From local to global scale - marine emissions of the climate relevant sulfur gases carbonyl sulfide, carbon disulfide and dimethyl sulfide

Oceanic emissions of sulfur containing trace gases alter global atmospheric chemistry. The gases act for example as aerosol precursors and change the radiative budget of the Earth, with a significant impact on climate. Large uncertainties exist in the amount of sulfur gases emitted from the ocean, and a gap in the atmospheric budget of carbonyl sulfide – the most abundant sulfur gas in the atmosphere – has been suggested to result from tropical ocean emissions. This thesis uses new shipbased measurements from the tropical Pacific and Indian Ocean together with models to quantify these emissions. Three studies were performed: 1) A 3D model study to test how oceanic emissions can be represented in atmospheric chemistry climate models, 2) A combination of new shipbased data and box model calculation to derive a global emission estimate of carbonyl sulfide and 3) a detailed process study of production processes and their drivers for the gases carbonyl sulfide and carbon disulfide in the Eastern tropical South Pacific. Together, the results yield a new temporally and spatially resolved emission climatology of the three gases

Von lokaler zu globaler Skala: Marine Emissionen der klimarelevanten Spurengase Karbonylsulfid, Karbondisulfid und Dimethylsulfid

Oceanic emissions of sulfur containing trace gases alter global atmospheric chemistry. The gases act for example as aerosol precursors and change the radiative budget of the Earth, with a significant impact on climate. Large uncertainties exist in the amount of sulfur gases emitted from the ocean, and a gap in the atmospheric budget of carbonyl sulfide – the most abundant sulfur gas in the atmosphere – has been suggested to result from tropical ocean emissions. This thesis uses new shipbased measurements from the tropical Pacific and Indian Ocean together with models to quantify these emissions. Three studies were performed: 1) A 3D model study to test how oceanic emissions can be represented in atmospheric chemistry climate models, 2) A combination of new shipbased data and box model calculation to derive a global emission estimate of carbonyl sulfide and 3) a detailed process study of production processes and their drivers for the gases carbonyl sulfide and carbon disulfide in the Eastern tropical South Pacific. Together, the results yield a new temporally and spatially resolved emission climatology of the three gases.Ozeanemissionen schwefelhaltiger Spurengase beeinflussen die Atmosphärenchemie, indem sie z.B. Ausgangsstoffe für Aerosole sind, die das Strahlungsbudget der Erde und damit das Klima verändern. Große Unsicherheiten bestehen in der Quantifizierung der Schwefelemissionen aus dem Ozean, und eine Lücke im atmosphärischen Budget von Karbonylsulfid, dem häufigsten Schwefelgas der Atmosphäre, wurde Emissionen aus dem tropischen Ozean zugeschrieben. Diese Arbeit verwendet neue schiffsbasierte Messungen aus dem tropischen Pazifik und Indik zusammen mit Modellberechnungen, um diese Emissionen genauer zu quantifizieren. Drei Studien wurden durchgeführt: 1) Eine 3D Modellstudie, um zu testen, wie sich Ozeanemissionen am besten in atmosphärischen Chemie-Klima-Modellen abbilden lassen, 2) eine Kombination aus neuen schiffsbasierten Konzentrationsmessungen und Box-Modell-Berechnungen, um eine globale Emissionsabschätzung für das Gas Karbonylsulfid aufzustellen und 3) eine detaillierte Prozessstudie über die Produktionsprozesse der Gase Karbonylsulfid und Karbondisulfid im tropischen Ostpazifik. Die Ergebnisse bilden zusammen eine neue, zeitlich und räumlich aufgelöste Klimatologie der drei Gase

A decade of methane measurements at the Boknis Eck Time Series Station in Eckernförde Bay (southwestern Baltic Sea)

Coastal areas contribute significantly to the emissions of methane (CH4) from the ocean. In order to decipher its temporal variability in the whole water column, dissolved CH4 was measured on a monthly basis at the Boknis Eck Time-series Station (BE) located in the Eckernförde Bay (SW Baltic Sea) from 2006 to 2017. BE has a water depth of about 28 m and dissolved CH4 was measured at six water depths ranging from 0 to 25 m. In general CH4 concentrations increased with depth, indicating a sedimentary release of CH4. Pronounced enhancement of the CH4 concentrations in the bottom layer (15–25 m) was found during February, May–June and October. CH4 was not correlated with Chlorophyll a or O2 over the measurement period. Unusually high CH4 concentrations (of up to 696 nM) were sporadically observed in the upper layer (0–10 m) (e.g. in November 2013 and December 2014) and were coinciding with Major Baltic Inflow (MBI) events. Surface CH4 concentrations were always supersaturated throughout the monitoring period, indicating that the Eckernförde Bay is an intense but highly variable source of atmospheric CH4. We did not detect significant temporal trends in CH4 concentrations or emissions, despite of ongoing environmental changes such as warming and deoxygenation in the Eckernförde Bay. Overall, the CH4 variability at BE is driven by a complex interplay of various biological and physical processes

Monthly resolved modelled oceanic emissions of carbonyl sulfide and carbon disulfide for the period 2000–2019

Carbonyl sulfide (OCS) is the most abundant, long-lived sulphur gas in the atmosphere and a major supplier of sulfur to the stratospheric sulfate aerosol layer. The short-lived gas carbon disulfide (CS2) is oxidized to OCS and constitutes a major indirect source to the atmospheric OCS budget. The atmospheric budget of OCS is not well constrained due to a large missing source needed to compensate for substantial evidence that was provided for significantly higher sinks. Oceanic emissions are associated with major uncertainties. Here we provide a first, monthly resolved ocean emission inventory of both gases for the period 2000–2019 (available at https://doi.org/10.5281/zenodo.4297010) (Lennartz et al., 2020a). Emissions are calculated with a numerical box model (resolution 2.8° × 2.8° at equator, T42 grid) for the surface mixed layer. We find that interannual variability in OCS emissions is smaller than seasonal variability, and is mainly driven by variations in chromophoric dissolved organic matter (CDOM), which influences both photochemical and light-independent production. A comparison with a global database of more than 2500 measurements reveals overall good agreement. Emissions of CS2 constitute a larger sulfur source to the atmosphere than OCS, and equally show interannual variability connected to variability of CDOM. The emission estimate of CS2 is associated with higher uncertainties, as process understanding of the marine cycling of CS2 is incomplete. We encourage the use of the data provided here as input for atmospheric modelling studies to further assess the atmospheric OCS budget and the role of OCS in climate

A multi-year observation of nitrous oxide at the Boknis Eck Time-Series Station in the Eckernförde Bay (southwestern Baltic Sea)

Nitrous oxide (N2O) is a potent greenhouse gas, and it is involved in stratospheric ozone depletion. Its oceanic production is mainly influenced by dissolved nutrient and oxygen (O2) concentrations in the water column. Here we examined the seasonal and annual variations in dissolved N2O at the Boknis Eck (BE) Time Series Station located in Eckernförde Bay (southwestern Baltic Sea). Monthly measurements of N2O started in July 2005. We found a pronounced seasonal pattern for N2O with high concentrations (supersaturations) in winter and early spring and low concentrations (undersaturations) in autumn when hypoxic or anoxic conditions prevail. Unusually low N2O concentrations were observed during October 2016–April 2017, which was presumably a result of prolonged anoxia and the subsequent nutrient deficiency. Unusually high N2O concentrations were found in November 2017 and this event was linked to the occurrence of upwelling which interrupted N2O consumption via denitrification and potentially promoted ammonium oxidation (nitrification) at the oxic–anoxic interface. Nutrient concentrations (such as nitrate, nitrite and phosphate) at BE have been decreasing since the 1980s, but oxygen concentrations in the water column are still decreasing. Our results indicate a close coupling of N2O anomalies to O2 concentration, nutrients, and stratification. Given the long-term trends of declining nutrient and oxygen concentrations at BE, a decrease in N2O concentration, and thus emissions, seems likely due to an increasing number of events with low N2O concentrations

Brominated VSLS and their influence on ozone under a changing climate

Very short-lived substances (VSLS) contribute as source gases significantly to the tropospheric and stratospheric bromine loading. At present, an estimated 25 % of stratospheric bromine is of oceanic origin. In this study, we investigate how climate change may impact the ocean–atmosphere flux of brominated VSLS, their atmospheric transport, and chemical transformations and evaluate how these changes will affect stratospheric ozone over the 21st century. Under the assumption of fixed ocean water concentrations and RCP6.0 scenario, we find an increase of the ocean–atmosphere flux of brominated VSLS of about 8–10 % by the end of the 21st century compared to present day. A decrease in the tropospheric mixing ratios of VSLS and an increase in the lower stratosphere are attributed to changes in atmospheric chemistry and transport. Our model simulations reveal that this increase is counteracted by a corresponding reduction of inorganic bromine. Therefore the total amount of bromine from VSLS in the stratosphere will not be changed by an increase in upwelling. Part of the increase of VSLS in the tropical lower stratosphere results from an increase in the corresponding tropopause height. As the depletion of stratospheric ozone due to bromine depends also on the availability of chlorine, we find the impact of bromine on stratospheric ozone at the end of the 21st century reduced compared to present day. Thus, these studies highlight the different factors influencing the role of brominated VSLS in a future climate

Long-term trends at the Time Series Station Boknis Eck (Baltic Sea), 1957–2013: does climate change counteract the decline in eutrophication?

The Boknis Eck (BE) time series station, initiated in 1957, is one of the longest-operated time series stations worldwide. We present the first statistical evaluation of a data set of nine physical, chemical and biological parameters in the period of 1957–2013. In the past three to five decades, all of the measured parameters underwent significant long-term changes. Most striking is an ongoing decline in bottom water oxygen concentration, despite a significant decrease of nutrient and chlorophyll a concentrations. Temperature-enhanced oxygen consumption in the bottom water and a prolongation of the stratification period are discussed as possible reasons for the ongoing oxygen decline despite declining eutrophication. Observations at the BE station were compared with model output of the Kiel Baltic Sea Ice Ocean Model (BSIOM). Reproduced trends were in good agreement with observed trends for temperature and oxygen, but generally the oxygen concentration at the bottom has been overestimated