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  • 1
    Publication Date: 2021-02-08
    Description: Large-scale climatic forcing is impacting oceanic biogeochemical cycles and is expected to influence the water-column distribution of trace gases, including methane and nitrous oxide. Our ability as a scientific community to evaluate changes in the water-column inventories of methane and nitrous oxide depends largely on our capacity to obtain robust and accurate concentration measurements that can be validated across different laboratory groups. This study represents the first formal international intercomparison of oceanic methane and nitrous oxide measurements whereby participating laboratories received batches of seawater samples from the subtropical Pacific Ocean and the Baltic Sea. Additionally, compressed gas standards from the same calibration scale were distributed to the majority of participating laboratories to improve the analytical accuracy of the gas measurements. The computations used by each laboratory to derive the dissolved gas concentrations were also evaluated for inconsistencies (e.g., pressure and temperature corrections, solubility constants). The results from the intercomparison and intercalibration provided invaluable insights into methane and nitrous oxide measurements. It was observed that analyses of seawater samples with the lowest concentrations of methane and nitrous oxide had the lowest precisions. In comparison, while the analytical precision for samples with the highest concentrations of trace gases was better, the variability between the different laboratories was higher: 36% for methane and 27% for nitrous oxide. In addition, the comparison of different batches of seawater samples with methane and nitrous oxide concentrations that ranged over an order of magnitude revealed the ramifications of different calibration procedures for each trace gas. Finally, this study builds upon the intercomparison results to develop recommendations for improving oceanic methane and nitrous oxide measurements, with the aim of precluding future analytical discrepancies between laboratories.
    Type: Article , PeerReviewed , info:eu-repo/semantics/article
    Format: text
    Format: archive
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  • 2
    Publication Date: 2019-07-11
    Description: We present measurements of pCO2, O2 concentration, biological oxygen saturation (ΔO2/Ar), and N2 saturation (ΔN2) in Southern Ocean surface waters during austral summer, 2010–2011. Phytoplankton biomass varied strongly across distinct hydrographic zones, with high chlorophyll a (Chl a) concentrations in regions of frontal mixing and sea ice melt. pCO2 and ΔO2/Ar exhibited large spatial gradients (range 90 to 450 µatm and −10 to 60%, respectively) and covaried strongly with Chl a. However, the ratio of biological O2 accumulation to dissolved inorganic carbon (DIC) drawdown was significantly lower than expected from photosynthetic stoichiometry, reflecting the differential time scales of O2 and CO2 air-sea equilibration. We measured significant oceanic CO2 uptake, with a mean air-sea flux (~ −10 mmol m−2 d−1) that significantly exceeded regional climatological values. N2 was mostly supersaturated in surface waters (mean ΔN2 of +2.5%), while physical processes resulted in both supersaturation and undersaturation of mixed layer O2 (mean ΔO2phys = 2.1%). Box model calculations were able to reproduce much of the spatial variability of ΔN2 and ΔO2phys along the cruise track, demonstrating significant effects of air-sea exchange processes (e.g., atmospheric pressure changes and bubble injection) and mixed layer entrainment on surface gas disequilibria. Net community production (NCP) derived from entrainment-corrected surface ΔO2/Ar data, ranged from ~ −40 to 〉 300 mmol O2 m−2 d−1 and showed good coherence with independent NCP estimates based on seasonal mixed layer DIC deficits. Elevated NCP was observed in hydrographic frontal zones and stratified regions of sea ice melt, reflecting physical controls on surface water light fields and nutrient availability.
    Type: Article , PeerReviewed , info:eu-repo/semantics/article
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  • 3
    Publication Date: 2022-01-31
    Description: Nitrous oxide (N2O) is an important atmospheric trace gas involved in tropospheric warming and stratospheric ozone depletion. Estimates of the global ocean contribution to N2O emissions average 21% (range: 10 to 53%). Ongoing environmental changes such as warming, deoxygenation and acidification are affecting oceanic N2O cycling and emissions to the atmosphere. International activities over the last decades aimed at improving estimates of global N2O emissions, including (i) the MarinE MethanE and NiTrous Oxide database (MEMENTO) for archiving of quality-controlled data, and (ii) a recent large-scale inter-laboratory comparison by Working Group 143 of the Scientific Committee on Ocean Research (SCOR). To reduce uncertainties in oceanic N2O emission estimates and to characterize the spatial and temporal variability in N2O distributions in a changing ocean, we propose the establishment of a harmonized N2O Observation Network (N2O-ON) combining discrete and continuous data from various platforms. The network will integrate observations obtained by calibrated techniques, using time series measurements at fixed stations and repeated hydrographic sections on voluntary observing ships and research vessels. In addition to exploiting existing oceanographic infrastructure, we propose the establishment of central calibration facilities in selected international laboratories to improve accuracy, and ensure standardization and comparability of N2O measurements. Final data products will include a harmonized global N2O concentration and emission fields for use in model validation and projections of future oceanic N2O emissions, to inform the global research community and policy makers.
    Type: Article , PeerReviewed , info:eu-repo/semantics/article
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  • 4
    Publication Date: 2017-02-10
    Repository Name: EPIC Alfred Wegener Institut
    Type: Conference , notRev
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  • 5
    Publication Date: 2018-05-31
    Description: The Arctic and subarctic shelf seas, which sustain large fisheries and contribute to global biogeochemical cycling, are particularly sensitive to ongoing ocean acidification (that is, decreasing seawater pH due to anthropogenic CO2 emissions). Yet, little information is available on the effects of ocean acidification on natural phytoplankton assemblages, which are the main primary producers in high-latitude waters. Here we show that coastal Arctic and subarctic primary production is largely insensitive to ocean acidification over a large range of light and temperature levels in different experimental designs. Out of ten CO2-manipulation treatments, significant ocean acidification effects on primary productivity were observed only once (at temperatures below 2 °C), and shifts in the species composition occurred only three times (without correlation to specific experimental conditions). These results imply a high capacity to compensate for environmental variability, which can be understood in light of the environmental history, tolerance ranges and intraspecific diversity of the dominant phytoplankton species.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
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  • 6
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2015. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Oceans 120 (2015): 3542-3566, doi:10.1002/2014JC010620.
    Description: We present the results of a 6 week time series of carbonate system and stable isotope measurements investigating the effects of sea ice on air-sea CO2 exchange during the early melt period in the Canadian Arctic Archipelago. Our observations revealed significant changes in sea ice and sackhole brine carbonate system parameters that were associated with increasing temperatures and the buildup of chlorophyll a in bottom ice. The warming sea-ice column could be separated into distinct geochemical zones where biotic and abiotic processes exerted different influences on inorganic carbon and pCO2 distributions. In the bottom ice, biological carbon uptake maintained undersaturated pCO2 conditions throughout the time series, while pCO2 was supersaturated in the upper ice. Low CO2 permeability of the sea ice matrix and snow cover effectively impeded CO2 efflux to the atmosphere, despite a strong pCO2 gradient. Throughout the middle of the ice column, brine pCO2 decreased significantly with time and was tightly controlled by solubility, as sea ice temperature and in situ melt dilution increased. Once the influence of melt dilution was accounted for, both CaCO3 dissolution and seawater mixing were found to contribute alkalinity and dissolved inorganic carbon to brines, with the CaCO3 contribution driving brine pCO2 to values lower than predicted from melt-water dilution alone. This field study reveals a dynamic carbon system within the rapidly warming sea ice, prior to snow melt. We suggest that the early spring period drives the ice column toward pCO2 undersaturation, contributing to a weak atmospheric CO2 sink as the melt period advances.
    Description: We acknowledge support from the Polar Continental Shelf Program (PCSP) of Natural Resources Canada, the Natural Sciences and Engineering Research Council of Canada, the Northern Scientific Training Program, Canada Economic Development, and Fisheries and Oceans Canada.
    Description: 2015-11-19
    Keywords: Sea ice ; Carbon cycling ; CO2 ; Brines ; Stable isotopes ; Arctic Ocean
    Repository Name: Woods Hole Open Access Server
    Type: Article
    Format: application/pdf
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  • 7
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2017. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Oceans 122 (2017): 3269–3286, doi:10.1002/2016JC012465.
    Description: Concentrations of dimethylsulfide (DMS), measured in the Subarctic Pacific during summer 2010 and 2011, ranged from ∼1 to 40 nM, while dissolved dimethylsulfoxide (DMSO) concentrations (range 13-23 nM) exceeded those of dissolved dimethyl sulfoniopropionate (DMSP) (range 1.3–8.8 nM). Particulate DMSP dominated the reduced sulfur pool, reaching maximum concentrations of 100 nM. Coastal and off shore waters exhibited similar overall DMS concentration ranges, but sea-air DMS fluxes were lower in the oceanic waters due to lower wind speeds. Surface DMS concentrations showed statistically significant correlations with various hydrographic variables including the upwelling intensity (r2 = 0.52, p 〈 0.001) and the Chlorophyll a/mixed layer depth ratio (r2 = 0.52, p 〈 0.001), but these relationships provided little predictive power at small scales. Stable isotope tracer experiments indicated that the DMSP cleavage pathway always exceeded the DMSO reduction pathway as a DMS source, leading to at least 85% more DMS production in each experiment. Gross DMS production rates were positively correlated with the upwelling intensity, while net rates of DMS production were significantly correlated to surface water DMS concentrations. This latter result suggests that our measurements captured dominant processes driving surface DMS accumulation across a coastal-oceanic gradient.
    Description: Natural Sciences and Engineering Research Council of Canada, from the Peter Wall Institute for Advanced Studies
    Description: 2017-10-24
    Keywords: Dimethylsulfide ; DMSP ; DMSO ; DMS turnover ; Rate measurements ; Isotopic tracers ; Sea-air flux ; Upwelling
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 8
    Publication Date: 2022-05-25
    Description: © The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 15 (2018): 2449–2465, doi:10.5194/bg-15-2449-2018.
    Description: We present seawater concentrations of dimethyl sulfide (DMS) and dimethylsulfoniopropionate (DMSP) measured across a transect from the Labrador Sea to the Canadian Arctic Archipelago during summer 2015. Using an automated ship-board gas chromatography system and a membrane-inlet mass spectrometer, we measured a wide range of DMS (∼ 1 to 18 nM) and DMSP (∼ 1 to 150 nM) concentrations. The highest DMS and DMSP concentrations occurred in a localized region of Baffin Bay, where surface waters were characterized by high chlorophyll a (chl a) fluorescence, indicative of elevated phytoplankton biomass. Across the full sampling transect, there were only weak relationships between DMS(P), chl a fluorescence and other measured variables, including positive relationships between DMSP : chl a ratios and several taxonomic marker pigments, and elevated DMS(P) concentrations in partially ice-covered areas. Our high spatial resolution measurements allowed us to examine DMS variability over small scales (〈 1 km), documenting strong DMS concentration gradients across surface hydrographic frontal features. Our new observations fill in an important observational gap in the Arctic Ocean and provide additional information on sea–air DMS fluxes from this ocean region. In addition, this study constitutes a significant contribution to the existing Arctic DMS(P) dataset and provides a baseline for future measurements in the region.
    Description: This work was supported by grants from the Natural Sciences and Engineering Research Council of Canada (NSERC) through the Climate Change and Atmospheric Research program (Arctic-GEOTRACES).
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 9
    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 Journal of Geophysical Research: Oceans 121 (2016): 2918–2936, doi:10.1002/2015JC011535.
    Description: We examine the dissolved inorganic carbon maximum in the Canada Basin halocline using a suite of geochemical tracers to gain insight into the factors that contribute to the persistence of this feature. Hydrographic and geochemical samples were collected in the upper 500 m of the southwestern Canada Basin water column in the summer of 2008 and fall of 2009. These observations were used to identify conservative and nonconservative processes that contribute dissolved inorganic carbon to halocline source waters, including shelf sediment organic matter remineralization, air-sea gas exchange, and sea-ice brine export. Our results indicate that the remineralization of organic matter that occurs along the Bering and Chukchi Sea shelves is the overwhelming contributor of dissolved inorganic carbon to Pacific Winter Water that occupies the middle halocline in the southwestern Canada Basin. Nonconservative contributions from air-sea exchange and sea-ice brine are not significant. The broad salinity range associated with the DIC maximum, compared to the narrow salinity range of the nutrient maximum, is due to mixing between Pacific and Atlantic water and not abiotic addition of DIC.
    Description: NSERC; Fisheries and Oceans Canada; US National Science Foundation Office of Polar Programs Grant Number: OPP-0424864; Canadian International Polar Year Office
    Description: 2016-11-04
    Keywords: Arctic Ocean ; Dissolved inorganic carbon ; Nutrients ; Stable isotopes ; Shelf-basin CO2 pump
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 10
    Publication Date: 2022-05-25
    Description: © The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 15 (2018): 5891-5907, doi:10.5194/bg-15-5891-2018.
    Description: Large-scale climatic forcing is impacting oceanic biogeochemical cycles and is expected to influence the water-column distribution of trace gases, including methane and nitrous oxide. Our ability as a scientific community to evaluate changes in the water-column inventories of methane and nitrous oxide depends largely on our capacity to obtain robust and accurate concentration measurements that can be validated across different laboratory groups. This study represents the first formal international intercomparison of oceanic methane and nitrous oxide measurements whereby participating laboratories received batches of seawater samples from the subtropical Pacific Ocean and the Baltic Sea. Additionally, compressed gas standards from the same calibration scale were distributed to the majority of participating laboratories to improve the analytical accuracy of the gas measurements. The computations used by each laboratory to derive the dissolved gas concentrations were also evaluated for inconsistencies (e.g., pressure and temperature corrections, solubility constants). The results from the intercomparison and intercalibration provided invaluable insights into methane and nitrous oxide measurements. It was observed that analyses of seawater samples with the lowest concentrations of methane and nitrous oxide had the lowest precisions. In comparison, while the analytical precision for samples with the highest concentrations of trace gases was better, the variability between the different laboratories was higher: 36% for methane and 27% for nitrous oxide. In addition, the comparison of different batches of seawater samples with methane and nitrous oxide concentrations that ranged over an order of magnitude revealed the ramifications of different calibration procedures for each trace gas. Finally, this study builds upon the intercomparison results to develop recommendations for improving oceanic methane and nitrous oxide measurements, with the aim of precluding future analytical discrepancies between laboratories.
    Description: U.S. National Science Foundation (OCE-1546580); Funding for the gas standards was provided by the Center for Microbial Oceanography: Research and Education (C-MORE; EF0424599 to David M. Karl), SCOR, the EU FP7 funded Integrated non-CO2 Greenhouse gas Observation System (InGOS) (grant agreement no. 284274), and NOAA’s Climate Program Office, Climate Observations Division. Additional support was provided by the Gordon and Betty Moore Foundation no. 3794 (David M. Karl), the Simons Collaboration on Ocean Processes and Ecology (SCOPE; no. 329108 to David M. Karl), and the Global Research Laboratory Program (no. 2013K1A1A2A02078278 to David M. Karl) through the National Research Foundation of Korea (NRF); Alyson E. Santoro would like to acknowledge NSF OCE-1437310. Mercedes de la Paz would like to acknowledge the support of the Spanish Ministry of Economy and Competitiveness (CTM2015-74510-JIN). Laura Farías received financial support from FONDAP 1511009 and FONDECYT no. 1161138
    Repository Name: Woods Hole Open Access Server
    Type: Article
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