Description: Methyl iodide (CH3I}, bromoform (CHBr3) and dibromomethane (CH2Br2), which are produced naturally in the oceans, take part in ozone chemistry both in the troposphere and the stratosphere. The significance of oceanic upwelling regions for emissions of these trace gases in the global context is still uncertain although they have been identified as important source regions. To better quantify the role of upwelling areas in current and future climate, this paper analyzes major factors that influenced halocarbon emissions from the tropical North East Atlantic including the Mauritanian upwelling during the DRIVE expedition. Diel and regional variability of oceanic and atmospheric CH3I, CHBr3 and CH2Br2 was determined along with biological and meteorological parameters at six 24 h-stations. Low oceanic concentrations of CH3I from 0.1–5.4 pmol L-1 were equally distributed throughout the investigation area. CHBr3 of 1.0–42.4 pmol L-1 and CH2Br2 of 1.0–9.4 pmol L-1 were measured with maximum concentrations close to the Mauritanian coast. Atmospheric mixing rations of CH3I of up to 3.3, CHBr3 to 8.9 and CH2Br2 to 3.1 ppt above the upwelling and 1.8, 12.8, respectively 2.2 ppt at a Cape Verdean coast were detected during the campaign. While diel variability in CH3I emissions could be mainly ascribed to oceanic non-biological production, no main driver was identified for its emissions in the entire study region. In contrast, oceanic bromocarbons resulted from biogenic sources which were identified as regional drivers of their sea-to-air fluxes. The diel impact of wind speed on bromocarbon emissions increased with decreasing distance to the coast. The height of the marine atmospheric boundary layer (MABL) was determined as an additional factor influencing halocarbon emissions. Oceanic and atmospheric halocarbons correlated well in the study region and in combination with high oceanic CH3I, CHBr3 and CH2Br2 concentrations, local hot spots of atmospheric halocarbons could solely be explained by marine sources. This conclusion is in contrast with previous studies that hypothesized the occurrence of elevated atmospheric halocarbons over the eastern tropical Atlantic mainly originating from the West-African continent.

Description: Dimethylsulphide (DMS) and dissolved and particulate dimethylsulfoniopropionate (DMSPd, DMSPp) were measured in near-surface waters along theMauritanian coast, Northwest Africa, during the upwelling season in February 2008. DMS, DMSPd and DMSPp surface concentrations of up to 10 nmol L−1, 15 nmol L−1 and 990 nmol L−1, respectively, were measured. However, the DMS concentrations measured are in the low range compared to other upwelling regions. The maximum DMSPp concentration is the highest reported from upwelling regions so far, which might indicate that the Mauritanian upwelling is a hot spot for DMSP. Within the phytoplankton groups, dinoflagellates were identified as important contributors to DMS concentrations, while other algae seemed to have only a minor or no influence on DMS and DMSP concentrations. A pronounced switch from high DMSP to high DMS concentrations was observed when the nitrogen to phosphorus ratio (N:P) was below 7. The high DMS/DMSP ratios at N:P ratios 〈7 indicate that nitrogen limitation presumably triggered a switch from DMSP to DMS independent of the species composition. Our results underline the importance of coastal upwelling regions as a local source for surface seawater sulphur.

Description: The Arctic Ocean plays a key role in regulating the global climate, while being highly sensitive to climate change. Temperature in the Arctic increases faster than the global average, causing a loss of multiyear sea-ice and affecting marine ecosystem structure and functioning. As a result, Arctic primary production and biogeochemical cycling are changing. Here, we investigated inter-annual changes in the concentrations of particulate and dissolved organic carbon (POC, DOC) together with biological drivers, such as phyto- and bacterioplankton abundance in the Fram Strait, the Atlantic gateway to the Central Arctic Ocean. Data have been collected in summer at the Long-Term Ecological Research observatory HAUSGARTEN during eight cruises from 2009 to 2017. Our results suggest that the dynamic physical system of the Fram Strait induces strong heterogeneity of the ecosystem that displays considerable intra-seasonal as well as inter-annual variability. Over the observational period, DOC concentrations were significantly negatively related to temperature and salinity, suggesting that outflow of Central Arctic waters carrying a high DOC load is the main control of DOC concentration in this region. POC concentration was not linked to temperature or salinity but tightly related to phytoplankton biomass as estimated from chlorophyll-a concentrations (Chl-a). For the years 2009–2017, no temporal trends in the depth-integrated (0–100 m) amounts of DOC and Chl-a were observed. In contrast, depth-integrated (0–100 m) amounts of POC, as well as the ratio [POC]:[TOC], decreased significantly over time. This suggests a higher partitioning of organic carbon into the dissolved phase. Potential causes and consequences of the observed changes in organic carbon stocks for food-web structure and CO2 sequestration are discussed.

Description: We have combined the first satellite maps of the global distribution of phytoplankton functional type and new measurements of phytoplankton-specific isoprene productivities, with available remote marine isoprene observations and a global model, to evaluate our understanding of the marine isoprene source and its impacts on organic aerosol abundances. Using satellite products to scale up data on phytoplankton-specific isoprene productivity to the global oceans, we infer a mean "bottom-up" oceanic isoprene emission of 0.31±0.08 (1σ) Tg/yr. By minimising the mean bias between the model and isoprene observations in the marine atmosphere remote from the continents, we produce a "top-down" oceanic isoprene source estimate of 1.9 Tg/yr. We suggest our reliance on limited atmospheric isoprene data, difficulties in simulating in-situ isoprene production rates in laboratory phytoplankton cultures, and limited knowledge of isoprene production mechanisms across the broad range of phytoplankton communities in the oceans under different environmental conditions as contributors to this difference between the two estimates. Inclusion of secondary organic aerosol (SOA) production from oceanic isoprene in the model with a 2% yield produces small contributions (0.01–1.4%) to observed organic carbon (OC) aerosol mass at three remote marine sites in the Northern and Southern Hemispheres. Based on these findings we suggest an insignificant role for isoprene in modulating remote marine aerosol abundances, giving further support to a recently postulated primary OC source in the remote marine atmosphere.

Description: The interaction between iron availability and the phytoplankton elemental composition was investigated during the in situ iron fertilization experiment EIFEX and in laboratory experiments with the Southern Ocean diatom species Fragilariopsis kerguelensis and Chaetoceros dichaeta. Contrary to other in situ iron fertilization experiments we observed an increase in the BSi:POC, BSi:PON, and BSi:POP ratios within the iron fertilized patch during EIFEX. This is possibly caused by a relatively stronger increase in diatom abundance compared to other phytoplankton groups and does not necessarily represent the amount of silicification of single diatom cells. In laboratory experiments with F. kerguelensis and C. dichaeta no changes in the POC:PON, PON:POP, and POC:POP ratios were found with changing iron availability in both species. BSi:POC, BSi:PON, and BSi:POP ratios were significantly lower in the high iron treatments compared to the controls. In F. kerguelensis this was caused by a decrease in cellular BSi concentrations and therefore possibly less silicification. In C. dichaeta no change in cellular BSi concentration was found. Here lower BSi:POC, BSi:PON, and BSi:POP ratios were caused by an increase in cellular C, N, and P under high iron conditions. These results indicate that iron limitation does not always increase silicification in diatoms and that changes in the BSi:POC, BSi:PON, and BSi:POP ratios under iron fertilization in the field are caused by a variety of different mechanisms. Our results therefore imply that simple cause-and-effect relationships are not always applicable for modeling of elemental ratios.

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: We determined the composition and structure of late summer eukaryotic protist assemblages along a west–east transect in the Amundsen Sea. We used state-of-the-art molecular approaches, such as automated ribosomal intergenic spacer analysis (ARISA) and 454-pyrosequencing, combined with pigment measurements via high performance liquid chromatography (HPLC) to study the protist assemblage. We found characteristic offshore and inshore communities. In general, total chlorophyll a and microeukaryotic contribution were higher in inshore samples. Diatoms were the dominant group across the entire area, of which Eucampia sp. and Pseudo-nitzschia sp. were dominant inshore and Chaetoceros sp. was dominant offshore. At the most eastern station, the assemblage was dominated by Phaeocystis sp. Under the ice, ciliates showed their highest and haptophytes their lowest abundance. This study delivers a taxon detailed overview of the eukaryotic protist composition in the Amundsen Sea during the summer 2010.

Description: Assessing the role of sea ice algal biomass and primary production for polar ecosystems remains challenging due to the strong spatio-temporal variability of sea ice algae. Therefore, the spatial representativeness of sea ice algal biomass and primary production sampling remains a key issue in large-scale models and climate change predictions of polar ecosystems. To address this issue, we presented two novel approaches to up-scale ice algal chl a biomass and net primary production (NPP) estimates based on profiles covering distances of 100 to 1,000 s of meters. This was accomplished by combining ice core-based methods with horizontal under-ice spectral radiation profiling conducted in the central Arctic Ocean during summer 2012. We conducted a multi-scale comparison of ice-core based ice algal chl a biomass with two profiling platforms: a remotely operated vehicle and surface and under ice trawl (SUIT). NPP estimates were compared between ice cores and remotely operated vehicle surveys. Our results showed that ice core-based estimates of ice algal chl a biomass and NPP do not representatively capture the spatial variability compared to the remotely operated vehicle-based estimates, implying considerable uncertainties for pan-Arctic estimates based on ice core observations alone. Grouping sea ice cores based on region or ice type improved the representativeness. With only a small sample size, however, a high risk of obtaining non-representative estimates remains. Sea ice algal chl a biomass estimates based on the dominant ice class alone showed a better agreement between ice core and remotely operated vehicle estimates. Grouping ice core measurements yielded no improvement in NPP estimates, highlighting the importance of accounting for the spatial variability of both the chl a biomass and bottom-ice light in order to get representative estimates. Profile-based measurements of ice algae chl a biomass identified sea ice ridges as an underappreciated component of the Arctic ecosystem because chl a biomass was significantly greater in this unique habitat. Sea ice ridges are not easily captured with ice coring methods and thus require more attention in future studies. Based on our results, we provide recommendations for designing an efficient and effective sea ice algal sampling program for the summer season.

Description: We derive the chlorophyll a concentration (Chla) for three main phytoplankton functional types (PFTs) – diatoms, coccolithophores and cyanobacteria – by combining satellite multispectral-based information, being of a high spatial and temporal resolution, with retrievals based on high resolution of PFT absorption properties derived from hyperspectral satellite measurements. The multispectral-based PFT Chla retrievals are based on a revised version of the empirical OC-PFT algorithm applied to the Ocean Color Climate Change Initiative (OC-CCI) total Chla product. The PhytoDOAS analytical algorithm is used with some modifications to derive PFT Chla from SCIAMACHY hyperspectral measurements. To combine synergistically these two PFT products (OC-PFT and PhytoDOAS), an optimal interpolation is performed for each PFT in every OC-PFT sub-pixel within a PhytoDOAS pixel, given its Chla and its a priori error statistics. The synergistic product (SynSenPFT) is presented for the period of August 2002 March 2012 and evaluated against PFT Chla data obtained from in situ marker pigment data and the NASA Ocean Biogeochemical Model simulations and satellite information on phytoplankton size. The most challenging aspects of the SynSenPFT algorithm implementation are discussed. Perspectives on SynSenPFT product improvements and prolongation of the time series over the next decades by adaptation to Sentinel multi- and hyperspectral instruments are highlighted.