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- ItemGreenhouse gas effects on the solar cycle response of water vapour and noctilucent clouds(Katlenburg, Lindau : Copernicus, 2023) Vellalassery, Ashique; Baumgarten, Gerd; Grygalashvyly, Mykhaylo; Lübken, Franz-JosefThe responses of water vapour (H2O) and noctilucent clouds (NLCs) to the solar cycle are studied using the Leibniz Institute for Middle Atmosphere (LIMA) model and the Mesospheric Ice Microphysics And tranSport (MIMAS) model. NLCs are sensitive to the solar cycle because their formation depends on background temperature and the H2O concentration. The solar cycle affects the H2O concentration in the upper mesosphere mainly in two ways: directly through the photolysis and, at the time and place of NLC formation, indirectly through temperature changes. We found that H2O concentration correlates positively with the temperature changes due to the solar cycle at altitudes above about 82 km, where NLCs form. The photolysis effect leads to an anti-correlation of H2O concentration and solar Lyman-α radiation, which gets even more pronounced at altitudes below ∼83 km when NLCs are present. We studied the H2O response to Lyman-α variability for the period 1992 to 2018, including the two most recent solar cycles. The amplitude of Lyman-α variation decreased by about 40 % in the period 2005 to 2018 compared to the preceding solar cycle, resulting in a lower H2O response in the late period. We investigated the effect of increasing greenhouse gases (GHGs) on the H2O response throughout the solar cycle by performing model runs with and without increases in carbon dioxide (CO2) and methane (CH4). The increase of methane and carbon dioxide amplifies the response of water vapour to the solar variability. Applying the geometry of satellite observations, we find a missing response when averaging over altitudes of 80 to 85 km, where H2O has a positive response and a negative response (depending on altitude), which largely cancel each other out. One main finding is that, during NLCs, the solar cycle response of H2O strongly depends on altitude.
- ItemElectrocatalytic Reduction of CO2 to Acetic Acid by a Molecular Manganese Corrole Complex(Weinheim : Wiley-VCH, 2020) De, Ratnadip; Gonglach, Sabrina; Paul, Shounik; Haas, Michael; Sreejith, S.S.; Gerschel, Philipp; Apfel, Ulf-Peter; Vuong, Thanh Huyen; Rabeah, Jabor; Roy, Soumyajit; Schöfberger, WolfgangThe controlled electrochemical reduction of carbon dioxide to value added chemicals is an important strategy in terms of renewable energy technologies. Therefore, the development of efficient and stable catalysts in an aqueous environment is of great importance. In this context, we focused on synthesizing and studying a molecular MnIII-corrole complex, which is modified on the three meso-positions with polyethylene glycol moieties for direct and selective production of acetic acid from CO2. Electrochemical reduction of MnIII leads to an electroactive MnII species, which binds CO2 and stabilizes the reduced intermediates. This catalyst allows to electrochemically reduce CO2 to acetic acid in a moderate acidic aqueous medium (pH 6) with a selectivity of 63 % and a turn over frequency (TOF) of 8.25 h−1, when immobilized on a carbon paper (CP) electrode. In terms of high selectivity towards acetate, we propose the formation and reduction of an oxalate type intermediate, stabilized at the MnIII-corrole center. © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
- ItemLong-term behavior of the concentration of the minor constituents in the mesosphere-a model study(Göttingen : Copernicus, 2009) Grygalashvyly, M.; Sonnemann, G.R.; Hartogh, P.We investigate the influence the rising concentrations of methane, nitrous oxide and carbon dioxide which have occurred since the pre-industrial era, have had on the chemistry of the mesosphere. For this investigation we use our global 3-D-model COMMA-IAP which was designed for the exploration of the MLT-region and in particular the extended mesopause region. Assumptions and approximations for the trends in the Lyman-flux (needed for the water vapor dissociation rate), methane and the water vapor mixing ratio at the hygropause are necessary to accomplish this study. To approximate the solar Lyman-α flux back to the pre-industrial time, we derived a quadratic fit using the sunspot number record which extends back to 1749 and is the only solar proxy available for the Lyman-α flux prior to 1947. We assume that methane increases with a constant growth rate from the pre-industrial era to the present. An unsolved problem for the model calculations consists of how the water vapor mixing ratio at the hygropause should be specified during this period. We assume that the hygropause was dryer during pre-industrial times than the present. As a consequence of methane oxidation, the model simulation indicates that the middle atmosphere has become more humid as a result of the rising methane concentration, but with some dependence on height and with a small time delay of few years. The solar influence on the water vapor mixing ratio is insignificant below about 80 km in summer high latitudes, but becomes increasingly more important above this altitude. The enhanced water vapor concentration increasesthe hydrogen radical concentration and reduces the mesospheric ozone. A second region of stronger ozone decrease is located in the vicinity of the stratopause. Increases in CO2 concentration enhance slightly the concentration of CO in the mesosphere. However, its influence upon the chemistry is small and its main effect is connected with a cooling of the upper atmosphere. The long-term behavior of water vapor is discussed in particular with respect to its impact on the NLC region.
- ItemFootprint-weighted tile approach for a spruce forest and a nearby patchy clearing using the ACASA model(Katlenburg-Lindau [u.a.] : Copernicus, 2018) Gatzsche, Kathrin; Babel, Wolfgang; Falge, Eva; Pyles, Rex David; Paw U., Kyaw Tha; Raabe, Armin; Foken, ThomasThe ACASA (Advanced Canopy-Atmosphere-Soil Algorithm) model, with a higher-order closure for tall vegetation, has already been successfully tested and validated for homogeneous spruce forests. The aim of this paper is to test the model using a footprint-weighted tile approach for a clearing with a heterogeneous structure of the underlying surface. The comparison with flux data shows a good agreement with a footprint-aggregated tile approach of the model. However, the results of a comparison with a tile approach on the basis of the mean land use classification of the clearing is not significantly different. It is assumed that the footprint model is not accurate enough to separate small-scale heterogeneities. All measured fluxes are corrected by forcing the energy balance closure of the test data either by maintaining the measured Bowen ratio or by the attribution of the residual depending on the fractions of sensible and latent heat flux to the buoyancy flux. The comparison with the model, in which the energy balance is closed, shows that the buoyancy correction for Bowen ratios > 1.5 better fits the measured data. For lower Bowen ratios, the correction probably lies between the two methods, but the amount of available data was too small to make a conclusion. With an assumption of similarity between water and carbon dioxide fluxes, no correction of the net ecosystem exchange is necessary for Bowen ratios > 1.5.
- ItemHow the extreme 2019-2020 Australian wildfires affected global circulation and adjustments(Katlenburg-Lindau : EGU, 2023) Senf, Fabian; Heinold, Bernd; Kubin, Anne; Müller, Jason; Schrödner, Roland; Tegen, InaWildfires are a significant source of absorbing aerosols in the atmosphere. Extreme fires in particular, such as those during the 2019-2020 Australian wildfire season (Black Summer fires), can have considerable large-scale effects. In this context, the climate impact of extreme wildfires unfolds not only because of the emitted carbon dioxide but also due to smoke aerosol released up to an altitude of 17ĝ€¯km. The overall aerosol effects depend on a variety of factors, such as the amount emitted, the injection height, and the composition of the burned material, and is therefore subject to considerable uncertainty. In the present study, we address the global impact caused by the exceptionally strong and high-reaching smoke emissions from the Australian wildfires using simulations with a global aerosol-climate model. We show that the absorption of solar radiation by the black carbon contained in the emitted smoke led to a shortwave radiative forcing of more than +5ĝ€¯Wm-2 in the southern mid-latitudes of the lower stratosphere. Subsequent adjustment processes in the stratosphere slowed down the diabatically driven meridional circulation, thus redistributing the heating perturbation on a global scale. As a result of these stratospheric adjustments, a positive temperature perturbation developed in both hemispheres, leading to additional longwave radiation emitted back to space. According to the model results, this adjustment occurred in the stratosphere within the first 2 months after the event. At the top of the atmosphere (TOA), the net effective radiative forcing (ERF) averaged over the Southern Hemisphere was initially dominated by the instantaneous positive radiative forcing of about +0.5ĝ€¯Wm-2, for which the positive sign resulted mainly from the presence of clouds above the Southern Ocean. The longwave adjustments led to a compensation of the initially net positive TOA ERF, which is seen in the Southern Hemisphere, the tropics, and the northern mid-latitudes. The simulated changes in the lower stratosphere also affected the upper troposphere through a thermodynamic downward coupling. Subsequently, increased temperatures were also obtained in the upper troposphere, causing a global decrease in relative humidity, cirrus amount, and the ice water path of about 0.2ĝ€¯%. As a result, surface precipitation also decreased by a similar amount, which was accompanied by a weakening of the tropospheric circulation due to the given energetic constraints. In general, it appears that the radiative effects of smoke from single extreme wildfire events can lead to global impacts that affect the interplay of tropospheric and stratospheric budgets in complex ways. This emphasizes that future changes in extreme wildfires need to be included in projections of aerosol radiative forcing.
- ItemSpatial, temporal and source contribution assessments of black carbon over the northern interior of South Africa(Katlenburg-Lindau : EGU, 2017) Chiloane, Kgaugelo Euphinia; Beukes, Johan Paul; van Zyl, Pieter Gideon; Maritz, Petra; Vakkari, Ville; Josipovic, Miroslav; Venter, Andrew Derick; Jaars, Kerneels; Tiitta, Petri; Kulmala, Markku; Wiedensohler, Alfred; Liousse, Catherine; Mkhatshwa, Gabisile Vuyisile; Ramandh, Avishkar; Laakso, LauriAfter carbon dioxide (CO2), aerosol black carbon (BC) is considered to be the second most important contributor to global warming. This paper presents equivalent black carbon (eBC) (derived from an optical absorption method) data collected from three sites in the interior of South Africa where continuous measurements were conducted, i.e. Elandsfontein, Welgegund and Marikana, as well elemental carbon (EC) (determined by evolved carbon method) data at five sites where samples were collected once a month on a filter and analysed offline, i.e. Louis Trichardt, Skukuza, Vaal Triangle, Amersfoort and Botsalano. Analyses of eBC and EC spatial mass concentration patterns across the eight sites indicate that the mass concentrations in the South African interior are in general higher than what has been reported for the developed world and that different sources are likely to influence different sites. The mean eBC or EC mass concentrations for the background sites (Welgegund, Louis Trichardt, Skukuza, Botsalano) and sites influenced by industrial activities and/or nearby settlements (Elandsfontein, Marikana, Vaal Triangle and Amersfoort) ranged between 0.7 and 1.1, and 1.3 and 1.4 μg m-3, respectively. Similar seasonal patterns were observed at all three sites where continuous measurement data were collected (Elandsfontein, Marikana and Welgegund), with the highest eBC mass concentrations measured from June to October, indicating contributions from household combustion in the cold winter months (June-August), as well as savannah and grassland fires during the dry season (May to mid-October). Diurnal patterns of eBC at Elandsfontein, Marikana and Welgegund indicated maximum concentrations in the early mornings and late evenings, and minima during daytime. From the patterns it could be deduced that for Marikana and Welgegund, household combustion, as well as savannah and grassland fires, were the most significant sources, respectively. Possible contributing sources were explored in greater detail for Elandsfontein, with five main sources being identified as coal-fired power stations, pyrometallurgical smelters, traffic, household combustion, as well as savannah and grassland fires. Industries on the Mpumalanga Highveld are often blamed for all forms of pollution, due to the NO2 hotspot over this area that is attributed to NOx emissions from industries and vehicle emissions from the Johannesburg. Pretoria megacity. However, a comparison of source strengths indicated that household combustion as well as savannah and grassland fires were the most significant sources of eBC, particularly during winter and spring months, while coal-fired power stations, pyrometallurgical smelters and traffic contribute to eBC mass concentration levels year round.
- ItemGeoengineering climate by stratospheric sulfur injections: Earth system vulnerability to technological failure(Dordrecht [u.a.] : Springer, 2009) Brovkin, V.; Petoukhov, V.; Claussen, M.; Bauer, E.; Archer, D.; Jaeger, C.We use a coupled climate-carbon cycle model of intermediate complexity to investigate scenarios of stratospheric sulfur injections as a measure to compensate for CO2-induced global warming. The baseline scenario includes the burning of 5,000 GtC of fossil fuels. A full compensation of CO2-induced warming requires a load of about 13 MtS in the stratosphere at the peak of atmospheric CO2 concentration. Keeping global warming below 2°C reduces this load to 9 MtS. Compensation of CO 2 forcing by stratospheric aerosols leads to a global reduction in precipitation, warmer winters in the high northern latitudes and cooler summers over northern hemisphere landmasses. The average surface ocean pH decreases by 0.7, reducing the calcifying ability of marine organisms. Because of the millennial persistence of the fossil fuel CO2 in the atmosphere, high levels of stratospheric aerosol loading would have to continue for thousands of years until CO2 was removed from the atmosphere. A termination of stratospheric aerosol loading results in abrupt global warming of up to 5°C within several decades, a vulnerability of the Earth system to technological failure. © 2008 The Author(s).
- ItemGlobal and regional effects of land-use change on climate in 21st century simulations with interactive carbon cycle(Göttingen : Copernicus GmbH, 2014) Boysen, L.R.; Brovkin, V.; Arora, V.K.; Cadule, P.; De Noblet-Ducoudré, N.; Kato, E.; Pongratz, J.; Gayler, V.Biogeophysical (BGP) and biogeochemical (BGC) effects of land-use and land cover change (LULCC) are separated at the global and regional scales in new interactive CO2simulations for the 21st century. Results from four earth system models (ESMs) are analyzed for the future RCP8.5 scenario from simulations with and without land-use and land cover change (LULCC), contributing to the Land-Use and Climate, IDentification of robust impacts (LUCID) project. Over the period 2006-2100, LULCC causes the atmospheric CO2concentration to increase by 12, 22, and 66 ppm in CanESM2, MIROC-ESM, and MPI-ESM-LR, respectively. Statistically significant changes in global near-surface temperature are found in three models with a BGC-induced global mean annual warming between 0.07 and 0.23 K. BGP-induced responses are simulated by three models in areas of intense LULCC of varying sign and magnitude (between g 0.47 and 0.10 K). Modifications of the land carbon pool by LULCC are disentangled in accordance with processes that can lead to increases and decreases in this carbon pool. Global land carbon losses due to LULCC are simulated by all models: 218, 57, 35 and 34 Gt C by MPI-ESM-LR, MIROC-ESM, IPSL-CM5A-LR and CanESM2, respectively. On the contrary, the CO2-fertilization effect caused by elevated atmospheric CO2concentrations due to LULCC leads to a land carbon gain of 39 Gt C in MPI-ESM-LR and is almost negligible in the other models. A substantial part of the spread in models' responses to LULCC is attributed to the differences in implementation of LULCC (e.g., whether pastures or crops are simulated explicitly) and the simulation of specific processes. Simple idealized experiments with clear protocols for implementing LULCC in ESMs are needed to increase the understanding of model responses and the statistical significance of results, especially when analyzing the regional-scale impacts of LULCC.
- ItemTracing the Snowball bifurcation of aquaplanets through time reveals a fundamental shift in critical-state dynamics(Göttingen : Copernicus, 2023) Feulner, Georg; Bukenberger, Mona; Petri, StefanThe instability with respect to global glaciation is a fundamental property of the climate system caused by the positive ice-albedo feedback. The atmospheric concentration of carbon dioxide (CO2) at which this Snowball bifurcation occurs changes through Earth's history, most notably because of the slowly increasing solar luminosity. Quantifying this critical CO2 concentration is not only interesting from a climate dynamics perspective but also constitutes an important prerequisite for understanding past Snowball Earth episodes, as well as the conditions for habitability on Earth and other planets. Earlier studies are limited to investigations with very simple climate models for Earth's entire history or studies of individual time slices carried out with a variety of more complex models and for different boundary conditions, making comparisons and the identification of secular changes difficult. Here, we use a coupled climate model of intermediate complexity to trace the Snowball bifurcation of an aquaplanet through Earth's history in one consistent model framework. We find that the critical CO2 concentration decreased more or less logarithmically with increasing solar luminosity until about 1 billion years ago but dropped faster in more recent times. Furthermore, there was a fundamental shift in the dynamics of the critical state about 1.2 billion years ago (unrelated to the downturn in critical CO2 values), driven by the interplay of wind-driven sea-ice dynamics and the surface energy balance: for critical states at low solar luminosities, the ice line lies in the Ferrel cell, stabilised by the poleward winds despite moderate meridional temperature gradients under strong greenhouse warming. For critical states at high solar luminosities, on the other hand, the ice line rests at the Hadley cell boundary, stabilised against the equatorward winds by steep meridional temperature gradients resulting from the increased solar energy input at lower latitudes and stronger Ekman transport in the ocean.
- ItemHighly active and selective photochemical reduction of CO2 to CO using molecular-defined cyclopentadienone iron complexes(Cambridge : Soc., 2015) Rosas-Hernández, Alonso; Alsabeh, Pamela G.; Barsch, Enrico; Junge, Hernrik; Ludwig, Ralf; Beller, MatthiasHerein, we report highly active (cyclopentadienone)iron–tricarbonyl complexes for CO2 photoreduction using visible light with an Ir complex as photosensitizer and TEOA as electron/proton donor. Turnover numbers (TON) of ca. 600 (1 h) with initial turnover frequencies (TOF) up to 22.2 min−1 were observed. Operando FTIR measurements allowed for the proposal of a plausible mechanism for catalyst activation.