Description: Oceanic bromocarbons are highly reactive volatile organic compounds and may contribute up to 40% of stratospheric ozone depletion in mid latitudes. High sea-air fluxes of bromocarbons in the tropical regions have been related to biological cycling in the surface ocean, mainly by phytoplankton and bacteria, but the underlying processes and magnitude of the biogenic sources and sinks are poorly known. In order to understand temporal and spatial fluctuations of oceanic bromocarbon emissions, we studied microbial production and removal processes in the surface ocean during a research cruise with RV ‘Sonne’ (OASIS-Sonne) to the tropical Indian Ocean and combined them with observational data of bromocarbon concentrations in the water and atmosphere. Water samples were incubated with 13C-labelled bromoform substrate in gas tight bottles to determine bromocarbon consumption rates. Oxygen production and consumption were monitored to estimate the auto- or heterotrophic process rates in the water body. Additional controls were sterile-filtered to differentiate between biological and chemical processes. Attained rates will be compared to measured depth profiles of bromocarbon concentrations, bacteria and phytoplankton biomass as well as organic matter concentrations.

Description: Oceanic bromocarbons are highly reactive volatile organic compounds and may contribute up to 40% of stratospheric ozone depletion in mid latitudes. High sea-air fluxes of bromocarbons in the tropical regions have been related to biological cycling in the surface ocean, mainly by phytoplankton and bacteria, but the underlying processes and magnitude of the biogenic sources and sinks are poorly known. In order to understand temporal and spatial fluctuations of oceanic bromocarbons emissions, we studied microbial production and removal processes in the surface ocean during research cruises with RV SONNE (Tropical Indian Ocean) and RV ALKOR (Central Baltic Sea).

Description: The transit of RV SONNE from Las Palmas (departure: 11.12.2021) to Guayaquil, Ecuador (arrival: 11.01.2022) is directly related to the international collaborative project SO287-CONNECT of GEOMAR in cooperation with Hereon and the University of Bremen, supported by the German Federal Ministry of Education and Research (BMBF) between October 15 2021 and January 15 2024. The research expedition was conducted to decipher the coupling of biogeochemical and ecological processes and their influence on atmospheric chemistry along the transport pathway of water from the upwelling zones off Africa into the Sargasso Sea and further to the Caribbean and the equatorial Pacific. Nutrient-rich water rises from the deep and promotes the growth of plant and animal microorganisms, and fish at the ocean surface off West Africa. The North Equatorial Current water carries the water from the upwelling, which contains large amounts of organic material across the Atlantic to the Caribbean, supporting bacterial activity along the way. But how the nutritious remnants of algae and other substances are processed on their long journey, biochemically transformed, decomposed into nutrients and respired to carbon dioxide, has so far only been partially investigated. Air, seawater and particles were sampled in order to provide new details about the large cycles of carbon and nitrogen, but also of many other elements such as oxygen, iodine, bromine and sulfur. Inorganic and organic bromine and iodine compounds are generally emitted naturally from the ocean into the atmosphere, promote cloud formation and affect climate, and some even reach the stratosphere where they contribute to ozone depletion. We measured how much of these compounds are released from the ocean, and at what locations and how they are transformed in the ocean and in the atmosphere. Sargassum algae, which have become a nuisance on beaches in the western and eastern Atlantic, support life and contribute to carbon cycling in the middle of the Atlantic, the Sargasso Sea and in the Caribbean, while their contribution to halogen cycling and marine bromine and iodine emissions was previously unknown. We investigated the influence of various natural parameters such as temperature and solar radiation on the biogeochemical transformation processes in order to understand the influence of climate change on these processes in incubation experiments with seawater and algae. We investigated how anthropogenic signals such as shipping traffic influence the nitrogen and sulphur cycle in the ocean, as well as the impact of nitrogen oxides from ship exhaust and sulphurous, acidic and dirty water from purification systems on organisms and biochemical processes. Plastic debris was sampled from the surface waters to investigate its contribution to global biogeochemical transformation processes. The working hypotheses of the research program were:  Bioavailability of dissolved organic carbon in surface waters decreases along the productivity gradient and transport pathway from the Eastern to the Western Tropical North Atlantic.  Nutrient gradients from East to West constrain the microbial utilization of organic matter- contributing to an accumulation of C-rich organic matter due to a) limited mineralization and b) enhanced exudation- also leading to gel-like particles accumulation in the western tropical North Atlantic and Sargasso Sea.  Tropospheric and stratospheric ozone are strongly impacted by biogeochemical and ecological processes occurring around and in the NA gyre system related to marine iodine and bromine cycles.  The long-range transport of natural and anthropogenic organic matter in water and of gases and aerosols in the air impact carbon-export, biogeochemical cycles in the water column, and the release of gases and particles from the ocean significantly. 4 SONNE -Berichte, SO287, Las Palmas - Guayaquil, 11.12.2021 - 11.01.202 The data and samples obtained specifically target carbon, nutrient and halogen cycling, the composition of phytoplankton, bacteria, the transport and sequestration of macro algae and the air-sea exchange processes of climate relevant gases and aerosols. The influence of ecological and transport processes, as well as anthropogenic impacts on the North Atlantic gyre system, specifically in the Sargasso Sea and the influence of ship emissions throughout the Atlantic towards the west and into the Pacific will be investigated with the data.

Description: Halocarbons are produced naturally in the oceans by biological and chemical processes. They are emitted from surface seawater into the atmosphere, where they take part in numerous chemical processes such as ozone destruction and the oxidation of mercury and dimethyl sulfide. Here we present oceanic and atmospheric halocarbon data for the Peruvian upwelling zone obtained during the M91 cruise onboard the research vessel METEOR in December 2012. Surface waters during the cruise were characterized by moderate concentrations of bromoform (CHBr3) and dibromomethane (CH2Br2) correlating with diatom biomass derived from marker pigment concentrations, which suggests this phytoplankton group is a likely source. Concentrations measured for the iodinated compounds methyl iodide (CH3I) of up to 35.4 pmol L−1, chloroiodomethane (CH2ClI) of up to 58.1 pmol L−1 and diiodomethane (CH2I2) of up to 32.4 pmol L−1 in water samples were much higher than previously reported for the tropical Atlantic upwelling systems. Iodocarbons also correlated with the diatom biomass and even more significantly with dissolved organic matter (DOM) components measured in the surface water. Our results suggest a biological source of these compounds as a significant driving factor for the observed large iodocarbon concentrations. Elevated atmospheric mixing ratios of CH3I (up to 3.2 ppt), CH2ClI (up to 2.5 ppt) and CH2I2 (3.3 ppt) above the upwelling were correlated with seawater concentrations and high sea-to-air fluxes. During the first part of the cruise, the enhanced iodocarbon production in the Peruvian upwelling contributed significantly to tropospheric iodine levels, while this contribution was considerably smaller during the second part.

Description: We investigate the contribution of oceanic methyl iodide (CH3I) to the stratospheric iodine budget. Based on CH3I measurements from three tropical ship campaigns and the Lagrangian transport model FLEXPART, we provide a detailed analysis of CH3I transport from the ocean surface to the cold point in the upper tropical tropopause layer (TTL). While average oceanic emissions differ by less than 50% from campaign to campaign, the measurements show much stronger variations within each campaign. A positive correlation between the oceanic CH3I emissions and the efficiency of CH3I troposphere–stratosphere transport has been identified for some cruise sections. The mechanism of strong horizontal surface winds triggering large emissions on the one hand and being associated with tropical convective systems, such as developing typhoons, on the other hand, could explain the identified correlations. As a result of the simultaneous occurrence of large CH3I emissions and strong vertical uplift, localized maximum mixing ratios of 0.6 ppt CH3I at the cold point have been determined for observed peak emissions during the SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere)-Sonne research vessel campaign in the coastal western Pacific. The other two campaigns give considerably smaller maxima of 0.1 ppt CH3I in the open western Pacific and 0.03 ppt in the coastal eastern Atlantic. In order to assess the representativeness of the large local mixing ratios, we use climatological emission scenarios to derive global upper air estimates of CH3I abundances. The model results are compared with available upper air measurements, including data from the recent ATTREX and HIPPO2 aircraft campaigns. In the eastern Pacific region, the location of the available measurement campaigns in the upper TTL, the comparisons give a good agreement, indicating that around 0.01 to 0.02 ppt of CH3I enter the stratosphere. However, other tropical regions that are subject to stronger convective activity show larger CH3I entrainment, e.g., 0.08 ppt in the western Pacific. Overall our model results give a tropical contribution of 0.04 ppt CH3I to the stratospheric iodine budget. The strong variations in the geographical distribution of CH3I entrainment suggest that currently available upper air measurements are not representative of global estimates and further campaigns will be necessary in order to better understand the CH3I contribution to stratospheric iodine.

Description: Methyl iodide (CH3I) is a volatile organic halogen compound that contributes significantly to the transport of iodine from the ocean to the atmosphere, where it plays an important role in tropospheric chemistry. CH3I is naturally produced and occurs in the global ocean. The processes involved in the formation of CH3I, however, are not fully understood. In fact, there is an ongoing debate whether production by phytoplankton or photochemical degradation of organic matter is the main source term. Here, both the biological and photochemical production mechanisms are considered in a biogeochemical module that is coupled to a one-dimensional water column model for the eastern tropical Atlantic. The model is able to reproduce observed subsurface maxima of CH3I concentrations. But, the dominating source process cannot be clearly identified as subsurface maxima can occur due to both direct biological and photochemical production. However, good agreement between the observed and simulated difference between surface and subsurface methyl iodide concentrations is achieved only when direct biological production is taken into account. Production rates for the biological CH3I source that were derived from published laboratory studies are shown to be inappropriate for explaining CH3I concentrations in the eastern tropical Atlantic.