ALBERT

Description: Oxygen-deficient zones (ODZs) are major sites of net natural nitrous oxide (N2O) production and emissions. In order to understand changes in the magnitude of N2O production in response to global change, knowledge on the individual contributions of the major microbial pathways (nitrification and denitrification) to N2O production and their regulation is needed. In the ODZ in the coastal area off Peru, the sensitivity of N2O production to oxygen and organic matter was investigated using 15N tracer experiments in combination with quantitative PCR (qPCR) and microarray analysis of total and active functional genes targeting archaeal amoA and nirS as marker genes for nitrification and denitrification, respectively. Denitrification was responsible for the highest N2O production with a mean of 8.7 nmol L−1 d−1 but up to 118±27.8 nmol L−1 d−1 just below the oxic–anoxic interface. The highest N2O production from ammonium oxidation (AO) of 0.16±0.003 nmol L−1 d−1 occurred in the upper oxycline at O2 concentrations of 10–30 µmol L−1 which coincided with the highest archaeal amoA transcripts/genes. Hybrid N2O formation (i.e., N2O with one N atom from NH4+ and the other from other substrates such as NO2-) was the dominant species, comprising 70 %–85 % of total produced N2O from NH4+, regardless of the ammonium oxidation rate or O2 concentrations. Oxygen responses of N2O production varied with substrate, but production and yields were generally highest below 10 µmol L−1 O2. Particulate organic matter additions increased N2O production by denitrification up to 5-fold, suggesting increased N2O production during times of high particulate organic matter export. High N2O yields of 2.1 % from AO were measured, but the overall contribution by AO to N2O production was still an order of magnitude lower than that of denitrification. Hence, these findings show that denitrification is the most important N2O production process in low-oxygen conditions fueled by organic carbon supply, which implies a positive feedback of the total oceanic N2O sources in response to increasing oceanic deoxygenation.

Description: Coastal areas contribute significantly to the emissions of methane (CH4) from the ocean. In order to decipher its temporal variability in the whole water column, dissolved CH4 was measured on a monthly basis at the Boknis Eck Time Series Station (BE) located in Eckernförde Bay (SW Baltic Sea) from 2006 to 2017. BE has a water depth of about 28 m, and dissolved CH4 was measured at six water depths ranging from 0 to 25 m. In general, CH4 concentrations increased with depth, indicating a sedimentary release of CH4. Pronounced enhancement of the CH4 concentrations in the bottom layer (15–25 m) was found during February, May–June and October. CH4 was not correlated with Chlorophyll a or O2 over the measurement period. Unusually high CH4 concentrations (of up to 696 nM) were sporadically observed in the upper layer (0–10 m; e.g., in November 2013 and December 2014) and coincided with major Baltic inflow (MBI) events. Surface CH4 concentrations were always supersaturated throughout the monitoring period, indicating that Eckernförde Bay is an intense but highly variable source of atmospheric CH4. We did not detect significant temporal trends in CH4 concentrations or emissions, despite ongoing environmental changes such as warming and deoxygenation in Eckernförde Bay. Overall, the CH4 variability at BE is driven by a complex interplay of various biological and physical processes.

Description: The flow (flux) of climate-critical gases, such as carbon dioxide (CO2), between the ocean and the atmosphere is a fundamental component of our climate and an important driver of the biogeochemical systems within the oceans. Therefore, the accurate calculation of these air–sea gas fluxes is critical if we are to monitor the oceans and assess the impact that these gases are having on Earth's climate and ecosystems. FluxEngine is an open-source software toolbox that allows users to easily perform calculations of air–sea gas fluxes from model, in situ, and Earth observation data. The original development and verification of the toolbox was described in a previous publication. The toolbox has now been considerably updated to allow for its use as a Python library, to enable simplified installation, to ensure verification of its installation, to enable the handling of multiple sparingly soluble gases, and to enable the greatly expanded functionality for supporting in situ dataset analyses. This new functionality for supporting in situ analyses includes user-defined grids, time periods and projections, the ability to reanalyse in situ CO2 data to a common temperature dataset, and the ability to easily calculate gas fluxes using in situ data from drifting buoys, fixed moorings, and research cruises. Here we describe these new capabilities and demonstrate their application through illustrative case studies. The first case study demonstrates the workflow for accurately calculating CO2 fluxes using in situ data from four research cruises from the Surface Ocean CO2 ATlas (SOCAT) database. The second case study calculates air–sea CO2 fluxes using in situ data from a fixed monitoring station in the Baltic Sea. The third case study focuses on nitrous oxide (N2O) and, through a user-defined gas transfer parameterisation, identifies that biological surfactants in the North Atlantic could suppress individual N2O sea–air gas fluxes by up to 13 %. The fourth and final case study illustrates how a dissipation-based gas transfer parameterisation can be implemented and used. The updated version of the toolbox (version 3) and all documentation is now freely available.

Description: Coastal seas may account for more than 75 % of global oceanic methane emissions. There, methane is mainly produced microbially in anoxic sediments from which it can escape to the overlying water column. Aerobic methane oxidation (MOx) in the water column acts as a biological filter, reducing the amount of methane that eventually evades to the atmosphere. The efficiency of the MOx filter is potentially controlled by the availability of dissolved methane and oxygen, as well as temperature, salinity, and hydrographic dynamics, and all of these factors undergo strong temporal fluctuations in coastal ecosystems. In order to elucidate the key environmental controls, specifically the effect of oxygen availability, on MOx in a seasonally stratified and hypoxic coastal marine setting, we conducted a 2-year time-series study with measurements of MOx and physico-chemical water column parameters in a coastal inlet in the south-western Baltic Sea (Eckernförde Bay). We found that MOx rates generally increased toward the seafloor, but were not directly linked to methane concentrations. MOx exhibited a strong seasonal variability, with maximum rates (up to 11.6 nmol L−1 d−1) during summer stratification when oxygen concentrations were lowest and bottom-water temperatures were highest. Under these conditions, 2.4–19.0 times more methane was oxidized than emitted to the atmosphere, whereas about the same amount was consumed and emitted during the mixed and oxygenated periods. Laboratory experiments with manipulated oxygen concentrations in the range of 0.2–220 µmol L−1 revealed a submicromolar oxygen optimum for MOx at the study site. In contrast, the fraction of methane–carbon incorporation into the bacterial biomass (compared to the total amount of oxidized methane) was up to 38-fold higher at saturated oxygen concentrations, suggesting a different partitioning of catabolic and anabolic processes under oxygen-replete and oxygen-starved conditions, respectively. Our results underscore the importance of MOx in mitigating methane emission from coastal waters and indicate an organism-level adaptation of the water column methanotrophs to hypoxic conditions.

Description: We developed a new method for the determination of dissolved nitric oxide (NO) in discrete seawater samples based on the combination of a purge-and-trap setup and a fluorometric detection of NO. 2,3-diaminonaphthalene (DAN) reacts with NO in seawater to form the highly fluorescent 2,3-naphthotriazole (NAT). The fluorescence intensity was linear for NO concentrations in the range from 0.14 to 19 nmol L−1. We determined a detection limit of 0.068 nmol L−1, an average recovery coefficient of 83.8 % (80.2–90.0 %), and a relative standard deviation of ±7.2 %. With our method we determined for the first time the temporal and spatial distributions of NO surface concentrations in coastal waters of the Yellow Sea off Qingdao and in Jiaozhou Bay during a cruise in November 2009. The concentrations of NO varied from below the detection limit to 0.50 nmol L−1 with an average of 0.26 ± 0.14 nmol L−1. NO surface concentrations were generally enhanced significantly during daytime, implying that NO formation processes such as NO2− photolysis are much higher during daytime than chemical NO consumption, which, in turn, lead to a significant decrease in NO concentrations during nighttime. In general, NO surface concentrations and measured NO production rates were higher compared to previously reported measurements. This might be caused by the high NO2− surface concentrations encountered during the cruise. Moreover, additional measurements of NO production rates implied that the occurrence of particles and a temperature increase can enhance NO production rates. With the method introduced here, we have a reliable and comparably easy to use method at hand to measure oceanic NO surface concentrations, which can be used to decipher both its temporal and spatial distributions as well as its biogeochemical pathways in the oceans.

Description: We developed a new method for the determination of dissolved nitric oxide (NO) in discrete seawater samples based on a combination of a purge-and-trap set-up and fluorometric detection of NO. 2,3-diaminonaphthalene (DAN) reacts with NO in seawater to form the highly fluorescent 2,3-naphthotriazole (NAT). The fluorescence intensity was linear for NO concentrations in the range from 0.14 nmol L−1 to 19 nmol L−1. We determined a detection limit of 0.068 nmol L−1, an average recovery coefficient of 83.8 % (80.2–90.0 %), and a relative standard deviation of ±7.2 %. With our method we determined for the first time the temporal and spatial distributions of NO surface concentrations in coastal waters of the Yellow Sea off Qingdao and in Jiaozhou Bay during a cruise in November 2009. The concentrations of NO varied from below the detection limit to 0.50 nmol L−1 with an average of 0.26 ± 0.14 nmol L−1. NO surface concentrations were generally enhanced significantly during daytime implying that NO formation processes such as NO2− photolysis are much higher during daytime than chemical NO consumption which, in turn, lead to a significant decrease of NO concentrations during nighttime. In general, NO surface concentrations and measured NO production rates were higher compared to previously reported measurements. This might be caused by the high NO2− surface concentrations encountered during the cruise. Moreover, additional measurements of NO production rates implied that the occurrence of particles and a temperature increase can enhance NO production rates. With the method introduced here we have a reliable and comparably easy to use method at hand to measure oceanic NO surface concentrations which can be used to decipher both its temporal and spatial distributions as well as its biogeochemical pathways in the oceans.

Description: The flow (flux) of climate critical gases, such as carbon dioxide (CO2), between the ocean and the atmosphere is a fundamental component of our climate and the biogeochemical development of the oceans. Therefore, the accurate calculation of these air-sea gas fluxes is critical if we are to monitor the health of our oceans and changes to our climate. FluxEngine is an open source software toolbox that allows users to easily perform calculations of air-sea gas fluxes from model, in-situ and Earth observation data. The original development and verification of the toolbox was described in a previous publication and the toolbox is already being used by scientists across multiple disciplines. The toolbox has now been considerably updated to allow its use as a Python library, to enable simplified installation, verification of its installation, to enable the handling of multiple sparingly soluble gases and greatly expanded functionality for supporting in situ dataset analyses. This new functionality for supporting in situ analyses includes user defined grids, time periods and projections, the ability to re-analyse in situ CO2 data to a common temperature dataset and the ability to easily calculate gas fluxes using in situ data from drifting buoys, fixed moorings and research cruises. Here we describe these new capabilities and then demonstrate their application through illustrative case studies. The first case study demonstrates the workflow for accurately calculating CO2 fluxes using in situ data from four research cruises from the Surface Ocean CO2 Atlas (SOCAT) database. The second case study shows that reanalysing an eight month time series of pCO2 data collected from a fixed station in the Baltic Sea can remove errors equal to 35 % of the net air-sea gas flux. The third case study demonstrates that biological surfactants could supress individual nitrous oxide sea-air gas fluxes by up to 13 %. The final case study illustrates how a dissipation-based gas transfer parameterisation can be implemented and used. The updated version of the toolbox (version 3) and all documentation is now freely available.

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: The presence of surface methanogenesis, located within the sulfate-reducing zone (0–30 centimeters below seafloor, cmbsf), was investigated in sediments of the seasonally hypoxic Eckernförde Bay, southwestern Baltic Sea. Water column parameters like oxygen, temperature and salinity together with porewater geochemistry and benthic methanogenesis rates were determined in the sampling area ''Boknis Eck'' quarterly from March 2013 to September 2014, to investigate the effect of seasonal environmental changes on the rate and distribution of surface methanogenesis and to estimate its potential contribution to benthic methane emissions. The metabolic pathway of methanogenesis in the presence or absence of sulfate reducers and after the addition of a non-competitive substrate was studied in four experimental setups: 1) unaltered sediment batch incubations (net methanogenesis), 2) 14C-bicarbonate labeling experiments (hydrogenotrophic methanogenesis), 3) manipulated experiments with addition of either molybdate (sulfate reducer inhibitor), 2-bromoethane-sulfonate (methanogen inhibitor), or methanol (non-competitive substrate, potential methanogenesis), 4) addition of 13C-labeled methanol (potential methylotrophic methanogenesis). After incubation with methanol in the manipulated experiments, molecular analyses were conducted to identify key functional methanogenic groups. Hydrogenotrophic methanogenesis in sediments below the sulfate-reducing zone (〉 30 cmbsf) was determined by 14C-bicarbonate radiotracer incubation in samples collected in September 2013. Surface methanogenesis changed seasonally in the upper 30 cmbsf with rates increasing from March (0.2 nmol cm−3 d−1) to November (1.3 nmol cm−3 d−1) 2013 and March (0.2 nmol cm−3 d−1) to September (0.4 nmol cm−3 d−1) 2014, respectively. Its magnitude and distribution appeared to be controlled by organic matter availability, C / N, temperature, and oxygen in the water column, revealing higher rates in warm, stratified, hypoxic seasons (September/November) compared to colder, oxygenated seasons (March/June) of each year. The majority of surface methanogenesis was likely driven by the usage of non-competitive substrates (e.g., methanol and methylated compounds), to avoid competition with sulfate reducers, as it was indicated by the 1000–3000-fold increase in potential methanogenesis activity observed after methanol addition. Accordingly, competitive hydrogenotrophic methanogenesis increased in the sediment only below the depth of sulfate penetration (〉 30 cmbsf). Members of the family Methanosarcinaceae, which are known for methylotrophic methanogenesis, were detected by PCR using Methanosarcinaceae-specific primers and are likely to be responsible for the observed surface methanogenesis. The present study indicated that surface methanogenesis makes an important contribute to the benthic methane budget of Eckernförde Bay sediments as it could directly feed into methane oxidation above the sulfate-methane transition zone.

Description: Nitric oxide (NO) is a short-lived compound of the marine nitrogen cycle; however, our knowledge about its oceanic distribution and turnover is rudimentary. Here we present the measurements of dissolved NO in the surface and bottom layers at 75 stations in the Bohai Sea (BS) and the Yellow Sea (YS) in June 2011. Moreover, NO photoproduction rates were determined at 27 stations in both seas. The NO concentrations in the surface and bottom layers were highly variable and ranged from below the limit of detection (i.e., 32 pmol L−1) to 616 pmol L−1 in the surface layer and 482 pmol L−1 in the bottom layer. There was no significant difference (p〉0.05) between the mean NO concentrations in the surface (186±108 pmol L−1) and bottom (174±123 pmol L−1) layers. A decreasing trend of NO in bottom-layer concentrations with salinity indicates a NO input by submarine groundwater discharge. NO in the surface layer was supersaturated at all stations during both day and night and therefore the BS and YS were a persistent source of NO to the atmosphere at the time of our measurements. The average flux was about 4.5×10-16 mol cm−2 s−1 and the flux showed significant positive relationship with the wind speed. The accumulation of NO during daytime was a result of photochemical production, and photoproduction rates were correlated to illuminance. The persistent nighttime NO supersaturation pointed to an unidentified NO dark production. NO sea-to-air flux densities were much lower than the NO photoproduction rates. Therefore, we conclude that the bulk of the NO produced in the mixed layer was rapidly consumed before its release to the atmosphere.