Surfactants and chromophoric dissolved organic matter (CDOM) in the Atlantic Ocean surface microlayer and the corresponding underlying waters

PhD ThesisThe sea surface microlayer (SML; depth < 400 μm) is a physically and biogeochemically distinct interface covering the entire ocean surface. Biologically-derived surfactants are ubiquitous in the SML, where they limit air-sea gas exchange and the formation of marine boundary layer aerosols that impact atmospheric chemistry and climate. Total surfactant activity (SA) and chromophoric dissolved organic matter (CDOM) were measured in the SML, in depth profiles (≤ 100 m) and semi-continuously in sub-surface water (SSW: 7 m non-toxic seawater supply) on Atlantic Meridional Transect (AMT) cruises 24 (2014) and 25 (2015), from 50°N to 50°S. On-board estimates of the gas transfer velocity (kw) of CH4 (custom gas exchange tank) were related to SA distributions in the SML to evaluate surfactant control of air-sea gas exchange. SML and SSW SA (mg L-1 eq. T-X-100) was always higher in the Northern Hemisphere than in the Southern Hemisphere (0.10 - 1.76 in the Northern Hemisphere; 0.08 - 0.63 in the Southern Hemisphere). A constant enrichment of SA in the SML was observed at all wind speeds encountered. SA enrichment factors (EF = SASML/SASSW) ranged between 0.95 – 4.25 in the Atlantic Ocean, higher in the Northern Hemisphere than in the Southern Hemisphere. EF >1 up to the maximum mean wind speed recorded (~13 m s-1) challenges the idea that high latitude wind speeds > 12 m s-1 preclude high EFs and implies that the SML is self-sustaining concerning SA. CDOM absorption coefficient (a300) in general was higher in the Northern Hemisphere (range 0.10 - 1.52 m-1) than in the Southern Hemisphere (range 0.17 - 0.82 m-1). CDOM spectral slope (S275-295) showed an inverse correlation with CDOM (a300) and was significantly lower (t-test, p < 0.001) in the SML than in the SSW (SML; 0.033 ± 0.005 nm-1, SSW; 0.038 ± 0.007 nm-1) suggesting in-situ CDOM production in the SML and more refractory CDOM in the SSW. CH4 k660 (kw for CO2 in seawater at 20°C) derived from the gas exchange tank (6.9 - 9.8 cm h-1) gave film factors (R660´; sample kw / surfactant-free MilliQ kw) that strongly correlated with SML SA (r2 = 0.63, p = 0.001, n = 13). Corresponding R660´ suppressions ~ 25% imply a strong control of Atlantic Ocean gas exchange by surfactant.supported by the UK Natural Environment Research Council (NERC: Grant# NE/K00252X/1) and is a component of RAGNARoCC (Radiatively active gases from the North Atlantic Region and Climate Change), which contributes to NERC’s Greenhouse Gas Emission and Feedbacks progra

6. Wochenbericht MSM105

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. - 20.02.202

N2O and CH4 underway measurements (atmosphere and ocean) during METEOR cruise M99

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

Nitrous oxide and methane from water samples during METEOR cruise M120

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

Nitrous oxide from water samples during METEOR cruise M99

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

N2O and CH4 underway measurements (atmosphere and ocean) during METEOR cruise M120

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

Hydrochemistry of water samples in the northern Benguela during METEOR expedition M120

We present data on distribution of inorganic nitrogen compounds including nitrate (NO2-) and nitrite (NO3-) in the northern Benguela and the Angola-Benguela Front regions between 10°S and 23°S. The fieldwork took place during the cruise No. M120 (Oct. 17th – Nov. 18th, 2015) onboard the R/V METEOR, which encompassed close-coastal and open ocean regions off Angola and Namibia. 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 photometrically with a Skalar San++ Autoanalyzer following the procedures detailed in Grasshoff et al. (1999). For the quality control, a reference standard was also measured at regular intervals

Trace gases CH4, N2O, and CO2 measured on discrete water samples during SONNE cruise SO283

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)

Trace gases air daily means during METEOR cruise M157

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

Surface trace gases during METEOR cruise M157

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