Description: Nitrous oxide (N2O) is a climate relevant trace gas, and its production in the ocean generally increases under suboxic conditions. The Atlantic Ocean is well ventilated, and unlike the major oxygen minimum zones (OMZ) of the Pacific and Indian Oceans, dissolved oxygen and N2O concentrations in the Atlantic OMZ are relatively high and low, respectively. This study, however, demonstrates that recently discovered low oxygen eddies in the eastern tropical North Atlantic (ETNA) can produce N2O concentrations much higher (up to 115 nmol L−1) than those previously reported for the Atlantic Ocean, and which are within the range of the highest concentrations found in the open-ocean OMZs of the Pacific and Indian Oceans. N2O isotope and isotopomer signatures, as well as molecular genetic results, also point towards a major shift in the N2O cycling pathway in the core of the low oxygen eddy discussed here, and we report the first evidence for potential N2O cycling via the denitrification pathway in the open Atlantic Ocean. Finally, we consider the implications of low oxygen eddies for bulk, upper water column N2O at the regional scale, and point out the possible need for a reevaluation of how we view N2O cycling in the ETNA.

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: Nitrous oxide (N2O) is one of the most important greenhouse gases and a major sink for stratospheric ozone. Estuaries are sites of intense biological production and N2O emissions. We aimed to identify hot spots of N2O production and potential pathways contributing to N2O concentrations in the surface water of the tidal Elbe estuary. During two research cruises in April and June 2015, surface water N2O concentrations were measured along the salinity gradient of the Elbe estuary by using a laser-based on-line analyzer coupled to an equilibrator. Based on these high-resolution N2O profiles, N2O saturations, and fluxes across the surface water/atmosphere interface were calculated. Additional measurements of DIN concentrations, oxygen concentration, and salinity were performed. Highest N2O concentrations were determined in the Hamburg port region reaching maximum values of 32.3 nM in April 2015 and 52.2 nM in June 2015. These results identify the Hamburg port region as a significant hot spot of N2O production, where linear correlations of AOU-N2Oxs indicate nitrification as an important contributor to N2O production in the freshwater part. However, in the region with lowest oxygen saturation, sediment denitrification obviously affected water column N2O saturation. The average N2O saturation over the entire estuary was 201% (SD: ±94%), with an average estuarine N2O flux density of 48 μmol m−2 d−1 and an overall emission of 0.18 Gg N2O y−1. In comparison to previous studies, our data indicate that N2O production pathways over the whole estuarine freshwater part have changed from predominant denitrification in the 1980s toward significant production from nitrification in the present estuary. Despite a significant reduction in N2O saturation compared to the 1980s, N2O concentrations nowadays remain on a high level, comparable to the mid-90s, although a steady decrease of DIN inputs occurred over the last decades. Hence, the Elbe estuary still remains an important source of N2O to the atmosphere.

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 domain of the surface ocean and lower atmosphere is a complex, highly dynamic component of the Earth system. Better understanding of the physics and biogeochemistry of the air–sea interface and the processes that control the exchange of mass and energy across that boundary define the scope of the Surface Ocean-Lower Atmosphere Study (SOLAS) project. The scientific questions driving SOLAS research, as laid out in the SOLAS Science Plan and Implementation Strategy for the period 2004–2014, are highly challenging, inherently multidisciplinary and broad. During that decade, SOLAS has significantly advanced our knowledge. Discoveries related to the physics of exchange, global trace gas budgets and atmospheric chemistry, the CLAW hypothesis (named after its authors, Charlson, Lovelock, Andreae and Warren), and the influence of nutrients and ocean productivity on important biogeochemical cycles, have substantially changed our views of how the Earth system works and revealed knowledge gaps in our understanding. As such SOLAS has been instrumental in contributing to the International Geosphere–Biosphere Programme (IGBP) mission of identification and assessment of risks posed to society and ecosystems by major changes in the Earth’s biological, chemical and physical cycles and processes during the Anthropocene epoch. SOLAS is a bottom-up organization, whose scientific priorities evolve in response to scientific developments and community needs, which has led to the launch of a new 10-year phase. SOLAS (2015–2025) will focus on five core science themes that will provide a scientific basis for understanding and projecting future environmental change and for developing tools to inform societal decision-making.

Description: The tropical Atlantic exerts a major influence in climate variability through strong air-sea interactions. Within this region, the eastern side of the equatorial band is characterized by strong seasonality, whereby the most prominent feature is the annual development of the Atlantic Cold Tongue (ACT). This band of low sea surface temperatures (∼22-23°C) is typically associated with upwelling-driven enhancement of surface nutrient concentrations and primary production. Based on a detailed investigation of the distribution and sea-to-air fluxes of N2O in the eastern equatorial Atlantic (EEA), we show that the onset and seasonal development of the ACT can be clearly observed in surface N2O concentrations, which increase progressively as the cooling in the equatorial region proceeds during spring-summer. We observed a strong influence of the surface currents of the EEA on the N2O distribution, which allowed identifying “high” and “low” concentration regimes that were, in turn, spatially delimited by the extent of the warm eastward-flowing North Equatorial Countercurrent and the cold westward-flowing South Equatorial Current. Estimated sea-to-air fluxes of N2O from the ACT (mean 5.18±2.59 µmol m−2 d−1) suggests that in May-July 2011 this cold-water band doubled the N2O efflux to the atmosphere with respect to the adjacent regions, highlighting its relevance for marine tropical emissions of N2O. This article is protected by copyright. All rights reserved.

Description: Sea surface and atmospheric measurements of dimethylsulphide (DMS) were performed during the TransBrom cruise in the western Pacific Ocean between Japan and Australia in October 2009. Air–sea DMS fluxes were computed between 0 and 30 μmol m−2 d−1, which are in agreement with those computed by the current climatology, and peak emissions of marine DMS into the atmosphere were found during the occurrence of tropical storm systems. Atmospheric variability in DMS, however, did not follow that of the computed fluxes and was more related to atmospheric transport processes. The computed emissions were used as input fields for the Lagrangian dispersion model FLEXPART, which was set up with actual meteorological fields from ERA-Interim data and different chemical lifetimes of DMS. A comparison with aircraft in situ data from the adjacent HIPPO2 campaign revealed an overall good agreement between modelled versus observed DMS profiles over the tropical western Pacific Ocean. Based on observed DMS emissions and meteorological fields along the cruise track, the model projected that up to 30 g S per month in the form of DMS, emitted from an area of 6 × 104 m2, can be transported above 17 km. This surprisingly large DMS entrainment into the stratosphere is disproportionate to the regional extent of the area of emissions and mainly due to the high convective activity in this region as simulated by the transport model. Thus, if DMS can cross the tropical tropopause layer (TTL), we suggest that the considerably larger area of the tropical western Pacific Ocean can be a source of sulphur to the stratosphere, which has not been considered as yet.

Description: Microbial nitrous oxide (N2O) production in the ocean is enhanced under low-oxygen (O2) conditions. This is especially important in the context of increasing hypoxia (i.e., oceanic zones with extremely reduced O2 concentrations). Here, we present a study on the interannual variation in summertime nitrous oxide (N2O) concentrations in the bottom waters of the northern Gulf of Mexico (nGOM), which is well-known as the site of the second largest seasonally occurring hypoxic zone worldwide. To this end we developed a simple model that computes bottom-water N2O concentrations with a tri-linear 1N2O/O2 relationship based on water-column O2 concentrations, derived from summer (July) Texas–Louisiana shelf-wide hydrographic data between 1985 and 2007. 1N2O (i.e., excess N2O) was computed including nitrification and denitrification as the major microbial production and consumption pathways of N2O. The mean modeled bottom-water N2O concentration for July in the nGOM was 14.5±2.3 nmol L−1 (min: 11.0±4.5 nmol L−1 in 2000 and max: 20.6±11.3 nmol L−1 in 2002). The mean bottom-water N2O concentrations were significantly correlated with the areal extent of hypoxia in the nGOM. Our modeling analysis indicates that the nGOM is a persistent summer source of N2O, and nitrification is dominating N2O production in this region. Based on the ongoing increase in the areal extent of hypoxia in the nGOM, we conclude that N2O production (and its subsequent emissions)from this environmentally stressed region will probably continue to increase into the future.

Description: Ocean observations carried out in the framework of the Collaborative Research Center 754 (SFB 754) "Climate-Biogeochemistry Interactions in the Tropical Ocean" are used to study (1) the structure of tropical oxygen minimum zones (OMZs), (2) the processes that contribute to the oxygen budget, and (3) long-term changes in the oxygen distribution. The OMZ of the eastern tropical North Atlantic (ETNA), located between the well-ventilated subtropical gyre and the equatorial oxygen maximum, is composed of a deep OMZ at about 400 m depth with its core region centred at about 20° W, 10° N and a shallow OMZ at about 100 m depth with lowest oxygen concentrations in proximity to the coastal upwelling region off Mauritania and Senegal. The oxygen budget of the deep OMZ is given by oxygen consumption mainly balanced by the oxygen supply due to meridional eddy fluxes (about 60%) and vertical mixing (about 20%, locally up to 30%). Advection by zonal jets is crucial for the establishment of the equatorial oxygen maximum. In the latitude range of the deep OMZ, it dominates the oxygen supply in the upper 300 to 400 m and generates the intermediate oxygen maximum between deep and shallow OMZs. Water mass ages from transient tracers indicate substantially older water masses in the core of the deep OMZ (about 120–180 years) compared to regions north and south of it. The deoxygenation of the ETNA OMZ during recent decades suggests a substantial imbalance in the oxygen budget: about 10% of the oxygen consumption during that period was not balanced by ventilation. Long-term oxygen observations show variability on interannual, decadal and multidecadal time scales that can partly be attributed to circulation changes. In comparison to the ETNA OMZ the eastern tropical South Pacific OMZ shows a similar structure including an equatorial oxygen maximum driven by zonal advection, but overall much lower oxygen concentrations approaching zero in extended regions. As the shape of the OMZs is set by ocean circulation, the widespread misrepresentation of the intermediate circulation in ocean circulation models substantially contributes to their oxygen bias, which might have significant impacts on predictions of future oxygen levels.

Description: Recent modeling results suggest that oceanic oxygen levels will decrease significantly over the next decades to centuries in response to climate change and altered ocean circulation. Hence the future ocean may experience major shifts in nutrient cycling triggered by the expansion and intensification of tropical oxygen minimum zones (OMZs). There are numerous feedbacks between oxygen concentrations, nutrient cycling and biological productivity; however, existing knowledge is insufficient to understand physical, chemical and biological interactions in order to adequately assess past and potential future changes. We investigated the pelagic biogeochemistry of OMZs in the eastern tropical North Atlantic and eastern tropical South Pacific during a series of cruise expeditions and mesocosm studies. The following summarizes the current state of research on the influence of low environmental oxygen conditions on marine biota, viruses, organic matter formation and remineralization with a particular focus on the nitrogen cycle in OMZ regions. The impact of sulfidic events on water column biogeochemistry, originating from a specific microbial community capable of highly efficient carbon fixation, nitrogen turnover and N2O production is further discussed. Based on our findings, an important role of sinking particulate organic matter in controlling the nutrient stochiometry of the water column is suggested. These particles can enhance degradation processes in OMZ waters by acting as microniches, with sharp gradients enabling different processes to happen in close vicinity, thus altering the interpretation of oxic and anoxic environments.