Description: FS MARIA S. MERIAN Fahrt MSM105 11.01.2022 – 23.02.2022 Walvis Bay – Mindelo BUSUC II Das Benguela-System im Klimawandel - Auswirkungen der Variabilität des physikalischen Antriebs auf den Kohlenstoff- und Sauerstoffhaushalt 6. Wochenbericht 14. - 20.02.2022

Description: 19 March 2021 – 25 May 2021 Emden (Germany) – Emden (Germany) TRR181 / TRAFFIC / EVAR / BANINO

Description: We present data on distribution of inorganic nitrogen compounds i.e. nitrate, nitrite and ammonium, and also phosphate and silicate in the northern Benguela and the Angola-Benguela Front regions. The fieldwork took place during the cruise No. SO283 (March 19st - May 25st, 2021) onboard the R/V SONNE, which encompassed close-coastal and open ocean regions off Angola, Namibia and South Africa. All nutrient samples were retrieved with the ship's CTD rosette (SBE 9+). Immediately after sampling, a volume of about 40 ml of each sample was filtered through a disposable syringe filter (CA, 0.45 µm) and filled in a pre-rinsed 50 ml PE bottle. The bottles were securely closed and kept frozen at -20°C until further analysis. The concentrations of nutrients were determined colorimetrically after Grasshoff et al. (1999) using segmented flow analyzer (QuAAtro AutoAnalyzer, Seal Analytical) in the laboratory at IOW. For the quality control, a reference standard was also measured at regular intervals.

Description: The high surface productivity triggered by nutrient-rich Benguela upwelled waters results in significant enrichment of organic carbon in the sub-surface waters due to enhanced mineralization in the water column and benthic fluxes. Hence, microbial oxygen-consuming processes are promoted, driving oxygen depletion that favours trace gases i.e. methane (CH4) and nitrous oxide (N2O) production at relatively shallow depths. Also, gas-rich subsurface waters are transported towards the surface waters during upwelling, enhancing trace gas sea-air fluxes. Within the EVAR project, we investigate the variability of these fluxes on seasonal and shorter timescales to understand the intensity of the Benguela upwelling system as the source of these greenhouse gases relative to the atmosphere. The data might serve as a base for projections under a changing climate. The fieldwork took place during the cruise SO283 (March 19th – May 25th, 2021) onboard the R/V SONNE from and to Emden (Germany). The main area of the sampling was the Namibian shelf between 18°S and 25°S which is suggested to represent some regional hotspots of trace gas emissions to the atmosphere, in particular in the vicinity of the upwelling cells. Over 260 discrete water samples were collected from the Niskin bottles at different stations for the determination of the concentrations of CH4, N2O, and dissolved inorganic carbon (DIC). 200ml seawater samples were fixed with 200 µL of saturated HgCl2 solution straight after sampling and trace gas was quantified in return. Dissolved CH4 and N2O were measured by an in-house designed purge and trap system with a dynamic headspace method back on land. In brief, a subsample is purged with an inert ultrapure carrier gas of Helium, and the gases are focused on a cryo-trap operated at about -120°C. The volatile compounds are desorbed by rapid heating and analyzed by a gas chromatograph (GC; Agilent 7890B), equipped with capillary columns and a Deans Switch, which directed the components to the flamenionization detector for CH4 detection and electron capture detector ECD for N2O detection. To explore the carbonate system Dissolved Inorganic Carbon (DIC) was measured in the institute. About 5.00 ml of each fixed discrete sample was acidified by 10 % phosphoric acid, resulting in release of inorganic carbon content of the sample. An automated infra-red inorganic carbon analyzer (AIRICA, Marianda, Tulpenweg 28, D-24145 Kiel) equipped with an infrared detector LICOR 7000 (LI-COR Environmental – GmbH, Homburg, Germany) was used to quantify DIC. A 3-fold measurement of the pH was also carried out in 120 ml of discrete samples directly after sampling using the HydroFIA pH system (4H Jena Engineering, 24148 Kiel, Germany). We calculated the average pH value of the corresponding sample after Müller and Rehder (2018) and corresponding total alkalinity and pCO2 after Dickson et al. (2007).

Description: Upward transport and/or mixing of trace gas-enriched subsurface waters fosters the exchange of nitrous oxide (N2O) and methane (CH4) with the atmosphere in the Eastern-South Atlantic (ESA). To date, it is, however, unclear whether this source is maintained by local production or advection of trace-gas enriched water masses. So, the meridional and zonal variability of N2O and CH4 in the ESA were investigated to constrain the contributions of the major regional water masses to the overall budget of N2O and CH4. The fieldwork took place during the cruises M99 (July 31st - August 23rd, 2013) and M120 (October 17th - November 18th, 2015) onboard the R/V METEOR, which encompassed close-coastal and open ocean regions off Angola and Namibia. To investigate the regional concentration gradients of N2O and CH4 and corresponding sea-air fluxes, seven hydrographic sections (six zonal transects and one alongshore transect) were conducted between ~10°S and 26°S. Concentrations of dissolved N2O and CH4 in surface waters were continuously measured by using the Mobile Equilibrator Sensor System. To evaluate, the oceanic-atmospheric trace gas exchange, the atmospheric N2O and CH4 in ambient air were measured at several sporadic locations, with an inlet installed at 35 m height. The data were quality controlled by comparing with the data generated by NOAA in the nearest atmospheric sampling station (23.58° S, 15.03°E, Station NMB (Gobabeb, Namibia)). Also, to better understand the underlying patterns of the trace gas in the ESA, the vertical profiles were investigated by measuring discrete samples of N2O using the dynamic headspace method on M99. N2O and CH4 concentrations were also measured using a purge and trap system during M120 expedition.

Description: Upward transport and/or mixing of trace gas-enriched subsurface waters fosters the exchange of nitrous oxide (N2O) and methane (CH4) with the atmosphere in the Eastern-South Atlantic (ESA). To date, it is, however, unclear whether this source is maintained by local production or advection of trace-gas enriched water masses. So, the meridional and zonal variability of N2O and CH4 in the ESA were investigated to constrain the contributions of the major regional water masses to the overall budget of N2O and CH4. The fieldwork took place during the cruises M99 (July 31st - August 23rd, 2013) and M120 (October 17th - November 18th, 2015) onboard the R/V METEOR, which encompassed close-coastal and open ocean regions off Angola and Namibia. To investigate the regional concentration gradients of N2O and CH4 and corresponding sea-air fluxes, seven hydrographic sections (six zonal transects and one alongshore transect) were conducted between ~10°S and 26°S. Concentrations of dissolved N2O and CH4 in surface waters were continuously measured by using the Mobile Equilibrator Sensor System. To evaluate, the oceanic-atmospheric trace gas exchange, the atmospheric N2O and CH4 in ambient air were measured at several sporadic locations, with an inlet installed at 35 m height. The data were quality controlled by comparing with the data generated by NOAA in the nearest atmospheric sampling station (23.58° S, 15.03°E, Station NMB (Gobabeb, Namibia)). Also, to better understand the underlying patterns of the trace gas in the ESA, the vertical profiles were investigated by measuring discrete samples of N2O using the dynamic headspace method on M99. N2O and CH4 concentrations were also measured using a purge and trap system during M120 expedition.

Description: Upward transport and/or mixing of trace gas-enriched subsurface waters fosters the exchange of nitrous oxide (N2O) and methane (CH4) with the atmosphere in the Eastern-South Atlantic (ESA). To date, it is, however, unclear whether this source is maintained by local production or advection of trace-gas enriched water masses. So, the meridional and zonal variability of N2O and CH4 in the ESA were investigated to constrain the contributions of the major regional water masses to the overall budget of N2O and CH4. The fieldwork took place during the cruises M99 (July 31st - August 23rd, 2013) and M120 (October 17th - November 18th, 2015) onboard the R/V METEOR, which encompassed close-coastal and open ocean regions off Angola and Namibia. To investigate the regional concentration gradients of N2O and CH4 and corresponding sea-air fluxes, seven hydrographic sections (six zonal transects and one alongshore transect) were conducted between ~10°S and 26°S. Concentrations of dissolved N2O and CH4 in surface waters were continuously measured by using the Mobile Equilibrator Sensor System. To evaluate, the oceanic-atmospheric trace gas exchange, the atmospheric N2O and CH4 in ambient air were measured at several sporadic locations, with an inlet installed at 35 m height. The data were quality controlled by comparing with the data generated by NOAA in the nearest atmospheric sampling station (23.58° S, 15.03°E, Station NMB (Gobabeb, Namibia)). Also, to better understand the underlying patterns of the trace gas in the ESA, the vertical profiles were investigated by measuring discrete samples of N2O using the dynamic headspace method on M99. N2O and CH4 concentrations were also measured using a purge and trap system during M120 expedition.

Description: The high surface productivity triggered by nutrient-rich Benguela upwelled waters results in significant enrichment of organic carbon in the sub-surface waters due to enhanced mineralization in the water column and benthic fluxes. Hence, microbial O2-consuming processes are promoted, driving oxygen depletion that favors trace gases i.e. methane (CH4) and nitrous oxide (N2O) production at relatively shallow depths. During upwelling, gas-rich subsurface waters are also transported towards the surface waters, enhancing trace gas sea-air fluxes. We investigate the variability of these fluxes on seasonal and shorter timescales to understand the intensity of the Benguela upwelling system in gas emissions. The data might serve as a base for projections under a changing climate. The fieldwork took place during the cruise M157 (August 4th – September 16th, 2019) onboard the R/V METEOR, which encompassed close-coastal and open ocean regions between Mindelo (Cape Verde) and Walvis Bay. The main transect lines around 18, 23 and 25°S represents the Angola-Benguela frontal zone, Walvis Bay and Lüderitz upwelling cells respectively, which are suggested to represent some regional hotspots of trace gas emissions to the atmosphere, in particular in the vicinity of the upwelling cells. The partial pressures of CH4, N2O, and CO2 as well as oxygen saturation in surface water were determined using IOW's self-built Mobile Equilibrator Sensor System (MESS). The system was described in details elsewhere (Sabbaghzadeh et al., 2021) but in brief, it consists of a custom-built equilibrator (combined shower-head/bubble type) with a water flow rate of about 5 l min-1 and an airflow rate of ~ 4 l min-1, which is linked to two off-axis integrated cavity output laser spectrometers (oa-ICOS, Los Gatos Instruments) for the detection of CH4 / CO2 and N2O / CO. Seawater was supplied by a pump installed at a water depth of about 6 m in the moon pool on board of RV METEOR. oa-ICOS sensors combine a highly specific infrared band laser with a set of reflective mirrors and achieve an effective absorption path length of several kilometers. This enables the detection of the trace gases with high accuracy. Three standard gases, provided by the central calibration lab of the European Integrated Carbon Observation System Research Infrastructure (ICOS RI) were used to calibrate the sensors almost daily throughout the entire expedition. To estimate sea-air gas fluxes, the atmospheric concentration of trace gases was also measured at several positions during the cruise using a tube with the inlet positioned to minimize ship contamination. All other ancillary parameters out of the MESS system were synchronized with D-ship data with a simultaneous data reduction to one-minute intervals.

Description: Upward transport and/or mixing of trace gas-enriched subsurface waters fosters the exchange of nitrous oxide (N2O) and methane (CH4) with the atmosphere in the Eastern-South Atlantic (ESA). To date, it is, however, unclear whether this source is maintained by local production or advection of trace-gas enriched water masses. So, the meridional and zonal variability of N2O and CH4 in the ESA were investigated to constrain the contributions of the major regional water masses to the overall budget of N2O and CH4. The fieldwork took place during the cruises M99 (July 31st - August 23rd, 2013) and M120 (October 17th - November 18th, 2015) onboard the R/V METEOR, which encompassed close-coastal and open ocean regions off Angola and Namibia. To investigate the regional concentration gradients of N2O and CH4 and corresponding sea-air fluxes, seven hydrographic sections (six zonal transects and one alongshore transect) were conducted between ~10°S and 26°S. Concentrations of dissolved N2O and CH4 in surface waters were continuously measured by using the Mobile Equilibrator Sensor System. To evaluate, the oceanic-atmospheric trace gas exchange, the atmospheric N2O and CH4 in ambient air were measured at several sporadic locations, with an inlet installed at 35 m height. The data were quality controlled by comparing with the data generated by NOAA in the nearest atmospheric sampling station (23.58° S, 15.03°E, Station NMB (Gobabeb, Namibia)). Also, to better understand the underlying patterns of the trace gas in the ESA, the vertical profiles were investigated by measuring discrete samples of N2O using the dynamic headspace method on M99. N2O and CH4 concentrations were also measured using a purge and trap system during M120 expedition.

Description: The high surface productivity triggered by nutrient-rich Benguela upwelled waters results in significant enrichment of organic carbon in the sub-surface waters due to enhanced mineralization in the water column and benthic fluxes. Hence, microbial O2-consuming processes are promoted, driving oxygen depletion that favors trace gases i.e. methane (CH4) and nitrous oxide (N2O) production at relatively shallow depths. During upwelling, gas-rich subsurface waters are also transported towards the surface waters, enhancing trace gas sea-air fluxes. We investigate the variability of these fluxes on seasonal and shorter timescales to understand the intensity of the Benguela upwelling system in gas emissions. The data might serve as a base for projections under a changing climate. The fieldwork took place during the cruise M157 (August 4th – September 16th, 2019) onboard the R/V METEOR, which encompassed close-coastal and open ocean regions between Mindelo (Cape Verde) and Walvis Bay. The main transect lines around 18, 23 and 25°S represents the Angola-Benguela frontal zone, Walvis Bay and Lüderitz upwelling cells respectively, which are suggested to represent some regional hotspots of trace gas emissions to the atmosphere, in particular in the vicinity of the upwelling cells. To explore further, nearly 300 discrete water samples were collected from the Niskin bottles at different stations for determination of the concentrations of CH4, N2O, and total inorganic carbon (CT). Analysis for CH4 and N2O was performed using an in-house designed purge and trap system with a dynamic headspace. In brief, a subsample of the water is purged with an inert ultrapure carrier gas of Helium, and the gases are focused on a cryo-trap operated at about -120°C. The volatile compounds are desorbed by rapid heating and analyzed by a gas chromatograph (Agilent 7890 B), equipped with a Flame Ionization Detector for CH4 and an Electron Capture Detector for N2O measurements, respectively. Samples for CT were taken to investigate the carbonate system. CT was measured using an automated Infra-Red Inorganic Carbon Analyzer (AIRICA) system (Marianda e.K., 24145 Kiel) from discrete 250 ml samples. In brief, a subsample is drawn into a volume-calibrated syringe and injected into a purge vessel, where the discrete sample is acidified. All species of the inorganic carbon system are converted to CO2, which is purged from the water using a carrier gas that streams through the acidified probe. Then the gas flows through a Peltier cooler and a NAFION dryer to be dried. The concentration of CO2 is then measured by an infrared detector (LICOR 7000), which integrates the peak of the purged sample. The integrated signal is directly proportional to the carbon released, allowing the CT concentration to be calculated with high precision. Certified reference material (CRM) of known CT-concentration is used for standardization and to account for drift of the sensor response.