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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
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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: 2022-10-20
    Description: © The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Vrolijk, P., Summa, L., Ayton, B., Nomikou, P., Huepers, A., Kinnaman, F., Sylva, S., Valentine, D., & Camilli, R. Using a Ladder of Seeps with computer decision processes to explore for and evaluate cold seeps on the Costa Rica active margin. Frontiers in Earth Science, 9, (2021): 601019, https://doi.org/10.3389/feart.2021.601019.
    Description: Natural seeps occur at the seafloor as loci of fluid flow where the flux of chemical compounds into the ocean supports unique biologic communities and provides access to proxy samples of deep subsurface processes. Cold seeps accomplish this with minimal heat flux. While individual expertize is applied to locate seeps, such knowledge is nowhere consolidated in the literature, nor are there explicit approaches for identifying specific seep types to address discrete scientific questions. Moreover, autonomous exploration for seeps lacks any clear framework for efficient seep identification and classification. To address these shortcomings, we developed a Ladder of Seeps applied within new decision-assistance algorithms (Spock) to assist in seep exploration on the Costa Rica margin during the R/V Falkor 181210 cruise in December, 2018. This Ladder of Seeps [derived from analogous astrobiology criteria proposed by Neveu et al. (2018)] was used to help guide human and computer decision processes for ROV mission planning. The Ladder of Seeps provides a methodical query structure to identify what information is required to confirm a seep either: 1) supports seafloor life under extreme conditions, 2) supports that community with active seepage (possible fluid sample), or 3) taps fluids that reflect deep, subsurface geologic processes, but the top rung may be modified to address other scientific questions. Moreover, this framework allows us to identify higher likelihood seep targets based on existing incomplete or easily acquired data, including MBES (Multi-beam echo sounder) water column data. The Ladder of Seeps framework is based on information about the instruments used to collect seep information (e.g., are seeps detectable by the instrument with little chance of false positives?) and contextual criteria about the environment in which the data are collected (e.g., temporal variability of seep flux). Finally, the assembled data are considered in light of a Last-Resort interpretation, which is only satisfied once all other plausible data interpretations are excluded by observation. When coupled with decision-making algorithms that incorporate expert opinion with data acquired during the Costa Rica experiment, the Ladder of Seeps proved useful for identifying seeps with deep-sourced fluids, as evidenced by results of geochemistry analyses performed following the expedition.
    Description: Support for this research was provided through NASA PSTAR Grant #NNX16AL08G and National Science Foundation Navigating the New Arctic grant #1839063. Use of the R/V Falkor and ROV SuBastian were provided through a grant from the Schmidt Ocean Institute. The AUG Nemesis and the Aurora in-situ mass spectrometer was provided through in-kind support from Teledyne Webb Research and Navistry Corp, respectively.
    Keywords: Seep ; Autonomous exploration ; Costa Rica ; Geochemistry ; Water column data ; Temporal variability ; Decision-making algorithm
    Repository Name: Woods Hole Open Access Server
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  • 8
    Publication Date: 2022-05-27
    Description: © The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Gosselin, K. M., Nelson, R. K., Spivak, A. C., Sylva, S. P., Van Mooy, B. A. S., Aeppli, C., Sharpless, C. M., O’Neil, G. W., Arrington, E. C., Reddy, C. M., & Valentine, D. L. Production of two highly abundant 2-methyl-branched fatty acids by blooms of the globally significant marine cyanobacteria Trichodesmium erythraeum. ACS Omega, 6(35), (2021): 22803–22810, https://doi.org/10.1021/acsomega.1c03196.
    Description: The bloom-forming cyanobacteria Trichodesmium contribute up to 30% to the total fixed nitrogen in the global oceans and thereby drive substantial productivity. On an expedition in the Gulf of Mexico, we observed and sampled surface slicks, some of which included dense blooms of Trichodesmium erythraeum. These bloom samples contained abundant and atypical free fatty acids, identified here as 2-methyldecanoic acid and 2-methyldodecanoic acid. The high abundance and unusual branching pattern of these compounds suggest that they may play a specific role in this globally important organism.
    Description: This work was funded with grants from the National Science Foundation grants OCE-1333148, OCE-1333162, and OCE-1756254 and the Woods Hole Oceanographic Institution (IR&D). GCxGC analysis made possible by WHOI’s Investment in Science Fund.
    Keywords: Lipids ; Alkyls ; Bacteria ; Genetics ; Chromatography
    Repository Name: Woods Hole Open Access Server
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  • 9
    Publication Date: 2022-05-26
    Description: Author Posting. © American Chemical Society, 2019. This article is posted here by permission of American Chemical Society for personal use, not for redistribution. The definitive version was published in Kivenson, V., Lemkau, K. L., Pizarro, O., Yoerger, D. R., Kaiser, C., Nelson, R. K., Carmichael, C., Paul, B. G., Reddy, C. M., & Valentine, D. L. (2019). Ocean Dumping of Containerized DDT Waste Was a Sloppy Process. Environmental Science and Technology (2019), doi:10.1021/acs.est.8b05859.
    Description: Industrial-scale dumping of organic waste to the deep ocean was once common practice, leaving a legacy of chemical pollution for which a paucity of information exists. Using a nested approach with autonomous and remotely operated underwater vehicles, a dumpsite offshore California was surveyed and sampled. Discarded waste containers littered the site and structured the suboxic benthic environment. Dichlorodiphenyltrichloroethane (DDT) was reportedly dumped in the area, and sediment analysis revealed substantial variability in concentrations of p,p-DDT and its analogs, with a peak concentration of 257 μg g–1, ∼40 times greater than the highest level of surface sediment contamination at the nearby DDT Superfund site. The occurrence of a conspicuous hydrocarbon mixture suggests that multiple petroleum distillates, potentially used in DDT manufacture, contributed to the waste stream. Application of a two end-member mixing model with DDTs and polychlorinated biphenyls enabled source differentiation between shelf discharge versus containerized waste. Ocean dumping was found to be the major source of DDT to more than 3000 km2 of the region’s deep seafloor. These results reveal that ocean dumping of containerized DDT waste was inherently sloppy, with the contents readily breaching containment and leading to regional scale contamination of the deep benthos.
    Description: This material is based upon work supported by the National Science Foundation Graduate Research Fellowship for V.K. under Grant No. 1650114. Expeditions AT-18-11 and AT-26-06 were funded by the NSF (OCE-0961725 and OCE-1046144). Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. We thank the captain and crew of the RV Atlantis, the pilots and crew of the ROV Jason, the crew of the AUV Sentry, the scientific party of the AT-18-11 and AT-26-06 expeditions, Justin Tran for assistance with the preparation of multibeam data, M. Indira Venkatesan for a helpful discussion of the NOAA datasets, and Nathan Dodder for advice on the procedure for compound identification.
    Repository Name: Woods Hole Open Access Server
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  • 10
    Publication Date: 2022-05-26
    Description: Dataset: Sargasso Sea Hydrocarbons
    Description: Hydrocarbon concentrations, DIC isotopes, nutrients, and cyanobacteria counts from samples collected on R/V Neil Armstrong cruise AR16 in the western north Atlantic during May 2017. 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/826878
    Description: NSF Division of Ocean Sciences (NSF OCE) OCE-1756667, NSF Division of Ocean Sciences (NSF OCE) OCE-1635562, NSF Division of Ocean Sciences (NSF OCE) OCE-1634478
    Repository Name: Woods Hole Open Access Server
    Type: Dataset
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