Description: The sea surface microlayer (SML) covers more than 70% of the Earth’s surface and is the boundary layer interface between the ocean and the atmosphere. This important biogeochemical and ecological system is critical to a diverse range of Earth system processes, including the synthesis, transformation and cycling of organic material, and the air–sea exchange of gases, particles and aerosols. In this review we discuss the SML paradigm, taking into account physicochemical and biological characteristics that define SML structure and function. These include enrichments in biogenic molecules such as carbohydrates, lipids and proteinaceous material that contribute to organic carbon cycling, distinct microbial assemblages that participate in air–sea gas exchange, the generation of climate-active aerosols and the accumulation of anthropogenic pollutants with potentially serious implications for the health of the ocean. Characteristically large physical, chemical and biological gradients thus separate the SML from the underlying water and the available evidence implies that the SML retains its integrity over wide ranging environmental conditions. In support of this we present previously unpublished time series data on bacterioneuston composition and SML surfactant activity immediately following physical SML disruption; these imply timescales of the order of minutes for the reestablishment of the SML following disruption. A progressive approach to understanding the SML and hence its role in global biogeochemistry can only be achieved by considering as an integrated whole, all the key components of this complex environment. Highlights ► The sea surface microlayer is a biogenic film layer at the air-ocean interface. ► Distinct microbial assemblages have defining roles in microlayer functions. ► The sea surface microlayer is fundamentally involved in air-ocean transfer. ► The sea surface microlayer is linked to aerosol production. ► The sea surface microlayer is reservoir of pollutants.

Description: MILAN was a multidisciplinary, international study examining how the diel variability of sea-surface microlayer biogeochemical properties potentially impacts ocean-atmosphere interaction, in order to improve our understanding of this globally important process. The sea-surface microlayer (SML) at the air-sea interface is 〈 1 mm deep but it is physically, chemically and biologically distinct from the underlying water and the atmosphere above. Wind-driven turbulence and solar radiation are important drivers of SML physical and biogeochemical properties. Given that the SML is involved in all ocean-atmosphere exchanges of mass and energy, its response to solar radiation, especially in relation to how it regulates the air-sea exchange of climate-relevant gases and aerosols, is surprisingly poorly characterised. MILAN (sea-surface MIcroLAyer at Night) was an international, multidisciplinary campaign designed to specifically address this issue. In spring 2017, we deployed diverse sampling platforms (research vessels, radio-controlled catamaran, free-drifting buoy) to study full diel cycles in the coastal North Sea SML and in underlying water, and installed a land-based aerosol sampler. We also carried out concurrent ex situ experiments using several microsensors, a laboratory gas exchange tank, a solar simulator, and a sea spray simulation chamber. In this paper we outline the diversity of approaches employed and some initial results obtained during MILAN. Our observations of diel SML variability, e.g. the influence of changing solar radiation on the quantity and quality of organic material, and diel changes in wind intensity primarily forcing air-sea CO2 exchange, underline the value and the need of multidisciplinary campaigns for integrating SML complexity into the context of air-sea interaction.

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: Sea-surface microlayers and the corresponding underlying waters of the karstic Krka Estuary (Croatia) were studied with respect to optical and molecular properties of dissolved organic matter (DOM). Solid-phase extracted DOMwas separated by reversed-phase chromatography and analyzedwith ultra-high resolution Fourier transformion cyclotron resonance mass spectrometry (FT-ICRMS). The number and summedmagnitudes of FT-ICR MS peaks, enriched in themicrolayer, increased with increasing salinity along the estuary. The molecular hydrogen to carbon ratio (as ameasure of polarity) of enriched compounds was higher for the low salinity samples than for a high salinity marine station, which we propose is a consequence of a salt-mediated separation mechanism. Absorption and fluorescence of all samples decreased along the estuarywith themicrolayer samples showing higher absorption than the underlying water. Chromatographic and FT-ICR MS data revealed a distinct shift towards a smaller molecular size in the microlayer compared to the underlyingwater. The redistribution of dissolved organic carbonwithin chromatographic fractions and the decrease inmolecular sizewas interpreted to result from photo-degradation and/or microbial reprocessing. Collision induced dissociation of selected FT-ICR MS mass peaks revealed the presence of sulfur containing anthropogenic surfactants enriched in themicrolayer. Molecular level investigation of estuarine surfacemicrolayers will help to better understand the highly dynamic character of these systems, the accumulation of natural organicmatter and anthropogenic pollutants and the role of surface microlayers for the sea-air energy exchange.

Description: Despite the progress in the international and regional governance efforts at the level of climate change, ocean acidification (OA) remains a global problem with profoundly negative environmental, social, and economical consequences. This requires extensive mitigation and adaptation effective strategies that are hindered by current shortcomings of governance. This multidisciplinary chapter investigates the risks of ocean acidification (OA) for aquaculture and fisheries in the Mediterranean Sea and its sub-basins and the role of regional adaptive governance to tackle the problem. The identified risks are based on the biological sensitivities of the most important aquaculture species and biogenic habitats and their exposure to the current and future predicted (2100) RCP 8.5 conditions. To link OA exposure and biological sensitivity, we produced spatially resolved and depth-related pH and aragonite saturation state exposure maps and overlaid these with the existing aquaculture industry in the coastal waters of the Mediterranean basin to demonstrate potential risk for the aquaculture in the future. We also identified fisheries’ vulnerability through the indirect effects of OA on highly sensitive biogenic habitats that serve as nursery and spawning areas, showing that some of the biogenic habitats are already affected locally under existing OA conditions and will be more severely impacted across the entire Mediterranean basin under 2100 scenarios. This provided a regional vulnerability assessment of OA hotspots, risks and gaps that created the baseline for discussing the importance of adaptive governance and recommendations for future OA mitigation/adaptation strategies. By understanding the risks under future OA scenarios and reinforcing the adaptability of the governance system at the science-policy interface, best informed, “situated” management response capability can be optimised to sustain ecosystem services.

Description: Published

Description: 403–432

Description: 4A. Oceanografia e clima