Description: Biogeochemical cycles of carbon, nutrients, and oxygen transmit mean states, trends and variations of the physical realm in coastal upwelling systems to their food webs and determine their role in regional budgets of greenhouse gases. This contribution focuses on biogeochemical processes in the northern Benguela Upwelling System (NBUS), where low oxygen levels in upwelling source water are a major influence on carbon and nutrient cycles. Based on measurements during numerous expeditions and results of 3-D regional ecosystem modeling (project GENUS; Geochemistry and Ecology of the Namibian Upwelling System) we here examine source water character, effects of low oxygen conditions on nutrient masses and ratios, and of diazotrophic N2-fixation on productivity of the system and its transition to the adjacent eastern South Atlantic. In available observations, the effects of denitrification in water and sediment and phosphate release from sediments are minor influences on nitrate:phosphate ratios of the system, and excess phosphate in aged upwelling water is inherited from upwelling source water. Contrary to expectation and model results, the low N:P ratios do not trigger diazotrophic N2-fixation in the fringes of the upwelling system, possibly due to a lack of seeding populations of Trichodesmium. We also examine the flux of carbon from the sea surface to either sediment, the adjacent sub-thermocline ocean, or to regenerated nutrients and CO2. Observed fluxes out of the surface mixed layer are significantly below modeled fluxes, and suggest that regeneration of nutrients and CO2 is unusually intense in the mixed layer. This contributes to very high fluxes of CO2 from the ocean to the regional atmosphere, which is not compensated for by N2-fixation. Based on observations, the NBUS thus is a significant net CO2 source (estimated at 14.8 Tg C a− 1), whereas the CO2 balance is closed by N2-fixation in the model. Methane concentrations were low in surface waters in on-line measurements during 1 expedition, and based on these our estimate for the emission of methane for the entire Benguela system is below 0.2 Tg CH4 a− 1.

Description: Estuaries are sources of nitrous oxide (N2O) and methane (CH4) to the atmosphere. However, our present knowledge of N2O and CH4 emissions from estuaries in the tropics is very limited because data are scarce. In this study, we present first measurements of dissolved N2O and CH4 from two estuaries in a peat-dominated region of northwestern Borneo. Two campaigns (during the dry season in June 2013 and during the wet season in March 2014) were conducted in the estuaries of the Lupar and Saribas rivers. Median N2O concentrations ranged between 7.2 and 12.3 nmol L−1 and were higher in the marine end-member (13.0 ± 7.0 nmol L−1). CH4 concentrations were low in the coastal ocean (3.6 ± 0.2 nmol L−1) and higher in the estuaries (medians between 10.6 and 64.0 nmol L−1). The respiration of abundant organic matter and presumably anthropogenic input caused slight eutrophication, which did not lead to hypoxia or enhanced N2O concentrations, however. Generally, N2O concentrations were not related to dissolved inorganic nitrogen concentrations. Thus, the use of an emission factor for the calculation of N2O emissions from the inorganic nitrogen load leads to an overestimation of the flux from the Lupar and Saribas estuaries. N2O was negatively correlated with salinity during the dry season, which suggests a riverine source. In contrast, N2O concentrations during the wet season were not correlated with salinity but locally enhanced within the estuaries, implying that there were additional estuarine sources during the wet (i.e., monsoon) season. Estuarine CH4 distributions were not driven by freshwater input but rather by tidal variations. Both N2O and CH4 concentrations were more variable during the wet season. We infer that the wet season dominates the variability of the N2O and CH4 concentrations and subsequent emissions from tropical estuaries. Thus, we speculate that any changes in the Southeast Asian monsoon system will lead to changes in the N2O and CH4 emissions from these systems. We also suggest that the ongoing cultivation of peat soil in Borneo is likely to increase N2O emissions from these estuaries, while the effect on CH4 remains uncertain.

Description: Decreasing concentrations of dissolved oxygen in the ocean are considered one of the main threats to marine ecosystems as they jeopardize the growth of higher organisms. They also alter the marine nitrogen cycle, which is strongly bound to the carbon cycle and climate. While higher organisms in general start to suffer from oxygen concentrations 〈 ∼ 63 µM (hypoxia), the marine nitrogen cycle responds to oxygen concentration below a threshold of about 20 µM (microbial hypoxia), whereas anoxic processes dominate the nitrogen cycle at oxygen concentrations of 〈 ∼ 0.05 µM (functional anoxia). The Arabian Sea and the Bay of Bengal are home to approximately 21 % of the total volume of ocean waters revealing microbial hypoxia. While in the Arabian Sea this oxygen minimum zone (OMZ) is also functionally anoxic, the Bay of Bengal OMZ seems to be on the verge of becoming so. Even though there are a few isolated reports on the occurrence of anoxia prior to 1960, anoxic events have so far not been reported from the open northern Indian Ocean (i.e., other than on shelves) during the last 60 years. Maintenance of functional anoxia in the Arabian Sea OMZ with oxygen concentrations ranging between 〉 0 and ∼ 0.05 µM is highly extraordinary considering that the monsoon reverses the surface ocean circulation twice a year and turns vast areas of the Arabian Sea from an oligotrophic oceanic desert into one of the most productive regions of the oceans within a few weeks. Thus, the comparably low variability of oxygen concentration in the OMZ implies stable balances between the physical oxygen supply and the biological oxygen consumption, which includes negative feedback mechanisms such as reducing oxygen consumption at decreasing oxygen concentrations (e.g., reduced respiration). Lower biological oxygen consumption is also assumed to be responsible for a less intense OMZ in the Bay of Bengal. According to numerical model results, a decreasing physical oxygen supply via the inflow of water masses from the south intensified the Arabian Sea OMZ during the last 6000 years, whereas a reduced oxygen supply via the inflow of Persian Gulf Water from the north intensifies the OMZ today in response to global warming. The first is supported by data derived from the sedimentary records, and the latter concurs with observations of decreasing oxygen concentrations and a spreading of functional anoxia during the last decades in the Arabian Sea. In the Arabian Sea decreasing oxygen concentrations seem to have initiated a regime shift within the pelagic ecosystem structure, and this trend is also seen in benthic ecosystems. Consequences for biogeochemical cycles are as yet unknown, which, in addition to the poor representation of mesoscale features in global Earth system models, reduces the reliability of estimates of the future OMZ development in the northern Indian Ocean.

Description: We conducted extensive sediment trap experiments in the Benguela Upwelling System (BUS) in the south-eastern Atlantic Ocean to study the influence of zooplankton on the flux of particulate organic carbon (POC) through the water column and its sedimentation. Two long term moored and sixteen short term free-floating sediment trap systems were deployed. The mooring experiments were conducted for several years and the sixteen drifters were deployed on three different research cruises between 2019 and 2021. Zooplankton was separated from the trapped material and divided into 8 different zooplankton groups. In contrast to zooplankton which actively carries POC into the traps in the form of biomass (active POC flux), the remaining fraction of the trapped material was assumed to fall passively into the traps along with sinking particles (passive POC flux). The results show, in line with other studies, that copepods dominate the active POC flux, with the active POC flux in the southern BUS (sBUS) being about three times higher than in the northern BUS (nBUS). In contrast, the differences between the passive POC fluxes in the nBUS and sBUS were small. Despite large variations, which reflected the variability within the two subsystems, the mean passive POC fluxes from the drifters and the moored traps could be described using a common POC flux attenuation equation. However, the almost equal passive POC flux, on the one hand, and large variations in the POC concentration in the surface sediments between the nBUS and sBUS, on the other hand, imply that factors others than the POC supply exert the main control on POC sedimentation in the BUS. The varying intensity of the near-bottom oxygen minimum zone (OMZ), which is more pronounced in the nBUS than in the sBUS, could in turn explain the differences in the sediments, as the lack of oxygen reduces the POC degradation. Hence, globally expanding OMZs might favour POC sedimentation in regions formerly exposed to oxygenated bottom water but bear the risk of increasing the frequency of anoxic events in the oxygen-poor upwelling systems. Apart from associated release of CH4, which is a much more potent greenhouse gas than CO2, such events pose a major threat to the pelagic ecosystem and fisheries.

Description: Amino acids (AAs) mainly bound in proteins are major constituents of living biomass and non-living organic material in the oceanic particulate and dissolved organic matter pool. Uptake and cycling by heterotrophic organisms lead to characteristic changes in AA composition so that AA-based biogeochemical indicators are often used to elucidate processes of organic matter cycling and degradation. We analyzed particulate AA in a large sample set collected in various oceanic regions covering sinking and suspended particles in the water column, sediment samples, and dissolved AA from water column and pore water samples. The aim of this study was to test and improve the use of AA-derived biogeochemical indicators as proxies for organic matter sources and degradation and to better understand particle dynamics and interaction between the dissolved and particulate organic matter pools. A principal component analysis (PCA) of all data delineates diverging AA compositions of sinking and suspended particles with increasing water depth. A new sinking particle and sediment degradation indicator (SDI) allows a fine-tuned classification of sinking particles and sediments with respect to the intensity of degradation, which is associated with changes of stable isotopic ratios of nitrogen (δ15N). This new indicator is furthermore sensitive to sedimentary redox conditions and can be used to detect past anoxic early diagenesis. A second indicator emerges from the AA spectra of suspended particulate matter (SPM) in the epipelagic and that of the meso- and bathypelagic ocean and is a residence time indicator (RTI). The characteristic changes in AA patterns from shallow to deep SPM are recapitulated in the AA spectra of the dissolved organic matter (DOM) pool, so that deep SPM is more similar to DOM than to any of the other organic matter pools. This implies that there is equilibration between finely dispersed SPM and DOM in the deep sea, which may be driven by microbial activity combined with annealing and fragmentation of gels. As these processes strongly depend on physico-chemical conditions in the deep ocean, changes in quality and degradability of DOM may strongly affect the relatively large pool of suspended and dissolved AA in the ocean that amounts to 15 Pg amino acid carbon (AAC) and 89 ± 29 Pg AAC, respectively.

Description: The project MarParCloud (Marine biological production, organic aerosol Particles and marine Clouds: a process chain) aims to improve our understanding of the genesis, modification and impact of marine organic matter (OM) from its biological production, to its export to marine aerosol particles and, finally, to its ability to act as ice-nucleating particles (INPs) and cloud condensation nuclei (CCN). A field campaign at the Cape Verde Atmospheric Observatory (CVAO) in the tropics in September–October 2017 formed the core of this project that was jointly performed with the project MARSU (MARine atmospheric Science Unravelled). A suite of chemical, physical, biological and meteorological techniques was applied, and comprehensive measurements of bulk water, the sea surface microlayer (SML), cloud water and ambient aerosol particles collected at a ground-based and a mountain station took place. Key variables comprised the chemical characterization of the atmospherically relevant OM components in the ocean and the atmosphere as well as measurements of INPs and CCN. Moreover, bacterial cell counts, mercury species and trace gases were analyzed. To interpret the results, the measurements were accompanied by various auxiliary parameters such as air mass back-trajectory analysis, vertical atmospheric profile analysis, cloud observations and pigment measurements in seawater. Additional modeling studies supported the experimental analysis. During the campaign, the CVAO exhibited marine air masses with low and partly moderate dust influences. The marine boundary layer was well mixed as indicated by an almost uniform particle number size distribution within the boundary layer. Lipid biomarkers were present in the aerosol particles in typical concentrations of marine background conditions. Accumulation- and coarse-mode particles served as CCN and were efficiently transferred to the cloud water. The ascent of ocean-derived compounds, such as sea salt and sugar-like compounds, to the cloud level, as derived from chemical analysis and atmospheric transfer modeling results, denotes an influence of marine emissions on cloud formation. Organic nitrogen compounds (free amino acids) were enriched by several orders of magnitude in submicron aerosol particles and in cloud water compared to seawater. However, INP measurements also indicated a significant contribution of other non-marine sources to the local INP concentration, as (biologically active) INPs were mainly present in supermicron aerosol particles that are not suggested to undergo strong enrichment during ocean–atmosphere transfer. In addition, the number of CCN at the supersaturation of 0.30 % was about 2.5 times higher during dust periods compared to marine periods. Lipids, sugar-like compounds, UV-absorbing (UV: ultraviolet) humic-like substances and low-molecular-weight neutral components were important organic compounds in the seawater, and highly surface-active lipids were enriched within the SML. The selective enrichment of specific organic compounds in the SML needs to be studied in further detail and implemented in an OM source function for emission modeling to better understand transfer patterns, the mechanisms of marine OM transformation in the atmosphere and the role of additional sources. In summary, when looking at particulate mass, we see oceanic compounds transferred to the atmospheric aerosol and to the cloud level, while from a perspective of particle number concentrations, sea spray aerosol (i.e., primary marine aerosol) contributions to both CCN and INPs are rather limited.

Description: [1]  The northern Benguela upwelling system is a nutrient-replete region with high plankton biomass production and a seasonally changing oxygen minimum zone. Nitrate:phosphate ratios in fresh upwelling water are low due to denitrification in the near-seafloor oxygen minimum zone and phosphate efflux from sediments. This makes the region a candidate for substantial dinitrogen fixation, for which evidence is scarce. Nutrient and oxygen data, N isotope data of nitrate, nitrogen isotope ratios of particulate matter, particulate organic carbon content and suspended matter concentrations on a transect across the shelf and upper slope at 23°S illustrate N-cycling processes and are the basis for estimating the contribution of N-sources and N-sinks to the reactive nitrogen pool. It appears that N-removal due to denitrification exceeds N gain by N 2 fixation and physical mixing processes by a factor of 〉6, although inorganic N:P ratios again increase as surface water is advected offshore. Nitrate and ammonium regeneration, nutrient assimilation with N:P 〈 16, shelf break mixing, atmospheric input and N 2 fixation all contribute to the restoration of inorganic N:P ratios back to Redfield conditions, but in seasonally changing proportions. The Benguela upwelling system thus is a nutrient source for the oceanic mixed layer where N-sources and N-sinks are not in balance and Redfield conditions can only re-adjust by advection and mixing processes integrated over time.

Description: The project MarParCloud (Marine biological production, organic aerosol Particles and marine Clouds: a process chain) aims to improve our understanding of the genesis, modification and impact of marine organic matter (OM) from its biological production, to its export to marine aerosol particles and, finally, to its ability to act as ice-nucleating particles (INPs) and cloud condensation nuclei (CCN). A field campaign at the Cape Verde Atmospheric Observatory (CVAO) in the tropics in September–October 2017 formed the core of this project that was jointly performed with the project MARSU (MARine atmospheric Science Unravelled). A suite of chemical, physical, biological and meteorological techniques was applied, and comprehensive measurements of bulk water, the sea surface microlayer (SML), cloud water and ambient aerosol particles collected at a ground-based and a mountain station took place. Key variables comprised the chemical characterization of the atmospherically relevant OM components in the ocean and the atmosphere as well as measurements of INPs and CCN. Moreover, bacterial cell counts, mercury species and trace gases were analyzed. To interpret the results, the measurements were accompanied by various auxiliary parameters such as air mass back-trajectory analysis, vertical atmospheric profile analysis, cloud observations and pigment measurements in seawater. Additional modeling studies supported the experimental analysis. During the campaign, the CVAO exhibited marine air masses with low and partly moderate dust influences. The marine boundary layer was well mixed as indicated by an almost uniform particle number size distribution within the boundary layer. Lipid biomarkers were present in the aerosol particles in typical concentrations of marine background conditions. Accumulation- and coarse-mode particles served as CCN and were efficiently transferred to the cloud water. The ascent of ocean-derived compounds, such as sea salt and sugar-like compounds, to the cloud level, as derived from chemical analysis and atmospheric transfer modeling results, denotes an influence of marine emissions on cloud formation. Organic nitrogen compounds (free amino acids) were enriched by several orders of magnitude in submicron aerosol particles and in cloud water compared to seawater. However, INP measurements also indicated a significant contribution of other non-marine sources to the local INP concentration, as (biologically active) INPs were mainly present in supermicron aerosol particles that are not suggested to undergo strong enrichment during ocean–atmosphere transfer. In addition, the number of CCN at the supersaturation of 0.30 % was about 2.5 times higher during dust periods compared to marine periods. Lipids, sugar-like compounds, UV-absorbing (UV: ultraviolet) humic-like substances and low-molecular-weight neutral components were important organic compounds in the seawater, and highly surface-active lipids were enriched within the SML. The selective enrichment of specific organic compounds in the SML needs to be studied in further detail and implemented in an OM source function for emission modeling to better understand transfer patterns, the mechanisms of marine OM transformation in the atmosphere and the role of additional sources. In summary, when looking at particulate mass, we see oceanic compounds transferred to the atmospheric aerosol and to the cloud level, while from a perspective of particle number concentrations, sea spray aerosol (i.e., primary marine aerosol) contributions to both CCN and INPs are rather limited.