundance at the beginning of the EECO, although this decline is delayed by 165 kyr with respect to

Insights into the Processing of Carbon by Early Microbial Ecosystems

NASA Technical Reports Server (NTRS)

DesMarais, D.; Bebout, B.; Carpenter, S.; Discipulo, S.; Londry, K.; Habicht, K.; Turk, K.

2003-01-01

Interactions between Earth and the biosphere that were crucial for early biological evolution also influenced substantially the processes that circulate C between its reservoirs in the atmosphere, ocean, crust and mantle. The C-13 C-12 values of crustal carbonates and organics have recorded changes both in biological discrimination and in the relative rates of burial of organics and carbonates. A full interpretation of these patterns needs further isotopic studies of microbial ecosystems and individual anaerobes. Thus we measured carbon isotope discrimination during autotrophic and heterotrophic growth of pure cultures of sulfate-reducing bacteria and archaea (SRB and SRA). Discrimination during CO2 assimilation is significantly larger than during heterotrophic growth on lactate or acetate. SRB grown lithoautotrophically consumed less than 3% of available CO2 and exhibited substantial discrimination, as follows: Desulfobacterium autotrophicum (alpha 1.0100 to 1.0123), Desulfobacter hydrogenophilus (alpha = 0.0138), and Desulfotomuculum acetoxidans (alpha = 1.0310). Mixotrophic growth of Desulfovibrio desulfuricans on acetate and CO2 resulted in biomass with delta C-13 composition intermediate to that of the substrates. We have recently extended these experiments to include the thermophilic SRA Archeoglobus spp. Ecological forces also influence isotopic discrimination. Accordingly, we quantified the flow of C and other constituents in modern marine cyanobacterial mats, whose ancestry extends back billions of years. Such ecosystem processes shaped the biosignatures that entered sediments and atmospheres. At Guerrero Negro, BCS, Mexico, we examined mats dominated by Microcoleus (subtidal) and Lyngbya (intertidal to supratidal) cyanobacteria. During 24 hour cycles, we observed the exchange of O2 and dissolved inorganic C (DIC) between mats and the overlying water. Microcoleus mats assimilated near-equal amounts of DIC during the day as they released at night, but

Late diagenetic indicators of buried oil and gas

USGS Publications Warehouse

Donovan, Terrence J.; Dalziel, Mary C.

1977-01-01

At least three hydrocarbon seepage mechanisms are interpreted to operate over oil and gas fields. These are: (1) effusion ofh ydrocarbons through inadequate caprocks and along faults and fractures, (2) low-molecular-weight hydrocarbons dissolved in water moving vertically through capping shales as a result of a hydrodynamic or chemical potential drive, and (3) diffusion of gases dissolved in water. Combinations of these mechanisms may also occur. Seeping hydrocarbons are oxidized near the earth's surface, and the resulting carbon dioxide reacts with water producing bicarbonate ions, which combine with calcium and magnesium dissolved in ground waters to yield isotopically distinctive pore-filling carbonate cements and surface rocks. The passage of hydrocarbons and associated compounds such as hydrogen sulfide through surface rocks causes a reducing environment and consequent reduction, mobilization, and loss of iron from iron-bearing minerals commonly resulting in a discoloration. Other metals such as manganese are also mobilized and redistributed. These changes in the physical and chemical properties of surface rocks correlate with the subsurface distribution of petroleum, and potentially can be detected from both airborne and spaceborne platforms.

Origin of limestone-marlstone cycles: Astronomic forcing of organic-rich sedimentary rocks from the Cenomanian to early Coniacian of the Cretaceous Western Interior Seaway, USA

NASA Astrophysics Data System (ADS)

Eldrett, James S.; Ma, Chao; Bergman, Steven C.; Ozkan, Aysen; Minisini, Daniel; Lutz, Brendan; Jackett, Sarah-Jane; Macaulay, Calum; Kelly, Amy E.

2015-08-01

We present an integrated multidisciplinary study of limestone-marlstone couplets from a continuously cored section including parts of the upper Buda Limestone, the entire Eagle Ford Group (Boquillas Formation) and lower Austin Chalk from the Shell Iona-1 research borehole (Texas, USA), which provides a >8 million year (myr) distal, clastic sediment-starved, intrashelf basin record of the early Cenomanian to the earliest Coniacian Stages. Results show that despite variable yet minimal diagenetic overprints, several unambiguous primary environmental signals are preserved and support greater water-mass ventilation and current activity promoting increased silica/carbonate productivity during the deposition of limestone beds compared to deposition of marlstone beds which reflect greater organic matter productivity and preservation. Furthermore, our astronomical analyses demonstrate that the limestone-marlstone couplets in the Iona-1 core reflect climatic forcing driven by solar insolation resulting from integrated Milankovitch periodicities. In particular, we propose that obliquity and precession forcing on the latitudinal distribution of solar insolation may have been responsible for the observed lithological and environmental variations through the Cenomanian, Turonian and Coniacian in this mid-latitude epicontinental sea setting. Our data also suggests that rhythmic lithological alternations deposited in Greenhouse periods, in general, may simply reflect climate-driven cycles related to Earth-Sun dynamics without the need to invoke significant sea-level variations.

Sulphur and oxygen sequestration of n-C37 and n-C38 unsaturated ketones in an immature kerogen and the release of their carbon skeletons during early stages of thermal maturation

USGS Publications Warehouse

Koopmans, M.P.; Schaeffer-Reiss, C.; De Leeuw, J. W.; Lewan, M.D.; Maxwell, J.R.; Schaeffer, P.; Sinninghe, Damste J.S.

1997-01-01

Sedimentary rock from the Gessoso-solfifera Formation (Messinian) in the Vena del Gesso Basin (northern Italy) containing immature (Ro = 0.25%) S-rich organic matter was artificially matured by hydrous pyrolysis at temperatures from 160 to 330??C for 72 h to study the diagenetic fate of n-C37 and n-C38 di-and tri-unsaturated methyl and ethyl ketones (alkenones) biosynthesised by several prymnesiophyte algae. During early diagenesis, the alkenones are incorporated into the kerogen by both sulphur and oxygen cross-linking as indicated by chemical degradation experiments with the kerogen of the unheated sample. Heating at temperatures between 160 and 260??C, which still represents early stages of thermal maturation, produces large amounts (up to 1 mg/g TOC) of S-bound, O-bound, and both S-and O-bound n-C37 and n-C38 skeletons, saturated n-C37 and n-C38 methyl, ethyl, and mid-chain ketones, C37 and C38 mid-chain 2,5-di-n-alkylthiophenes, C37 and C38 1,2-di-n-alkylbenzenes, and C37 and C38 n-alkanes. With increasing thermal maturation, three forms of the n-C37 and n-C38 skeletons are relatively stable (saturated hydrocarbons, 1,2-di-n-alkylbenzenes and saturated ketones), whereas the S-and O-bound skeletons are relatively labile. These results suggest that in natural situations saturated ketones with an n-C37 and n-C38 skeleton can be expected as well as the corresponding hydrocarbons. Copyright ?? 1997 Elsevier Science Ltd.

Sulphur and oxygen sequestration of n-C 37 and n-C 38 unsaturated ketones in an immature kerogen and the release of their carbon skeletons during early stages of thermal maturation

NASA Astrophysics Data System (ADS)

Koopmans, Martin P.; Schaeffer-Reiss, Christine; de Leeuw, Jan W.; Lewan, Michael D.; Maxwell, James R.; Schaeffer, Philippe; Sinninghe Damsté, Jaap S.

1997-06-01

Sedimentary rock from the Gessoso-solfifera Formation (Messinian) in the Vena del Gesso Basin (northern Italy) containing immature ( Ro = 0.25%) S-rich organic matter was artificially matured by hydrous pyrolysis at temperatures from 160 to 330°C for 72 h to study the diagenetic fate of n-C 37 and n-C 38 di- and tri-unsaturated methyl and ethyl ketones (alkenones) biosynthesised by several prymnesiophyte algae. During early diagenesis, the alkenones are incorporated into the kerogen by both sulphur and oxygen cross-linking as indicated by chemical degradation experiments with the kerogen of the unheated sample. Heating at temperatures between 160 and 260°C, which still represents early stages of thermal maturation, produces large amounts (up to 1 mg/g TOC) of S-bound, O-bound, and both S- and O-bound n-C 37 and n-C 38 skeletons, saturated n-C 37 and n-C38 methyl, ethyl, and mid-chain ketones, C 37 and C 38 mid-chain 2,5-di- n-alkylthiophenes, C 37 and C 38 1,2-di- n-alkylbenzenes, and C 37 and C 38n-alkanes. With increasing thermal maturation, three forms of the n-C 37 and n-C 38 skeletons are relatively stable (saturated hydrocarbons, 1,2-di- n-alkylbenzenes and saturated ketones), whereas the S- and O-bound skeletons are relatively labile. These results suggest that in natural situations saturated ketones with an n-C 37 and n-C 38 skeleton can be expected as well as the corresponding hydrocarbons.

Influence of contemporary carbon originating from the 2003 Siberian forest fire on organic carbon in PM2.5 in Nagoya, Japan.

PubMed

Ikemori, Fumikazu; Honjyo, Koji; Yamagami, Makiko; Nakamura, Toshio

2015-10-15

In May 2003, high concentrations of organic carbon (OC) in PM2.5 were measured in Nagoya, a representative metropolitan area in Japan. To investigate the influence of possible forest fires on PM2.5 in Japan via long-range aerosol transport, the radiocarbon ((14)C) concentrations of PM2.5 samples from April 2003 to March 2004 were measured. (14)C concentrations in total carbon (TC) from May to early June showed higher values than those in other periods. The OC/elemental carbon (EC) ratios from May to early June were also significantly higher than the ones in other periods. In addition, OC concentrations from May to early June were typically high. These results indicate that the abundant OC fraction from May to early June in Nagoya consisted predominantly of contemporary carbon. Furthermore, simulations of diffusion and transport of organic matter (OM) in East Asia showed that abundant OM originating from East Siberia spread over East Asia and Japan in May and early June. Backward air mass trajectories from this time frame indicate that the air mass in Nagoya likely first passed through East Siberia where fire events were prevalent. However, the backward trajectories showed that the air mass after early June did not originate mainly from Siberia, and correspondingly, the (14)C and OC concentrations showed lower values than those from May to early June. Therefore, the authors conclude that contemporary carbon originating from the forest fire in East Siberia was transported to Nagoya, where it significantly contributed to the high observed concentrations of both OC and (14)C. Copyright © 2015 Elsevier B.V. All rights reserved.

Deep-water lithofacies and conodont faunas of the Lisburne Group, western Brooks Range, Alaska: A section in Geologic studies in Alaska by the U.S. Geological Survey, 1992

USGS Publications Warehouse

Dumoulin, Julie A.; Harris, Anita G.; Schmidt, Jeanine M.

1993-01-01

Deep-water lithofacies of the Lisburne Group occur in thrust sheets in the western part of the foreland fold and thrust belt of the Brooks Range and represent at least three discrete units. The Kuna Formation (Brooks Range allochthon) consists mostly of spiculitic mudstone and lesser shale; subordinate carbonate layers are chiefly diagenetic dolomite. Predominantly shale sections of the Kuna that contain few sponge spicules occur in the western part of the study area. The Akmalik Chert (Picnic Creek allochthon) is mostly radiolarian-spiculitic chert; rare limy beds are calcitized radiolarite. The Rim Butte unit (Ipnavik River allochthon) consists chiefly of calcareous turbidites, derived from both shallow- and deep-water sources, interbedded with spiculitic mudstone. Much of the material in the turbidites came from a contemporaneous carbonate platform and margin, but some fossils and lithic clasts were eroded from older, already lithified carbonate-platform rocks. All three units appear to be roughly coeval and are chiefly Osagean (late Early Mississippian) in age in the study area.Shallow-water lithofacies of the Lisburne Group exposed in the Howard Pass area (Brooks Range allochthon) are mostly of Meramecian (early Late Mississippian) age. Thus, these carbonate-platform rocks were not the source of the calcareous turbidites in the Rim Butte unit. Rim Butte turbidites could have been derived from older platform carbonate rocks such as those of the Utukok Formation (Kelly River allochthon) exposed mainly to the west of the Howard Pass quadrangle.

Early cements versus pore-water chemical composition in the subsurface of the sabkha of Abu Dhabi

NASA Astrophysics Data System (ADS)

Paul, Andreas; Yuan, Peng; Court, Wesley M.; Lokier, Stephen W.; Dutton, Kirsten E.; Van der Land, Cees; Lessa Andrade, Luiza; Sherry, Angela; Head, Ian M.

2017-04-01

The coastal sabkha of Abu Dhabi is a complex depositional system in an extremely arid climate. This depositional system is marked by the formation of primary carbonate and microbial deposits, and by the development of secondary evaporite and cement phases. A number of earlier studies have assessed the formation of these secondary phases, yet no research has established a relationship between lateral and vertical variations in the chemical composition of pore water and the nature of, in particular, the precipitating pore-filling cements, re-crystallisation features and dissolution. This study aims to establish an understanding of the environmental and sedimentary factors that control early post-depositional changes to sediment composition as a result of sediment - pore water interactions. A particular focus is to characterise changes in the chemistry of the pore water throughout a tidal cycle, aiming at understanding how the influx of 'fresh' lagoonal sea water influences the chemistry of the pore water, and which elements are replenished on a daily basis. The initial data presented here is based upon the relationship between the petrographic analysis of sediment samples and lateral and vertical variations in the chemistry of in-situ sampled pore water. The pore water is characterised with respect to pH, salinity, alkalinity, dissolved organic carbon, and the concentrations of a variety of common metallic and non-metallic elements, including (but not limited to) Ca, Fe, Mg, P, S and Sr. Initial results show that concentrations of Mg, P, and V, and the ratios Mg/Ca and Sr/Ca are highest at the seaward sampling locations. Contrastingly, individual concentrations for Ca, Sr, Fe, Si, and Cu are highest at the most landward locality. In particular the higher concentrations for Ca and Sr might indicate diagenetic processes and are thus enriched as a result of e.g. aragonite dissolution. A striking pattern in Mg concentrations show the highest values for this element

Tempo and scale of late Paleocene and early Eocene carbon isotope cycles: Implications for the origin of hyperthermals

NASA Astrophysics Data System (ADS)

Zachos, James C.; McCarren, Heather; Murphy, Brandon; Röhl, Ursula; Westerhold, Thomas

2010-10-01

The upper Paleocene and lower Eocene are marked by several prominent (> 1‰) carbon isotope (δ 13C) excursions (CIE) that coincide with transient global warmings, or thermal maxima, including the Paleocene-Eocene Thermal Maximum (PETM). The CIE, which are recorded mainly in marine sedimentary sequences, have also been identified in continental sequences, occurred episodically, and yet appear to be paced or triggered by orbital forcing. To constrain the timing and scale of the CIE relative to long-term baseline variability, we have constructed a 4.52 million year (myr) long, high-resolution (~ 3 kyr) bulk sediment carbon isotope record spanning the lower Eocene to upper Paleocene (C25r-C24n) from a pelagic sediment section recovered at ODP Site 1262 in the southeast Atlantic. This section, which was orbitally-tuned utilizing high-resolution core log physical property and geochemical records, is the most stratigraphically complete upper Paleocene to lower Eocene sequence recovered to date. Time-series analysis of the carbon isotope record along with a high-resolution Fe intensity record obtained by XRF core scanner reveal cyclicity with variance concentrated primarily in the precession (21 kyr) and eccentricity bands (100 and 400-kyr) throughout the upper Paleocene-lower Eocene. In general, minima in δ 13C correspond with peaks in Fe (i.e., carbonate dissolution), both of which appear to be in phase with maxima in eccentricity. This covariance is consistent with excess oceanic uptake of isotopically depleted carbon resulting in lower carbonate saturation during periods of high eccentricity. This relationship includes all late Paleocene and early Eocene CIE confirming pacing by orbital forcing. The lone exception is the PETM, which appears to be out of phase with the 400-kyr cycle, though possibly in phase with the 100-kyr cycle, reinforcing the notion that a mechanism other than orbital forcing and/or an additional source of carbon is required to account for the

Some open issues in the analysis of the storage and migration properties of fractured carbonate reservoirs

NASA Astrophysics Data System (ADS)

Agosta, Fabrizio

2017-04-01

evolution and diagenesis is not determined yet. Differently, porous rocks are mainly affected by deformation banding. The latter process involves the collapse of primary porosity within narrow bands, which often localize into well-developed clusters. Currently, researchers focus on the assessment of the 3D pore geometry of the shear bands, which may act as possible sites for residual C02 trapping. The fault-bounded rock volumes are mainly crosscut by background fractures. These diffuse fractures are often compartmentalized into discrete mechanical units, which are bounded by primary heterogeneities such as bed interfaces and transgressive erosional surfaces. Moreover, bed-parallel pressure solution seams, structural elements that commonly form in limestone rocks during burial diagenesis, can also act as mechanical interfaces during growth of background fractures. However, early embrittlement of carbonates was also documented, suggesting to further investigate their diagenetic evolution to determine the conditions at which the latter phenomenon takes place. Results could shed new lights into the storage properties and, hence, the amount of CO2 that can be securely stored within significant volumes of fractured carbonates in the underground.

Early Cretaceous Shallow-Water Platform Carbonates of the Bolkar Mountains, Central Taurides - South Turkey: Facies Analysis and Depositional Environments

NASA Astrophysics Data System (ADS)

Solak, Cemile; Taslı, Kemal; Koç, Hayati

2016-10-01

The study area comprises southern non-metamorphic part of the Bolkar Mountains which are situated in southern Turkey, eastern part of the Central Taurides. The studied five outcrops form geologically parts of the tectonostratigraphic units called as allochthonous Aladag Unit and autochthonous Geyikdagi Unit. The aim of this study is to describe microfacies and depositional environments of the Bolkar Mountains Early Cretaceous shallow- water platform carbonates. The Lower Cretaceous is represented by continuous thick- bedded to massive dolomite sequence ranging from 100 to 150 meters thick, which only contains locally laminated limestone intercalations in the Yüğlük section and thick to very thick-bedded uniform limestones ranging from approximately 50 to 120 meters, consist of mainly laminated- fenestral mudstone, peloidal-intraclastic grainstone-packstone, bioclastic packstone- wackestone, benthic foraminiferal-intraclastic grainstone-packstone, ostracod-fenestral wackestone-mudstone, dasycladacean algal packstone-wackestone and ooidal grainstone microfacies. Based on a combination sedimantological data, facies/microfacies and micropaleontological (predominantly dasycladacean algae and diverse benthic foraminifera) analysis, it is concluded that Early Cretaceous platform carbonates of the Bolkar Mountains reflect a tidally affected tidal-flat and restricted lagoon settings. During the Berriasian- Valanginian unfavourable facies for benthic foraminifera and dolomitization were predominate. In the Hauterivian-early Aptian, the effect of dolomitization largely disappeared and inner platform conditions still prevailed showing alternations of peritidal and lagoon facies, going from peritidal plains (representing various sub-environments including supratidal, intertidal area, tidal-intertidal ponds and ooid bars) dominated by ostracod and miliolids, to dasycladacean algae-rich restricted lagoons-subtidal. These environments show a transition in the vertical and

The Formation of Fe/Mg Smectite Under Mildly Acidic Conditions on Early Mars

NASA Technical Reports Server (NTRS)

Sutter, B.; Golden, D. C.; Ming, Douglas W.; Niles, P. B.

2011-01-01

The detection of Fe/Mg smectites and carbonate in Noachian and early Hesperian terrain of Mars suggests that neutral to mildly alkaline conditions prevailed during the early history of Mars. If early Mars surface geochemical conditions were neutral to moderately alkaline with a denser CO2 atmosphere than today, then large carbonates deposits should be more widely detected in Noachian terrain. Why have so few carbonate deposits been detected compared to Fe/Mg smectites? Fe/Mg smectites on early Mars formed under mildly acidic conditions, which would preclude the extensive formation of carbonate deposits. The goal of the proposed work is to evaluate the formation of Fe/Mg smectites under mildly acidic conditions.

Diagenesis in tephra-rich sediments from the Lesser Antilles Volcanic Arc: Pore fluid constraints

NASA Astrophysics Data System (ADS)

Murray, Natalie A.; McManus, James; Palmer, Martin R.; Haley, Brian; Manners, Hayley

2018-05-01

We present sediment pore fluid and sediment solid phase results obtained during IODP Expedition 340 from seven sites located within the Grenada Basin of the southern Lesser Antilles Volcanic Arc region. These sites are generally characterized as being low in organic carbon content and rich in calcium carbonate and volcanogenic material. In addition to the typical reactions related to organic matter diagenesis, pore fluid chemistry indicates that the diagenetic reactions fall within two broad categories; (1) reactions related to chemical exchange with volcanogenic material and (2) reactions related to carbonate dissolution, precipitation, or recrystallization. For locations dominated by reaction with volcanogenic material, these sites exhibit increases in dissolved Ca with coeval decreases in Mg. We interpret this behavior as being driven by sediment-water exchange reactions from the alteration of volcanic material that is dispersed throughout the sediment package, which likely result in formation of Mg-rich secondary authigenic clays. In contrast to this behavior, sediment sequences that exhibit decreases in Ca, Mg, Mn, and Sr with depth suggest that carbonate precipitation is an active diagenetic process affecting solute distributions. The distributions of pore fluid 87Sr/86Sr reflect these competitive diagenetic reactions between volcanic material and carbonate, which are inferred by the major cation distributions. From one site where we have solid phase 87Sr/86Sr (site U1396), the carbonate fraction is found to be generally consistent with the contemporaneous seawater isotope values. However, the 87Sr/86Sr of the non-carbonate fraction ranges from 0.7074 to 0.7052, and these values likely represent a mixture of local arc volcanic sources and trans-Atlantic eolian sources. Even at this site where there is clear evidence for diagenesis of volcanogenic material, carbonate diagenesis appears to buffer pore fluid 87Sr/86Sr from the larger changes that might be

Evaluation of carbonate diagenesis: A comparative study of minor elements, trace elements, and rare-earth elements (REE + Y) between Pleistocene corals and matrices from Grand Cayman, British West Indies

NASA Astrophysics Data System (ADS)

Li, Rong; Jones, Brian

2014-12-01

On Grand Cayman, the Pleistocene Ironshore Formation consists of six unconformity-bounded units of limestones that have been partially or completely altered to calcite by post-depositional meteoric diagenesis. In order to examine the diagenetic history from the perspective of geochemical elements, the concentrations of minor element (Sr, Na, Mg), trace elements (Ba, Fe, Mn, Al, Si), and rare-earth elements (REE) and yttrium (Y) were determined for 105 corals and 84 matrices collected from the Rogers Wreck Point (RWP), Western Onshore area (WO), and offshore George Town (GT) areas. With the transformation of aragonite to calcite, the Sr, Na, and Ba values decreased, but Mg increased, which are indicative of diagenetic alteration in an open water system. Due to intrinsic "vital effects" and the extrinsic diagenetic environment, the variations of Sr, Na, Ba, and Mg concentrations between Acropora and Montastrea from the GT area are different to those of their counterparts from RWP and WO. The signatures of Sr, Na, Ba, and Mg are in good agreement with the diagenetic history as determined from petrographic and stable isotopic criteria. The REE + Y (REY) concentrations (ΣREY) are higher in the matrices (0.2-6.9 ppm, average 2.6 ppm) than in the associated corals (0.1-5.4 ppm, average 0.6 ppm). Shale-normalized REY patterns of the Pleistocene Ironshore Formation are similar to those of oxygenated seawater, which are characterized by (1) light REE depletion relative to heavy REE (average DySN/SmSN = 1.7, n = 35), (2) positive La anomalies (average Pr/Pr* = 1.17, n = 53), and (3) negative Ce anomalies (average Ce/Ce* = 0.49, n = 53). The preserved seawater-like REY distribution pattern, the lack of correlation between ΣREY and mineralogy, and the lack of correlation between ΣREY and diagenesis-sensitive stable oxygen isotope (δ18O) indicate that meteoric diagenesis did not have a major impact on the REY distribution patterns. The matrices and corals in the GT area

Sedimentologic and paleoclimatic reconstructions of carbonate factory evolution in the Alborz Basin (northern Iran) indicate a global response to Early Carboniferous (Tournaisian) glaciations

NASA Astrophysics Data System (ADS)

Sardar Abadi, Mehrdad; Kulagina, Elena I.; Voeten, Dennis F. A. E.; Boulvain, Frédéric; Da Silva, Anne-Christine

2017-03-01

The Lower Carboniferous Mobarak Formation records the development of a storm-sensitive pervasive carbonate factory on the southern Paleo-Tethyan passive margin following the opening of the Paleo-Tethys Ocean into the Alborz Basin along the northern margin of Gondwana. Its depositional facies encompass inner ramp peritidal environments, peloidal to crinoidal shoals, storm to fair-weather influenced mid-ramps, proximal to distal shell beds and low energy outer ramps. Sedimentological analyses and foraminiferal biostratigraphy reveal four events affecting carbonate platform evolution in the Alborz Basin during the Lower Carboniferous: (1) A transgression following global temperature rise in the Early Tournaisian (middle Hastarian) caused the formation of thick-bedded argillaceous limestones. This interval correlates with Early Tournaisian nodular to argillaceous limestones in the Moravia Basin (Lisen Formation, Czech Republic), the Dinant Basin (Pont d'Arcole Formation, Belgium), and at the Rhenish Slate Mountains (Lower Alum shale, Germany). (2) Late Hastarian-early Ivorian glaciations previously identified in Southern Gondwana but had not yet recognized in Northern Gondwana were recorded through a sequence boundary. (3) During the Late Tournaisian-Early Visean?, a differential block faulting regime along the basin's margin caused uplift of the westernmost parts of the Alborz Basin and resulted in subsidence in the eastern part of the central basin. This tectonically controlled shift in depositional regime caused vast sub-aerial exposure and brecciation preserved in the top of the Mobarak Formation in the western portion of the Central Alborz Basin. (4) Tectonic activity coinciding with a progressive, multiphase sea level drop caused indirectly by the Viséan and Serpukhovian glaciations phases ultimately led to the stagnation of the carbonate factory. Paleothermometry proxies, the presence of foraminiferal taxa with a northern Paleo-Tethyan affinity and evidence for

SEDIMENT GEOCHEMICAL MODEL

EPA Science Inventory

Until recently, sediment geochemical models (diagenetic models) have been only able to explain sedimentary flux and concentration profiles for a few simplified geochemical cycles (e.g., nitrogen, carbon and sulfur). However with advances in numerical methods, increased accuracy ...