Nitrous oxide and methane in a changing Arctic Ocean.

Human activities are changing the Arctic environment at an unprecedented rate resulting in rapid warming, freshening, sea ice retreat and ocean acidification of the Arctic Ocean. Trace gases such as nitrous oxide (N2O) and methane (CH4) play important roles in both the atmospheric reactivity and radiative budget of the Arctic and thus have a high potential to influence the region's climate. However, little is known about how these rapid physical and chemical changes will impact the emissions of major climate-relevant trace gases from the Arctic Ocean. The combined consequences of these stressors present a complex combination of environmental changes which might impact on trace gas production and their subsequent release to the Arctic atmosphere. Here we present our current understanding of nitrous oxide and methane cycling in the Arctic Ocean and its relevance for regional and global atmosphere and climate and offer our thoughts on how this might change over coming decades.

Environmental changes affect the microbial release of hydrogen sulfide and methane from sediments at Boknis Eck (SW Baltic Sea).

Anthropogenic activities are modifying the oceanic environment rapidly and are causing ocean warming and deoxygenation, affecting biodiversity, productivity, and biogeochemical cycling. In coastal sediments, anaerobic organic matter degradation essentially fuels the production of hydrogen sulfide and methane. The release of these compounds from sediments is detrimental for the (local) environment and entails socio-economic consequences. Therefore, it is vital to understand which microbes catalyze the re-oxidation of these compounds under environmental dynamics, thereby mitigating their release to the water column. Here we use the seasonally dynamic Boknis Eck study site (SW Baltic Sea), where bottom waters annually fall hypoxic or anoxic after the summer months, to extrapolate how the microbial community and its activity reflects rising temperatures and deoxygenation. During October 2018, hallmarked by warmer bottom water and following a hypoxic event, modeled sulfide and methane production and consumption rates are higher than in March at lower temperatures and under fully oxic bottom water conditions. The microbial populations catalyzing sulfide and methane metabolisms are found in shallower sediment zones in October 2018 than in March 2019. DNA-and RNA profiling of sediments indicate a shift from primarily organotrophic to (autotrophic) sulfide oxidizing Bacteria, respectively. Previous studies using data collected over decades demonstrate rising temperatures, decreasing eutrophication, lower primary production and thus less fresh organic matter transported to the Boknis Eck sediments. Elevated temperatures are known to stimulate methanogenesis, anaerobic oxidation of methane, sulfate reduction and essentially microbial sulfide consumption, likely explaining the shift to a phylogenetically more diverse sulfide oxidizing community based on RNA.

The role of a changing Arctic Ocean and climate for the biogeochemical cycling of dimethyl sulphide and carbon monoxide.

Dimethyl sulphide (DMS) and carbon monoxide (CO) are climate-relevant trace gases that play key roles in the radiative budget of the Arctic atmosphere. Under global warming, Arctic sea ice retreats at an unprecedented rate, altering light penetration and biological communities, and potentially affect DMS and CO cycling in the Arctic Ocean. This could have socio-economic implications in and beyond the Arctic region. However, little is known about CO production pathways and emissions in this region and the future development of DMS and CO cycling. Here we summarize the current understanding and assess potential future changes of DMS and CO cycling in relation to changes in sea ice coverage, light penetration, bacterial and microalgal communities, pH and physical properties. We suggest that production of DMS and CO might increase with ice melting, increasing light availability and shifting phytoplankton community. Among others, policy measures should facilitate large-scale process studies, coordinated long term observations and modelling efforts to improve our current understanding of the cycling and emissions of DMS and CO in the Arctic Ocean and of global consequences.

Continuous Chemiluminescence Measurements of Dissolved Nitric Oxide (NO) and Nitrogen Dioxide (NO2) in the Ocean Surface Layer of the East China Sea.

Nitric oxide (NO) is a short-lived intermediate of the oceanic nitrogen cycle, and it is produced by biological and photochemical processes in the ocean. Nitrogen dioxide (NO2) is a reactive atmospheric compound which has not been determined in the ocean so far. Here, we present the setup and validation of a novel continuous underway measurement system to measure dissolved NO and NO2 in the surface ocean. The system consists of a seawater/gas equilibration component coupled to a chemiluminescence detector. It was successfully deployed during a 12 day cruise to the East China Sea in May 2018. Dissolved NO and NO2 surface concentrations ranged from

The marine nitrogen cycle: recent discoveries, uncertainties and the potential relevance of climate change.

The ocean's nitrogen cycle is driven by complex microbial transformations, including nitrogen fixation, assimilation, nitrification, anammox and denitrification. Dinitrogen is the most abundant form of nitrogen in sea water but only accessible by nitrogen-fixing microbes. Denitrification and nitrification are both regulated by oxygen concentrations and potentially produce nitrous oxide (N2O), a climate-relevant atmospheric trace gas. The world's oceans, including the coastal areas and upwelling areas, contribute about 30 per cent to the atmospheric N2O budget and are, therefore, a major source of this gas to the atmosphere. Human activities now add more nitrogen to the environment than is naturally fixed. More than half of the nitrogen reaches the coastal ocean via river input and atmospheric deposition, of which the latter affects even remote oceanic regions. A nitrogen budget for the coastal and open ocean, where inputs and outputs match rather well, is presented. Furthermore, predicted climate change will impact the expansion of the oceans' oxygen minimum zones, the productivity of surface waters and presumably other microbial processes, with unpredictable consequences for the cycling of nitrogen. Nitrogen cycling is closely intertwined with that of carbon, phosphorous and other biologically important elements via biological stoichiometric requirements. This linkage implies that human alterations of nitrogen cycling are likely to have major consequences for other biogeochemical processes and ecosystem functions and services.

Global oceanic production of nitrous oxide.

We use transient time distributions calculated from tracer data together with in situ measurements of nitrous oxide (N(2)O) to estimate the concentration of biologically produced N(2)O and N(2)O production rates in the ocean on a global scale. Our approach to estimate the N(2)O production rates integrates the effects of potentially varying production and decomposition mechanisms along the transport path of a water mass. We estimate that the oceanic N(2)O production is dominated by nitrification with a contribution of only approximately 7 per cent by denitrification. This indicates that previously used approaches have overestimated the contribution by denitrification. Shelf areas may account for only a negligible fraction of the global production; however, estuarine sources and coastal upwelling of N(2)O are not taken into account in our study. The largest amount of subsurface N(2)O is produced in the upper 500 m of the water column. The estimated global annual subsurface N(2)O production ranges from 3.1 ± 0.9 to 3.4 ± 0.9 Tg N yr(-1). This is in agreement with estimates of the global N(2)O emissions to the atmosphere and indicates that a N(2)O source in the mixed layer is unlikely. The potential future development of the oceanic N(2)O source in view of the ongoing changes of the ocean environment (deoxygenation, warming, eutrophication and acidification) is discussed.

Photochemical production of methane in natural waters: implications for its present and past oceanic source.

We conducted irradiation experiments with riverine, estuarine, and marine water samples to investigate the possibility of photochemical methane (CH4) formation. CH4 photoproduction was undetectable under oxic conditions or in the absence of methyl radical precursors indicating that its photochemical formation is negligible in the present ocean. Significant photochemical CH4 production was observed in the presence of a methyl radical precursor such as acetone under strictly anoxic conditions. Our results indicate an indirect formation mechanism with coloured dissolved organic matter acting as photosensitizer. We suggest that photochemical CH4 formation might have occurred in the anoxic ocean surface layer of the Archean prior to the onset of O2 accumulation in the atmosphere at around 2300 million years ago. Oceanic CH4 photoproduction via methyl radical (CH3) precursors and its subsequent release to the atmosphere may have contributed to high CH4 mixing ratios in the Archean atmosphere.