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  • 1
    Online Resource
    Online Resource
    American Association for the Advancement of Science (AAAS) ; 2023
    In:  Science Advances Vol. 9, No. 4 ( 2023-01-27)
    In: Science Advances, American Association for the Advancement of Science (AAAS), Vol. 9, No. 4 ( 2023-01-27)
    Abstract: Biogenic benzene and toluene emissions from the polar oceans enhance atmospheric secondary organic aerosol mass.
    Type of Medium: Online Resource
    ISSN: 2375-2548
    Language: English
    Publisher: American Association for the Advancement of Science (AAAS)
    Publication Date: 2023
    detail.hit.zdb_id: 2810933-8
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  • 2
    Online Resource
    Online Resource
    Copernicus GmbH ; 2022
    In:  Biogeosciences Vol. 19, No. 4 ( 2022-02-17), p. 1021-1045
    In: Biogeosciences, Copernicus GmbH, Vol. 19, No. 4 ( 2022-02-17), p. 1021-1045
    Abstract: Abstract. The marginal sea ice zone has been identified as a source of different climate-active gases to the atmosphere due to its unique biogeochemistry. However, it remains highly undersampled, and the impact of summertime changes in sea ice concentration on the distributions of these gases is poorly understood. To address this, we present measurements of dissolved methanol, acetone, acetaldehyde, dimethyl sulfide, and isoprene in the sea ice zone of the Canadian Arctic from the surface down to 60 m. The measurements were made using a segmented flow coil equilibrator coupled to a proton-transfer-reaction mass spectrometer. These gases varied in concentrations with depth, with the highest concentrations generally observed near the surface. Underway (3–4 m) measurements showed higher concentrations in partial sea ice cover compared to ice-free waters for most compounds. The large number of depth profiles at different sea ice concentrations enables the proposition of the likely dominant production processes of these compounds in this area. Methanol concentrations appear to be controlled by specific biological consumption processes. Acetone and acetaldehyde concentrations are influenced by the penetration depth of light and stratification, implying dominant photochemical sources in this area. Dimethyl sulfide and isoprene both display higher surface concentrations in partial sea ice cover compared to ice-free waters due to ice edge blooms. Differences in underway concentrations based on sampling region suggest that water masses moving away from the ice edge influences dissolved gas concentrations. Dimethyl sulfide concentrations sometimes display a subsurface maximum in ice -free conditions, while isoprene more reliably displays a subsurface maximum. Surface gas concentrations were used to estimate their air–sea fluxes. Despite obvious in situ production, we estimate that the sea ice zone is absorbing methanol and acetone from the atmosphere. In contrast, dimethyl sulfide and isoprene are consistently emitted from the ocean, with marked episodes of high emissions during ice-free conditions, suggesting that these gases are produced in ice-covered areas and emitted once the ice has melted. Our measurements show that the seawater concentrations and air–sea fluxes of these gases are clearly impacted by sea ice concentration. These novel measurements and insights will allow us to better constrain the cycling of these gases in the polar regions and their effect on the oxidative capacity and aerosol budget in the Arctic atmosphere.
    Type of Medium: Online Resource
    ISSN: 1726-4189
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2022
    detail.hit.zdb_id: 2158181-2
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  • 3
    In: Ocean Science, Copernicus GmbH, Vol. 15, No. 4 ( 2019-07-16), p. 925-940
    Abstract: Abstract. We present a technique that utilises a segmented flow coil equilibrator coupled to a proton-transfer-reaction mass spectrometer to measure a broad range of dissolved volatile organic compounds. Thanks to its relatively large surface area for gas exchange, small internal volume, and smooth headspace–water separation, the equilibrator is highly efficient for gas exchange and has a fast response time (under 1 min). The system allows for both continuous and discrete measurements of volatile organic compounds in seawater due to its low sample water flow (100 cm3 min−1) and the ease of changing sample intake. The equilibrator setup is both relatively inexpensive and compact. Hence, it can be easily reproduced and installed on a variety of oceanic platforms, particularly where space is limited. The internal area of the equilibrator is smooth and unreactive. Thus, the segmented flow coil equilibrator is expected to be less sensitive to biofouling and easier to clean than membrane-based equilibration systems. The equilibrator described here fully equilibrates for gases that are similarly soluble or more soluble than toluene and can easily be modified to fully equilibrate for even less soluble gases. The method has been successfully deployed in the Canadian Arctic. Some example data from underway surface water and Niskin bottle measurements in the sea ice zone are presented to illustrate the efficacy of this measurement system.
    Type of Medium: Online Resource
    ISSN: 1812-0792
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2019
    detail.hit.zdb_id: 2183769-7
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  • 4
    Online Resource
    Online Resource
    American Geophysical Union (AGU) ; 2020
    In:  Geophysical Research Letters Vol. 47, No. 13 ( 2020-07-16)
    In: Geophysical Research Letters, American Geophysical Union (AGU), Vol. 47, No. 13 ( 2020-07-16)
    Abstract: We present an algorithm for the retrieval of isoprene concentrations in the Southern Ocean from remote sensing Isoprene peaks in midsummer and is highest in coastal and near‐island waters and in the 40–50°S latitudinal band The annual isoprene emission from the entire Southern Ocean amounts 63 Gg C yr −1
    Type of Medium: Online Resource
    ISSN: 0094-8276 , 1944-8007
    Language: English
    Publisher: American Geophysical Union (AGU)
    Publication Date: 2020
    detail.hit.zdb_id: 2021599-X
    detail.hit.zdb_id: 7403-2
    SSG: 16,13
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  • 5
    In: Biogeosciences, Copernicus GmbH, Vol. 17, No. 9 ( 2020-05-15), p. 2593-2619
    Abstract: Abstract. Dimethyl sulfide and volatile organic compounds (VOCs) are important for atmospheric chemistry. The emissions of biogenically derived organic gases, including dimethyl sulfide and especially isoprene, are not well constrained in the Southern Ocean. Due to a paucity of measurements, the role of the ocean in the atmospheric budgets of atmospheric methanol, acetone, and acetaldehyde is even more poorly known. In order to quantify the air–sea fluxes of these gases, we measured their seawater concentrations and air mixing ratios in the Atlantic sector of the Southern Ocean, along a ∼ 11 000 km long transect at approximately 60∘ S in February–April 2019. Concentrations, oceanic saturations, and estimated fluxes of five simultaneously sampled gases (dimethyl sulfide, isoprene, methanol, acetone, and acetaldehyde) are presented here. Campaign mean (±1σ) surface water concentrations of dimethyl sulfide, isoprene, methanol, acetone, and acetaldehyde were 2.60 (±3.94), 0.0133 (±0.0063), 67 (±35), 5.5 (±2.5), and 2.6 (±2.7) nmol dm−3 respectively. In this dataset, seawater isoprene and methanol concentrations correlated positively. Furthermore, seawater acetone, methanol, and isoprene concentrations were found to correlate negatively with the fugacity of carbon dioxide, possibly due to a common biological origin. Campaign mean (±1σ) air mixing ratios of dimethyl sulfide, isoprene, methanol, acetone, and acetaldehyde were 0.17 (±0.09), 0.053 (±0.034), 0.17 (±0.08), 0.081 (±0.031), and 0.049 (±0.040) ppbv. We observed diel changes in averaged acetaldehyde concentrations in seawater and ambient air (and to a lesser degree also for acetone and isoprene), which suggest light-driven production. Campaign mean (±1σ) fluxes of 4.3 (±7.4) µmol m−2 d−1 DMS and 0.028 (±0.021) µmol m−2 d−1 isoprene are determined where a positive flux indicates from the ocean to the atmosphere. Methanol was largely undersaturated in the surface ocean with a mean (±1σ) net flux of −2.4 (±4.7) µmol m−2 d−1, but it also had a few occasional episodes of outgassing. This section of the Southern Ocean was found to be a source and a sink for acetone and acetaldehyde this time of the year, depending on location, resulting in a mean net flux of −0.55 (±1.14) µmol m−2 d−1 for acetone and −0.28 (±1.22) µmol m−2 d−1 for acetaldehyde. The data collected here will be important for constraining the air–sea exchange, cycling, and atmospheric impact of these gases, especially over the Southern Ocean.
    Type of Medium: Online Resource
    ISSN: 1726-4189
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2020
    detail.hit.zdb_id: 2158181-2
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  • 6
    Online Resource
    Online Resource
    Copernicus GmbH ; 2021
    In:  Atmospheric Chemistry and Physics Vol. 21, No. 13 ( 2021-07-06), p. 10111-10132
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 21, No. 13 ( 2021-07-06), p. 10111-10132
    Abstract: Abstract. Volatile organic compounds (VOCs) are ubiquitous in the atmosphere and are important for atmospheric chemistry. Large uncertainties remain in the role of the ocean in the atmospheric VOC budget because of poorly constrained marine sources and sinks. There are very few direct measurements of air–sea VOC fluxes near the coast, where natural marine emissions could influence coastal air quality (i.e. ozone, aerosols) and terrestrial gaseous emissions could be taken up by the coastal seas. To address this, we present air–sea flux measurements of acetone, acetaldehyde and dimethylsulfide (DMS) at the coastal Penlee Point Atmospheric Observatory (PPAO) in the south-west UK during the spring (April–May 2018). Fluxes of these gases were measured simultaneously by eddy covariance (EC) using a proton-transfer-reaction quadrupole mass spectrometer. Comparisons are made between two wind sectors representative of different air–water exchange regimes: the open-water sector facing the North Atlantic Ocean and the terrestrially influenced Plymouth Sound fed by two estuaries. Mean EC (± 1 standard error) fluxes of acetone, acetaldehyde and DMS from the open-water wind sector were −8.0 ± 0.8, −1.6 ± 1.4 and 4.7 ± 0.6 µmol m−2 d−1 respectively (“−” sign indicates net air-to-sea deposition). These measurements are generally comparable (same order of magnitude) to previous measurements in the eastern North Atlantic Ocean at the same latitude. In comparison, the Plymouth Sound wind sector showed respective fluxes of −12.9 ± 1.4, −4.5 ± 1.7 and 1.8 ± 0.8 µmol m−2 d−1. The greater deposition fluxes of acetone and acetaldehyde within the Plymouth Sound were likely to a large degree driven by higher atmospheric concentrations from the terrestrial wind sector. The reduced DMS emission from the Plymouth Sound was caused by a combination of lower wind speed and likely lower dissolved concentrations as a result of the estuarine influence (i.e. dilution). In addition, we measured the near-surface seawater concentrations of acetone, acetaldehyde, DMS and isoprene from a marine station 6 km offshore. Comparisons are made between EC fluxes from the open-water and bulk air–sea VOC fluxes calculated using air and water concentrations with a two-layer (TL) model of gas transfer. The calculated TL fluxes agree with the EC measurements with respect to the directions and magnitudes of fluxes, implying that any recently proposed surface emissions of acetone and acetaldehyde would be within the propagated uncertainty of 2.6 µmol m−2 d−1. The computed transfer velocities of DMS, acetone and acetaldehyde from the EC fluxes and air and water concentrations are largely consistent with previous transfer velocity estimates from the open ocean. This suggests that wind, rather than bottom-driven turbulence and current velocity, is the main driver for gas exchange within the open-water sector at PPAO (depth of ∼ 20 m).
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2021
    detail.hit.zdb_id: 2092549-9
    detail.hit.zdb_id: 2069847-1
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  • 7
    Online Resource
    Online Resource
    Springer Science and Business Media LLC ; 2021
    In:  Scientific Reports Vol. 11, No. 1 ( 2021-06-30)
    In: Scientific Reports, Springer Science and Business Media LLC, Vol. 11, No. 1 ( 2021-06-30)
    Abstract: The flux of CO 2 between the atmosphere and the ocean is often estimated as the air–sea gas concentration difference multiplied by the gas transfer velocity ( K 660 ). The first order driver for K 660 over the ocean is wind through its influence on near surface hydrodynamics. However, field observations have shown substantial variability in the wind speed dependencies of K 660 . In this study we measured K 660 with the eddy covariance technique during a ~ 11,000 km long Southern Ocean transect. In parallel, we made a novel measurement of the gas transfer efficiency (GTE) based on partial equilibration of CO 2 using a Segmented Flow Coil Equilibrator system. GTE varied by 20% during the transect, was distinct in different water masses, and related to K 660 . At a moderate wind speed of 7 m s −1 , K 660 associated with high GTE exceeded K 660 with low GTE by 30% in the mean. The sensitivity of K 660 towards GTE was stronger at lower wind speeds and weaker at higher wind speeds. Naturally-occurring organics in seawater, some of which are surface active, may be the cause of the variability in GTE and in K 660 . Neglecting these variations could result in biases in the computed air–sea CO 2 fluxes.
    Type of Medium: Online Resource
    ISSN: 2045-2322
    Language: English
    Publisher: Springer Science and Business Media LLC
    Publication Date: 2021
    detail.hit.zdb_id: 2615211-3
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  • 8
    In: Oceans, MDPI AG, Vol. 4, No. 2 ( 2023-04-04), p. 151-169
    Abstract: A range of volatile organic compounds (VOCs) have been found to be released during zooplankton grazing on microalgae cultivated for commercial purposes. However, production of grazing-derived VOCs from environmentally relevant species and their potential contribution to oceanic emissions to the atmosphere remains largely unexplored. Here, we aimed to qualitatively explore the suite of VOCs produced due to grazing using laboratory cultures of the marine microalga Isochrysis galbana and the herbivorous heterotrophic dinoflagellate Oxyrrhis marina with and without antibiotic treatment. The VOCs were measured using a Vocus proton-transfer-reaction time-of-flight mass spectrometer, coupled to a segmented flow coil equilibrator. We found alternative increases of dimethyl sulfide by up to 0.2 nmol dm−3 and methanethiol by up to 10 pmol dm−3 depending on the presence or absence of bacteria regulated by antibiotic treatment. Additionally, toluene and xylene increased by about 30 pmol dm−3 and 10 pmol dm−3, respectively during grazing only, supporting a biological source for these compounds. Overall, our results highlight that VOCs beyond dimethyl sulfide are released due to grazing, and prompt further quantification of this source in budgets and process-based understanding of VOC cycling in the surface ocean.
    Type of Medium: Online Resource
    ISSN: 2673-1924
    Language: English
    Publisher: MDPI AG
    Publication Date: 2023
    detail.hit.zdb_id: 3010033-1
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