Globale halogenierte Emissionen für die jüngste Vergangenheit und die Zukunft

Very short lived substances (VSLS) as bromoform (CHBr3), dibromomethane (CH2Br2) and methyl iodide (CH3I) are formed in the ocean by biological, non-biological and anthropogenic processes. Marine CHBr3, CH2Br2 and CH3I concentrations show strong geographical variability (vertical and horizontal) determined by their oceanic sources and sinks. After emitted into the atmosphere these halogenated compounds and their degradation products are involved in several chemical cycles, i.e. tropospheric and stratospheric ozone depletion. Although bromine is much less abundant than chlorine in the atmosphere, it is known to deplete stratospheric ozone 45 to 69 times more efficiently. CHBr3 and CH2Br2 are the major carriers of organic bromine from the ocean to the atmosphere and CH3I is a dominant source of organic iodine in the troposphere. Atmospheric concentrations of the three halogenated compounds are highly variable due to their heterogeneous distribution and seasonally varying natural sources. The tropical ocean is identified to be a key region for enhanced halogenated emissions and for transporting large amount of VSLS into the stratosphere. Different calculation techniques derive sea-to-air flux estimates, including bottom-up and top-down approaches, as well as laboratory experiments. These estimates are used as input for atmospheric transport models i.e. chemical transport models (CTM). The global emission strength and distributions are highly variable as well as poorly quantified. Further, many uncertainties still exist in the production processes, dimension of sources and sinks and chemical fates of VSLS in both the ocean and the atmosphere. Due to that it is difficult to parameterize reliable global emission maps of halogenated compounds. This thesis includes seven manuscripts and aims to reduce the uncertainties of global emission estimates based on in-situ measurements of the three VSLS and of their relevance on stratospheric ozone loss for the present and future.Flüchtige Substanzen (VSLS) mit kurzer atmosphärischer Lebenszeiten (0-0.5 Jahre) wie Bromoform (CHBr3), Dibrommethan (CH2Br2) und Methyliodid (CH3I) werden im Ozean durch biologische, nicht biologische oder anthropogene Prozesse gebildet. Bedingt durch ihre ozeanischen Quellen und Senken weisen marine CHBr3, CH2Br2 und CH3I Konzentrationen eine starke geographische Variabilität auf (vertikal und horizontal). Gelangen diese halogenierten Verbindungen sowie ihre Zerfallsprodukte in die Atmosphäre können sie in mehrere chemische Zyklen involviert sein, wie zum Beispiel beim troposphärischen und stratosphärischen Ozonabbau. Obwohl Brom in geringerer Konzentration als Chlor in der Atmosphäre vorhanden ist, wurde bewiesen, dass Brom 45- bis 69-mal effizienter im Abbau von stratosphärischem Ozon ist. CHBr3 und CH2Br2 sind die wichtigsten Zulieferer zu atmosphärischem organischem Brom und CH3I stellt eine bedeutende Quelle von organischem Jod in die Troposphäre dar. Die atmosphärischen Konzentrationen der drei halogenierten Verbindungen sind aufgrund ihrer Unterschiedlichen Verteilung und zeitlich variierenden natürlichen Quellen sehr variabel. Der tropische Ozean wurde als Schlüsselregion für erhöhte halogenierte Emissionen und für den Transport großer Mengen von VSLS in die Stratosphäre identifiziert. Es existieren verschiedene Verfahren wie Bottom-up oder Top-down, sowie Laborexperimente, die zur Berechnung von globalen Emissionskarten dienen. Sie werden als Inputdaten für atmosphärische Transportmodelle wie zum Beispiel chemische Transportmodelle (CTM) verwendet. Die globalen Emissionen variieren stark in ihrer Größenabschätzungen. Weiterhin existieren viele Unsicherheiten in den Bildungsprozessen, den Ausmaßen von Quellen und Senken und chemischen Prozessen der halogenierten VSLS im Ozean und der Atmosphäre. Daher ist es schwierig, aussagekräftige globale Emissionskarten von halogenierten Verbindungen zu berechnen. Die vorliegende Arbeit besteht aus sieben Manuskripten und zielt darauf ab, die existierenden Unsicherheiten der globalen Emissionsabschätzungen auf Grundlage von in-situ-Messungen der drei VSLS und ihre Relevanz auf den stratosphärischen Ozonverlust für die Gegenwart und Zukunft zu reduzieren

Impact of the marine atmospheric boundary layer conditions on VSLS abundances in the eastern tropical and subtropical North Atlantic Ocean

During the DRIVE (Diurnal and Regional Variability of Halogen Emissions) ship campaign we investigated the variability of the halogenated very short-lived substances (VSLS) bromoform (CHBr3), dibromomethane (CH2Br2) and methyl iodide (CH3I) in the marine atmospheric boundary layer in the eastern tropical and subtropical North Atlantic Ocean during May/June 2010. The highest VSLS mixing ratios were found near the Mauritanian coast and close to Lisbon (Portugal). With backward trajectories we identified predominantly air masses from the open North Atlantic with some coastal influence in the Mauritanian upwelling area, due to the prevailing NW winds. The maximum VSLS mixing ratios above the Mauritanian upwelling were 8.92 ppt for bromoform, 3.14 ppt for dibromomethane and 3.29 ppt for methyl iodide, with an observed maximum range of the daily mean up to 50% for bromoform, 26% for dibromomethane and 56% for methyl iodide. The influence of various meteorological parameters - such as wind, surface air pressure, surface air and surface water temperature, humidity and marine atmospheric boundary layer (MABL) height - on VSLS concentrations and fluxes was investigated. The strongest relationship was found between the MABL height and bromoform, dibromomethane and methyl iodide abundances. Lowest MABL heights above the Mauritanian upwelling area coincide with highest VSLS mixing ratios and vice versa above the open ocean. Significant high anti-correlations confirm this relationship for the whole cruise. We conclude that especially above oceanic upwelling systems, in addition to sea-air fluxes, MABL height variations can influence atmospheric VSLS mixing ratios, occasionally leading to elevated atmospheric abundances. This may add to the postulated missing VSLS sources in the Mauritanian upwelling region (Quack et al., 2007)

Variability and past long-term changes of brominated very short-lived substances at the tropical tropopause

Halogenated very short-lived substances (VSLSs), such as bromoform (CHBr3), can be transported to the stratosphere and contribute to the halogen loading and ozone depletion. Given their highly variable emission rates and their short atmospheric lifetimes, the exact amount as well as the spatio-temporal variability of their contribution to the stratospheric halogen loading are still uncertain. We combine observational data sets with Lagrangian atmospheric modelling in order to analyse the spatial and temporal variability of the CHBr3 injection into the stratosphere for the time period 1979–2013. Regional maxima with mixing ratios of up to 0.4–0.5 ppt at 17 km altitude are diagnosed to be over Central America (1) and over the Maritime Continent–west Pacific (2), both of which are confirmed by high-altitude aircraft campaigns. The CHBr3 maximum over Central America is caused by the co-occurrence of convectively driven short transport timescales and strong regional sources, which in conjunction drive the seasonality of CHBr3 injection. Model results at a daily resolution reveal isolated, exceptionally high CHBr3 values in this region which are confirmed by aircraft measurements during the ACCENT campaign and do not occur in spatially or temporally averaged model fields. CHBr3 injection over the west Pacific is centred south of the Equator due to strong oceanic sources underneath prescribed by the here-applied bottom-up emission inventory. The globally largest CHBr3 mixing ratios at the cold point level of up to 0.6 ppt are diagnosed to occur over the region of India, Bay of Bengal, and Arabian Sea (3); however, no data from aircraft campaigns are available to confirm this finding. Inter-annual variability of stratospheric CHBr3 injection of 10 %–20 % is to a large part driven by the variability of coupled ocean–atmosphere circulation systems. Long-term changes, on the other hand, correlate with the regional sea surface temperature trends resulting in positive trends of stratospheric CHBr3 injection over the west Pacific and Asian monsoon region and negative trends over the east Pacific. For the tropical mean, these opposite regional trends balance each other out, resulting in a relatively weak positive trend of 0.017±0.012 ppt Br per decade for 1979–2013, corresponding to 3 % Br per decade. The overall contribution of CHBr3 together with CH2Br2 to the stratospheric halogen loading accounts for 4.7 ppt Br, in good agreement with existing studies, with 50 % and 50 % being injected in the form of source and product gases, respectively

Importance of seasonally resolved oceanic emissions for bromoform delivery from the tropical Indian Ocean and west Pacific to the stratosphere

Oceanic very short-lived substances (VSLSs), such as bromoform (CHBr3), contribute to stratospheric halogen loading and, thus, to ozone depletion. However, the amount, timing, and region of bromine delivery to the stratosphere through one of the main entrance gates, the Indian summer monsoon circulation, are still uncertain. In this study, we created two bromoform emission inventories with monthly resolution for the tropical Indian Ocean and west Pacific based on new in situ bromoform measurements and novel ocean biogeochemistry modeling. The mass transport and atmospheric mixing ratios of bromoform were modeled for the year 2014 with the particle dispersion model FLEXPART driven by ERA-Interim reanalysis. We compare results between two emission scenarios: (1) monthly averaged and (2) annually averaged emissions. Both simulations reproduce the atmospheric distribution of bromoform from ship- and aircraft-based observations in the boundary layer and upper troposphere above the Indian Ocean reasonably well. Using monthly resolved emissions, the main oceanic source regions for the stratosphere include the Arabian Sea and Bay of Bengal in boreal summer and the tropical west Pacific Ocean in boreal winter. The main stratospheric injection in boreal summer occurs over the southern tip of India associated with the high local oceanic sources and strong convection of the summer monsoon. In boreal winter more bromoform is entrained over the west Pacific than over the Indian Ocean. The annually averaged stratospheric injection of bromoform is in the same range whether using monthly averaged or annually averaged emissions in our Lagrangian calculations. However, monthly averaged emissions result in the highest mixing ratios within the Asian monsoon anticyclone in boreal summer and above the central Indian Ocean in boreal winter, while annually averaged emissions display a maximum above the west Indian Ocean in boreal spring. In the Asian summer monsoon anticyclone bromoform atmospheric mixing ratios vary by up to 50% between using monthly averaged and annually averaged oceanic emissions. Our results underline that the seasonal and regional stratospheric bromine injection from the tropical Indian Ocean and west Pacific critically depend on the seasonality and spatial distribution of the VSLS emissions

Drivers of diel and regional variations of halocarbon emissions from the tropical North East Atlantic

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

The contribution of oceanic methyl iodide to stratospheric iodine

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

Higher airborne pollen concentrations correlated with increased SARS-CoV-2 infection rates, as evidenced from 31 countries across the globe

Pollen exposure weakens the immunity against certain seasonal respiratory viruses by diminishing the antiviral interferon response. Here we investigate whether the same applies to the pandemic severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), which is sensitive to antiviral interferons, if infection waves coincide with high airborne pollen concentrations. Our original hypothesis was that more airborne pollen would lead to increases in infection rates. To examine this, we performed a crosssectional and longitudinal data analysis on SARS-CoV-2 infection, airborne pollen, and meteorological factors. Our dataset is the most comprehensive, largest possible worldwide from 130 stations, across 31 countries and five continents. To explicitly investigate the effects of social contact, we additionally considered population density of each study area, as well as lockdown effects, in all possible combinations: without any lockdown, with mixed lockdown−no lockdown regime, and under complete lockdown. We found that airborne pollen, sometimes in synergy with humidity and temperature, explained, on average, 44% of the infection rate variability. Infection rates increased after higher pollen concentrations most frequently during the four previous days. Without lockdown, an increase of pollen abundance by 100 pollen/m3 resulted in a 4% average increase of infection rates. Lockdown halved infection rates under similar pollen concentrations. As there can be no preventive measures against airborne pollen exposure, we suggest wide dissemination of pollen−virus coexposure dire effect information to encourage high-risk individuals to wear particle filter masks during high springtime pollen concentrations. COVID-19 | pollen | viral infection | aerobiology</p