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  • 1
    Publication Date: 2021-05-11
    Description: The isotopic composition of methane is of longstanding geochemical interest, with important implications for understanding petroleum systems, atmospheric greenhouse gas concentrations, the global carbon cycle, and life in extreme environments. Recent analytical developments focusing on multiply substituted isotopologues (‘clumped isotopes’) are opening a valuable new window into methane geochemistry. When methane forms in internal isotopic equilibrium, clumped isotopes can provide a direct record of formation temperature, making this property particularly valuable for identifying different methane origins. However, it has also become clear that in certain settings methane clumped isotope measurements record kinetic rather than equilibrium isotope effects. Here we present a substantially expanded dataset of methane clumped isotope analyses, and provide a synthesis of the current interpretive framework for this parameter. In general, clumped isotope measurements indicate plausible formation temperatures for abiotic, thermogenic, and microbial methane in many geological environments, which is encouraging for the further development of this measurement as a geothermometer, and as a tracer for the source of natural gas reservoirs and emissions. We also highlight, however, instances where clumped isotope derived temperatures are higher than expected, and discuss possible factors that could distort equilibrium formation temperature signals. In microbial methane from freshwater ecosystems, in particular, clumped isotope values appear to be controlled by kinetic effects, and may ultimately be useful to study methanogen metabolism.
    Description: Published
    Description: 262-282
    Description: 6A. Geochimica per l'ambiente
    Description: JCR Journal
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 2
    Publication Date: 2022-05-25
    Description: Author Posting. © The Authors, 2006. This is the author's version of the work. It is posted here by permission of National Academy of Sciences for personal use, not for redistribution. The definitive version was published in Proceedings of the National Academy of Sciences of the United States of America 103 (2006): 13570-13574, doi:10.1073/pnas.0601304103.
    Description: Marine hydrocarbon seepage emits oil and gas, including methane (~30 Tg CH4/year), to the ocean and atmosphere. Sediments from the California margin contain preserved tar, primarily formed via hydrocarbon weathering at the sea surface. We present a record of variation in the abundance of tar in sediments for the past 32ky, providing evidence for increases in hydrocarbon emissions prior to and during Termination IA (16-14 ka) and again over Termination IB (11-10 ka). Our study provides the first direct evidence for increased hydrocarbon seepage associated with deglacial warming via tar abundance in marine sediments, independent of previous geochemical proxies. Climate-sensitive gas hydrates may modulate thermogenic hydrocarbon seepage during deglaciation.
    Description: This work has been supported by the U.S. National Science Foundation (OCE-0242041, Kennett; OCE-0447395, Valentine; IIS-0430835, Reddy) and UC Santa Barbara (Graduate Dissertation Fellowship to T. Hill).
    Keywords: Quaternary climate ; Paleoclimate ; Hydrocarbon ; Methane
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
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  • 3
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2016. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry, Geophysics, Geosystems 17 (2016): 3882–3892, doi:10.1002/2016GC006421.
    Description: Methane seeps were investigated in Hudson Canyon, the largest shelf-break canyon on the northern U.S. Atlantic Margin. The seeps investigated are located at or updip of the nominal limit of methane clathrate hydrate stability. The acoustic identification of bubble streams was used to guide water column sampling in a 32 km2 region within the canyon's thalweg. By incorporating measurements of dissolved methane concentration with methane oxidation rates and current velocity into a steady state box model, the total emission of methane to the water column in this region was estimated to be 12 kmol methane per day (range: 6–24 kmol methane per day). These analyses suggest that the emitted methane is largely retained inside the canyon walls below 300 m water depth, and that it is aerobically oxidized to near completion within the larger extent of Hudson Canyon. Based on estimated methane emissions and measured oxidation rates, the oxidation of this methane to dissolved CO2 is expected to have minimal influences on seawater pH.
    Description: National Science Foundation Grant Number: OCE-1318102; U.S. Department of Energy award Grant Numbers: DE-FE0013999 and NSF OCE-1352301, DOE-USGS, DE-FE0002911 and DE-FE0005806
    Description: 2017-04-13
    Keywords: Methane seeps ; Methane flux ; Methane oxidation ; Hudson Canyon
    Repository Name: Woods Hole Open Access Server
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  • 4
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2007. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 34 (2007): L22603, doi:10.1029/2007GL031344.
    Description: Large quantities of natural gas are emitted from the seafloor into the stratified coastal ocean near Coal Oil Point, Santa Barbara Channel, California. Methane was quantified in the down current surface water at 79 stations in a 280 km2 study area. The methane plume spread over an area of ~70 km2 and emitted on the order of 5 × 104 mol d−1 to the atmosphere. A monthly time series at 14 stations showed variable methane concentrations which were correlated with changing sub-mesoscale surface currents. Air-sea fluxes estimated from the time series indicate that the air-sea flux derived for the 280 km2 area is representative of the daily mean flux from this area. Only 1% of the dissolved methane originating from Coal Oil Point enters the atmosphere within the study area. Most of it appears to be transported below the surface and oxidized by microbial activity.
    Description: The research was supported by the University of California Energy Institute and the National Science Foundation (OCE 0447395).
    Keywords: Air-sea flux ; Shallow marine seep ; Methane
    Repository Name: Woods Hole Open Access Server
    Type: Article
    Format: application/postscript
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  • 5
    Publication Date: 2022-05-25
    Description: Author Posting. © The Author(s), 2011. This is the author's version of the work. It is posted here by permission of American Chemical Society for personal use, not for redistribution. The definitive version was published in Environmental Science & Technology 45 (2011):1298–1306, doi:10.1021/es103838p.
    Description: Response actions to the Deepwater Horizon oil spill included the injection of ~771,000 gallons (2,900,000 L) of chemical dispersant into the flow of oil near the seafloor. Prior to this incident, no deepwater applications of dispersant had been conducted and thus no data exists on the environmental fate of dispersants in deepwater. We used ultrahigh resolution mass spectrometry and liquid chromatography with tandem mass spectrometry (LC/MS/MS) to identify and quantify one key ingredient of the dispersant, the anionic surfactant DOSS (dioctyl sodium sulfosuccinate), in the Gulf of Mexico deepwater during active flow and again after flow had ceased. Here we show that DOSS was sequestered in deepwater hydrocarbon plumes at 1000-1200m water depth and did not intermingle with surface dispersant applications. Further, its concentration distribution was consistent with conservative transport and dilution at depth and it persisted up to 300 km from the well, 64 days after deepwater dispersant applications ceased. We conclude that DOSS was selectively associated with the oil and gas phases in the deepwater plume, yet underwent negligible, or slow, rates of biodegradation in the affected waters. These results provide important constraints on accurate modeling of the deepwater plume and critical geochemical contexts for future toxicological studies.
    Description: The authors gratefully acknowledge funding from the National Science Foundation’s RAPID program (OCE-1045811 to EBK, OCE-1042097 to DLV, OCE-1042650 to J. D. Kessler for R/V Cape Hatteras cruise) and from the WHOI Director of Research. Instrumentation in the WHOI FT-MS facility was funded by the National Science Foundation MRI program (OCE-0619608) and by the Gordon and Betty T. Moore Foundation. Stipend support for A. Boysen was provided by the WHOI Summer Student Fellow Program.
    Keywords: Deepwater Horizon ; Dispersants ; DOSS ; Dilution ; Deepwater plume
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
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  • 6
    Publication Date: 2022-05-25
    Description: Author Posting. © The Author(s), 2011. This is the author's version of the work. It is posted here by permission of National Academy of Sciences for personal use, not for redistribution. The definitive version was published in Proceedings of the National Academy of Sciences of the United States of America (2012), doi:10.1073/pnas.1110564109.
    Description: Detailed airborne, surface, and subsurface chemical measurements, primarily obtained in May and June 2010, are used to quantify initial hydrocarbon compositions along different transport pathways – in deep subsurface plumes, in the initial surface slick, and in the atmosphere – during the Deepwater Horizon (DWH) oil spill. Atmospheric measurements are consistent with a limited area of surfacing oil, with implications for leaked hydrocarbon mass transport and oil drop size distributions. The chemical data further suggest relatively little variation in leaking hydrocarbon composition over time. While readily soluble hydrocarbons made up ~25% of the leaking mixture by mass, subsurface chemical data show these compounds made up ~69% of the deep plume mass; only ~31% of deep plume mass was initially transported in the form of trapped oil droplets. Mass flows along individual transport pathways are also derived from atmospheric and subsurface chemical data. Subsurface hydrocarbon composition, dissolved oxygen, and dispersant data are used to provide a new assessment of release of hydrocarbons from the leaking well. We use the chemical measurements to estimate that (7.8±1.9) x106 kg of hydrocarbons leaked on June 10, 2010, directly accounting for roughly three-quarters of the total leaked mass on that day. The average environmental release rate of (10.1 ± 2.0) x106 kg/day derived using atmospheric and subsurface chemical data agrees within uncertainties with the official average leak rate of (10.2 ± 1.0) x106 kg/day derived using physical and optical methods.
    Description: This research was supported by the National Science Foundation through grants to D. Blake (AGS-1049952), J. Kessler (OCE-1042650 and OCE-0849246), D. Valentine (OCE-1042097 and OCE-0961725), E. Kujawinski (OCE-1045811), and R. Camilli (OCE-1043976), by U.S. Coast Guard contract to R. Camilli (Contract HSCG3210CR0020), and by U.S. Department of Energy grant to D. Valentine (DE- NT0005667). The August, September, and October research cruises were funded by NOAA through a contract with Consolidated Safety Services, Incorporated. The NOAA P-3 oil spill survey flights were funded in part by NOAA and in part by a U.S. Coast Guard Pollution Removal Funding Authorization to NOAA.
    Repository Name: Woods Hole Open Access Server
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  • 7
    Publication Date: 2022-10-26
    Description: Author Posting. © American Geophysical Union, 2019. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 46(12), (2019): 6745-6754, doi:10.1029/2019GL082867.
    Description: Although photochemical oxidation is an environmental process that drives organic carbon (OC) cycling, its quantitative detection remains analytically challenging. Here, we use samples from the Deepwater Horizon oil spill to test the hypothesis that the stable oxygen isotope composition of oil (δ18OOil) is a sensitive marker for photochemical oxidation. In less than one‐week, δ18OOil increased from −0.6 to 7.2‰, a shift representing ~25% of the δ18OOC dynamic range observed in nature. By accounting for different oxygen sources (H2O or O2) and kinetic isotopic fractionation of photochemically incorporated O2, which was −9‰ for a wide range of OC sources, a mass balance was established for the surface oil's elemental oxygen content and δ18O. This δ18O‐based approach provides novel insights into the sources and pathways of hydrocarbon photo‐oxidation, thereby improving our understanding of the fate and transport of petroleum hydrocarbons in sunlit waters, and our capacity to respond effectively to future spills.
    Description: We thank Robert Ricker and Greg Baker (NOAA) for helping secure the oil residues, James Payne (Payne Environmental Consultants, Inc.) for collecting many of the surface oil residues, Joy Matthews (UC Davis) for exceptional assistance in preparing and analyzing the oil residues for oxygen content and isotopes, Hank Levi and Art Gatenby at CSC Scientific Company for assistance with the water content measurements, Robyn Comny (US EPA) for providing the Alaska North Slope oil, and Rose Cory (UMich) for discussions about our findings. Special thanks to John Hayes who provided constructive feedback on a preliminary version of this dataset prior to his passing in February of 2017. We thank Alex Sessions (CalTech) for his constructive feedback during the review process. This work was supported, in part, by National Science Foundation grants RAPID OCE‐1043976 (CMR), OCE‐1333148 (CMR), OCE‐1333026 (CMS), OCE‐1333162 (DLV), OCE‐1841092 (CPW), NASA NESSF NNX15AR62H (KMS), the Gulf of Mexico Research Initiative grants ‐ 015, SA 16‐30, and DEEP‐C consortium, a fellowship through the Hansewissenschaftskolleg (Institute for Advanced Studies) to SDW, and assistant scientist salary support from the Frank and Lisina Hoch Endowed Fund (CPW).
    Description: 2019-11-30
    Keywords: Petroleum hydrocarbons ; Photochemical oxidation ; Deepwater Horizon ; Stable oxygen isotopes ; Organic carbon
    Repository Name: Woods Hole Open Access Server
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  • 8
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    Biological and Chemical Oceanography Data Management Office (BCO-DMO). Contact: bco-dmo-data@whoi.edu
    Publication Date: 2022-12-31
    Description: Dataset: BASIN 2019 Sediment properties
    Description: Sediments were collected in Fall 2019 across three transects in the Santa Barbara Basin using the ROV Jason during R/V Atlantis cruise AT42-19. This dataset consists of the sediment parameters porosity and density. For a complete list of measurements, refer to the full dataset description in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: https://www.bco-dmo.org/dataset/867113
    Description: NSF Division of Ocean Sciences (NSF OCE) OCE-1829981, NSF Division of Ocean Sciences (NSF OCE) OCE-1830033
    Description: 2022-12-31
    Keywords: Santa Barbara Basin ; Sediments ; Density ; Porosity
    Repository Name: Woods Hole Open Access Server
    Type: Dataset
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  • 9
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    Biological and Chemical Oceanography Data Management Office (BCO-DMO). Contact: bco-dmo-data@whoi.edu
    Publication Date: 2022-12-31
    Description: Dataset: BASIN 2019 Porewater geochemistry
    Description: Sediments were collected in Fall 2019 across three transects in the Santa Barbara Basin using the ROV Jason during R/V Atlantis cruise AT42-19. Porewater was separated from the sediments and geochemical properties measured. For a complete list of measurements, refer to the full dataset description in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: https://www.bco-dmo.org/dataset/867007
    Description: NSF Division of Ocean Sciences (NSF OCE) OCE-1829981, NSF Division of Ocean Sciences (NSF OCE) OCE-1830033
    Description: 2022-12-31
    Keywords: Santa Barbara Basin ; Sediments ; Porewater ; Geochemistry
    Repository Name: Woods Hole Open Access Server
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  • 10
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    Biological and Chemical Oceanography Data Management Office (BCO-DMO). Contact: bco-dmo-data@whoi.edu
    Publication Date: 2022-12-31
    Description: Dataset: BASIN 2019 Microbial activity
    Description: Sediments were collected in Fall 2019 across three transects in the Santa Barbara Basin using the ROV Jason during R/V Atlantis cruise AT42-19. Microbial activity in the sediments was determined by measuring sulfate reduction rates. For a complete list of measurements, refer to the full dataset description in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: https://www.bco-dmo.org/dataset/867221
    Description: NSF Division of Ocean Sciences (NSF OCE) OCE-1829981, NSF Division of Ocean Sciences (NSF OCE) OCE-1830033
    Description: 2022-12-31
    Keywords: Santa Barbara Basin ; Sediments ; Sulfate reduction
    Repository Name: Woods Hole Open Access Server
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