ALBERT

Description: The climate active trace-gas carbonyl sulfide (OCS) is the most abundant sulfur gas in the atmosphere. A missing source in its atmospheric budget is currently suggested, resulting from an upward revision of the vegetation sink. Tropical oceanic emissions have been proposed to close the resulting gap in the atmospheric budget. We present a bottom-up approach including (i) new observations of OCS in surface waters of the tropical Atlantic, Pacific and Indian oceans and (ii) a further improved global box model to show that direct OCS emissions are unlikely to account for the missing source. The box model suggests an undersaturation of the surface water with respect to OCS integrated over the entire tropical ocean area and, further, global annual direct emissions of OCS well below that suggested by top-down estimates. In addition, we discuss the potential of indirect emission from CS2 and dimethylsulfide (DMS) to account for the gap in the atmospheric budget. This bottom-up estimate of oceanic emissions has implications for using OCS as a proxy for global terrestrial CO2 uptake, which is currently impeded by the inadequate quantification of atmospheric OCS sources and sinks.

Description: The Benguela Upwelling System (BUS) is the most productive of all eastern boundary upwelling ecosystems and it hosts a well-developed oxygen minimum zone. As such, the BUS is a potential hotspot for production of N2O, a potent greenhouse gas derived from microbially driven decay of sinking organic matter. Yet, the extent at which near-surface waters emit N2O to the atmosphere in the BUS is highly uncertain. Here we present the first high-resolution surface measurements of N2O across the northern part of the BUS (nBUS). We found strong gradients with a threefold increase in N2O concentrations near the coast as compared with open ocean waters. Our observations show enhanced sea-to-air fluxes of N2O (up to 1.67 nmol m−2 s−1) in association with local upwelling cells. Based on our data we suggest that the nBUS can account for 13% of the total coastal upwelling source of N2O to the atmosphere. ©2019. American Geophysical Union. All Rights Reserved.

Description: A new system for continuous, highly-resolved oceanic and atmospheric measurements of N2O, CO and CO2 is described. The system is based upon off-axis integrated cavity output spectroscopy (OA-ICOS) and a non-dispersive infrared analyzer (NDIR) both coupled to a Weiss-type equilibrator. Performance of the combined setup was evaluated by testing its precision, accuracy, long-term stability, linearity and response time. Furthermore, the setup was tested during two oceanographic campaigns in the equatorial Atlantic Ocean in order to explore its potential for autonomous deployment onboard voluntary observing ships (VOS). Improved equilibrator response times for N2O (2.5 min) and CO (45 min) were achieved in comparison to response times from similar chamber designs used by previous studies. High stability of the OA-ICOS analyzer was demonstrated by low optimal integration times of 2 and 4 min for N2O and CO respectively, as well as detection limits of 〈 40 ppt and precision better than 0.3 ppb Hz−1/2. Results from a direct comparison of the method presented here and well-established discrete methods for oceanic N2O and CO2 measurements showed very good consistency. The favorable agreement between underway atmospheric N2O, CO and CO2 measurements and monthly means at Ascension Island (7.96° S 14.4° W) further suggests a reliable operation of the underway setup in the field. The potential of the system as an improved platform for measurements of trace gases was explored by using continuous N2O and CO2 data to characterize the development of the seasonal equatorial upwelling in the Atlantic Ocean during two R/V Maria S. Merian cruises. A similar record of high-resolution CO measurements was simultaneously obtained offering for the first time the possibility of a comprehensive view on the distribution and emissions of these climate relevant gases on the area. The relatively simple underway N2O/CO/CO2 setup is suitable for long-term deployment on board of research and commercial vessels although potential sources of drift such as cavity temperature and further technical improvements towards automation still need to be addressed.

Description: A new system for continuous, highly resolved oceanic and atmospheric measurements of N2O, CO and CO2 is described. The system is based upon off-axis integrated cavity output spectroscopy (OA-ICOS) and a non-dispersive infrared analyzer (NDIR), both coupled to a Weiss-type equilibrator. Performance of the combined setup was evaluated by testing its precision, accuracy, long-term stability, linearity and response time. Furthermore, the setup was tested during two oceanographic campaigns in the equatorial Atlantic Ocean in order to explore its potential for autonomous deployment onboard voluntary observing ships (VOS). Improved equilibrator response times for N2O (2.5 min) and CO (45 min) were achieved in comparison to response times from similar chamber designs used by previous studies. High stability of the OA-ICOS analyzer was demonstrated by low optimal integration times of 2 and 4 min for N2O and CO respectively, as well as detection limits of 〈 40 ppt and precision better than 0.3 ppb Hz–1/2. Results from a direct comparison of the method presented here and well-established discrete methods for oceanic N2O and CO2 measurements showed very good consistency. The favorable agreement between underway atmospheric N2O, CO and CO2 measurements and monthly means at Ascension Island (7.96° S 14.4° W) further suggests a reliable operation of the underway setup in the field. The potential of the system as an improved platform for measurements of trace gases was explored by using continuous N2O and CO2 data to characterize the development of the seasonal equatorial upwelling in the Atlantic Ocean during two R/V Maria S. Merian cruises. A similar record of high-resolution CO measurements was simultaneously obtained, offering, for the first time, the possibility of a comprehensive view of the distribution and emissions of these climate-relevant gases in the area studied. The relatively simple underway N2O/CO/CO2 setup is suitable for long-term deployment onboard research and commercial vessels although potential sources of drift, such as cavity temperature, and further technical improvements towards automation, still need to be addressed.

Description: Nitrous oxide is a potent greenhouse gas and a key compound in stratospheric ozone depletion. In the ocean, nitrous oxide is produced at intermediate depths through nitrification and denitrification, in particular at low oxygen concentrations. Although a third of natural emissions of nitrous oxide to the atmosphere originate from the ocean, considerable uncertainties in the distribution and magnitude of the emissions still exist. Here we present high-resolution surface measurements and vertical profiles of nitrous oxide that include the highest reported nitrous oxide concentrations in marine surface waters, suggesting that there is a hotspot of nitrous oxide emissions in high-productivity upwelling ecosystems along the Peruvian coast. We estimate that off Peru, the extremely high nitrous oxide supersaturations we observed drive a massive efflux of 0.2-0.9 Tg of nitrogen emitted as nitrous oxide per year, equivalent to 5-22% of previous estimates of global marine nitrous oxide emissions. Nutrient and gene abundance data suggest that coupled nitrification-denitrification in the upper oxygen minimum zone and transport of resulting nitrous oxide to the surface by upwelling lead to the high nitrous oxide concentrations. Our estimate of nitrous oxide emissions from the Peruvian coast surpasses values from similar, highly productive areas. © 2015 Macmillan Publishers Limited. All rights reserved.

Description: Depth profiles of nitrous oxide (N2O) were measured during six cruises to the upwelling area and oxygen minimum zone (OMZ) off Peru in 2009 and 2012/13, covering both the coastal shelf region and the adjacent open ocean. N2O profiles displayed a strong sensitivity towards oxygen concentrations. Open ocean profiles showed a transition from a broad maximum to a double-peak structure towards the centre of the OMZ where the oxygen minimum was more pronounced. Maximum N2O concentrations in the open ocean were about 80 nM. A linear relationship between ΔN2O and apparent oxygen utilization (AOU) could be found for all measurements within the upper oxycline, with a slope similar to studies in other oceanic regions. N2O profiles close to the shelf revealed a much higher variability, with N2O concentrations in the upper oxycline reaching up to several hundred nanomoles per liter at selected stations. Due to the extremely sharp oxygen gradients at the shelf, these maxima occurred in very shallow water depths of less than 50 m. In this area, a linear relationship between ΔN2O and AOU could not be observed. N2O concentrations above 100 nM were observed at oxygen concentrations ranging from close to saturation to suboxic conditions. Our results indicate that the coastal upwelling off Peru at the shelf causes conditions that lead to extreme N2O accumulation.

Description: Recent observations in the eastern tropical South Pacific (ETSP) demonstrated the key role of meso- and submesoscale processes (e.g. eddies) in shaping its hydrographic and biogeochemical properties. Off Peru, elevated primary production from coastal upwelling in combination with sluggish ventilation of subsurface waters fuels a prominent oxygen minimum zone (OMZ). Given that nitrous oxide (N2O) production/consumption processes on the water column are sensitive to oxygen (O2) concentrations, the ETSP is a region of particular interest to investigate its source-sink dynamics. To date, no detailed surveys linking mesoscale processes and N2O distributions as well as their relevance to nitrogen (N) cycling are available. In this study, we present the first measurements of N2O across three mesoscale eddies (two mode water or anticyclonic and one cyclonic) which were identified, tracked and sampled during two surveys carried out in the ETSP in November-December 2012. A "two peak" structure was observed for N2O, wherein the two maxima coincide with the upper and lower boundaries of the OMZ, indicating active nitrification and partial denitrification. This was further supported by the abundances of the key gene for nitrification amoA and the gene marker for N2O production during denitrification, nirS. Conversely, we found strong N2O depletion in the core of the OMZ (O2 〈 5 μmol L−1) to be consistent with nitrite (NO2−) accumulation and low levels of nitrate (NO3−), thus suggesting active denitrification. N2O depletion within the OMZ's core was substantially higher in the center of mode water eddies, supporting the view that eddy activity enhances N-loss processes off Peru, in particular near the shelf break where nutrient-rich, productive waters from upwelling are trapped before being transported offshore. Analysis of eddies during their propagation towards the open ocean showed that, in general, "aging" of mesoscale eddies tends to decrease N2O concentrations through the water column in response to reduced supply of material to fuel N-loss, although hydrographic variability might also significantly impact the pace of the production/consumption pathways for N2O. Our results demonstrate the relevance of mode water eddies for N2O distribution, thereby improving our understanding of the N-cycling processes, which are of crucial importance in times of climate change and ocean deoxygenation.

Description: Depth profiles of nitrous oxide (N2O) were measured during six cruises to the upwelling area and oxygen minimum zone (OMZ) off Peru in 2009 and 2012/2013, covering both the coastal shelf region and the adjacent open ocean. N2O profiles displayed a strong sensitivity towards oxygen concentrations. Open ocean profiles with distances to the shelf break larger than the first baroclinic Rossby radius of deformation showed a transition from a broad maximum close to the Equator to a double-peak structure south of 5° S where the oxygen minimum was more pronounced. Maximum N2O concentrations in the open ocean were about 80 nM. A linear relationship between ΔN2O and apparent oxygen utilization (AOU) could be found for measurements within the upper oxycline, with a slope similar to studies in other oceanic regions. In contrast, N2O profiles close to the shelf revealed a much higher variability, and N2O concentrations higher than 100 nM were often observed. The highest N2O concentration measured at the shelf was  ∼  850 nM. Due to the extremely sharp oxygen gradients at the shelf, N2O maxima occurred in very shallow water depths of less than 50 m. In the coastal area, a linear relationship between ΔN2O and AOU could not be observed as extremely high ΔN2O values were scattered over the full range of oxygen concentrations. The data points that showed the strongest deviation from a linear ΔN2O ∕ AOU relationship also showed signals of intense nitrogen loss. These results indicate that the coastal upwelling at the Peruvian coast and the subsequent strong remineralization in the water column causes conditions that lead to extreme N2O accumulation, most likely due to the interplay of intense mixing and high rates of remineralization which lead to a rapid switching of the OMZ waters between anoxic and oxic conditions. This, in turn, could trigger incomplete denitrification or pulses of increased nitrification with extreme N2O production.