2023, Vellalassery, Ashique, Baumgarten, Gerd, Grygalashvyly, Mykhaylo, Lübken, Franz-Josef

The 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.

2010, Lai, S.C., Baker, A.K., Schuck, T.J., van Velthoven, P., Oram, D.E., Zahn, A., Hermann, M., Weigelt, A., Slemr, F., Brenninkmeijer, C.A.M., Ziereis, H.

A strong pollution episode in the upper troposphere between South China and the Philippines was observed during CARIBIC flights in April 2007. Five pollution events were observed, where enhancements in aerosol and trace gas concentrations including CO, CO2, CH4, non-methane hydrocarbons (NMHCs) and halocarbons were observed along the flight tracks during four sequential flights. The importance of the contribution of biomass/biofuel burning was investigated using chemical tracers, emission factor analysis, back-trajectory analysis and satellite images. The Indochinese peninsula was identified as the probable source region of biomass/biofuel burning. However, enhancements in the urban/industrial tracer C2Cl4 during the events also indicate a substantial contribution from urban anthropogenic emissions. An estimation of the contribution of fossil fuel versus biomass/biofuel to the CO enhancement was made, indicating a biomass/biofuel burning contribution of ~54 to ~92% of the observed CO enhancements. Biomass/biofuel burning was found to be the most important source category during the sampling period.

2014, Sonnemann, G.R., Grygalashvyly, M.

We use the estimated lifetime of methane (CH4), the current methane concentration, and its annual growth rate to calculate the global methane emission rate. The upper and lower limits of the annual global methane emission rate, depending on loss of CH4 into the stratosphere and methane consuming bacteria, amounts to 648.0 Mt a-1 and 608.0 Mt a-1. These values are in reasonable agreement with satellite and with much more accurate in situ measurements of methane. We estimate a mean tropospheric and mass-weighted temperature related to the reaction rate and employ a mean OH-concentration to calculate a mean methane lifetime. The estimated atmospheric lifetime of methane amounts to 8.28 years and 8.84 years, respectively. In order to improve the analysis a realistic 3D-calculations should be performed.

2015, Schneider von Deimling, T., Grosse, G., Strauss, J., Schirrmeister, L., Morgenstern, A., Schaphoff, S., Meinshausen, M., Boike, J.

High-latitude soils store vast amounts of perennially frozen and therefore inert organic matter. With rising global temperatures and consequent permafrost degradation, a part of this carbon stock will become available for microbial decay and eventual release to the atmosphere. We have developed a simplified, two-dimensional multi-pool model to estimate the strength and timing of future carbon dioxide (CO2) and methane (CH4) fluxes from newly thawed permafrost carbon (i.e. carbon thawed when temperatures rise above pre-industrial levels). We have especially simulated carbon release from deep deposits in Yedoma regions by describing abrupt thaw under newly formed thermokarst lakes. The computational efficiency of our model allowed us to run large, multi-centennial ensembles under various scenarios of future warming to express uncertainty inherent to simulations of the permafrost carbon feedback. Under moderate warming of the representative concentration pathway (RCP) 2.6 scenario, cumulated CO2 fluxes from newly thawed permafrost carbon amount to 20 to 58 petagrams of carbon (Pg-C) (68% range) by the year 2100 and reach 40 to 98 Pg-C in 2300. The much larger permafrost degradation under strong warming (RCP8.5) results in cumulated CO2 release of 42 to 141 Pg-C and 157 to 313 Pg-C (68% ranges) in the years 2100 and 2300, respectively. Our estimates only consider fluxes from newly thawed permafrost, not from soils already part of the seasonally thawed active layer under pre-industrial climate. Our simulated CH4 fluxes contribute a few percent to total permafrost carbon release yet they can cause up to 40% of total permafrost-affected radiative forcing in the 21st century (upper 68% range). We infer largest CH4 emission rates of about 50 Tg-CH4 per year around the middle of the 21st century when simulated thermokarst lake extent is at its maximum and when abrupt thaw under thermokarst lakes is taken into account. CH4 release from newly thawed carbon in wetland-affected deposits is only discernible in the 22nd and 23rd century because of the absence of abrupt thaw processes. We further show that release from organic matter stored in deep deposits of Yedoma regions crucially affects our simulated circumpolar CH4 fluxes. The additional warming through the release from newly thawed permafrost carbon proved only slightly dependent on the pathway of anthropogenic emission and amounts to about 0.03–0.14 °C (68% ranges) by end of the century. The warming increased further in the 22nd and 23rd century and was most pronounced under the RCP6.0 scenario, adding 0.16 to 0.39 °C (68% range) to simulated global mean surface air temperatures in the year 2300.

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.

2009, Klocke, Michael, Nettmann, Edith, Bergmann, Ingo

Die Produktion von Biogas aus landwirtschaftlichen Primärprodukten oder Reststoffen stellt einen wesentlichen Beitrag zur Reduktion des Co2-Ausstoßes sowie zur Entwicklung einer nachhaltigen Landbewirtschaftung dar. Im Rahmen dieses Projektes soll daher die Artenzusammensetzung der methanogenen Mikroflora in ausgewählten Praxis-Biogasanlagen anhand ihrer 16S rDNA analysisert werden.

2017, Meinshausen, Malte, Vogel, Elisabeth, Nauels, Alexander, Lorbacher, Katja, Meinshausen, Nicolai, Etheridge, David M., Fraser, Paul J., Montzka, Stephen A., Rayner, Peter J., Trudinger, Cathy M., Krummel, Paul B., Beyerle, Urs, Canadell, Josep G., Daniel, John S., Enting, Ian G., Law, Rachel M. Law, Lunder, Chris R., O'Doherty, Simon, Prinn, Ron G., Reimann, Stefan, Rubino, Mauro, Velders, Guus J.M., Vollmer, Martin K., Wang, Ray H.J., Weiss, Ray

Atmospheric greenhouse gas (GHG) concentrations are at unprecedented, record-high levels compared to the last 800000 years. Those elevated GHG concentrations warm the planet and – partially offset by net cooling effects by aerosols – are largely responsible for the observed warming over the past 150 years. An accurate representation of GHG concentrations is hence important to understand and model recent climate change. So far, community efforts to create composite datasets of GHG concentrations with seasonal and latitudinal information have focused on marine boundary layer conditions and recent trends since the 1980s. Here, we provide consolidated datasets of historical atmospheric concentrations (mole fractions) of 43 GHGs to be used in the Climate Model Intercomparison Project – Phase 6 (CMIP6) experiments. The presented datasets are based on AGAGE and NOAA networks, firn and ice core data, and archived air data, and a large set of published studies. In contrast to previous intercomparisons, the new datasets are latitudinally resolved and include seasonality. We focus on the period 1850–2014 for historical CMIP6 runs, but data are also provided for the last 2000 years. We provide consolidated datasets in various spatiotemporal resolutions for carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O), as well as 40 other GHGs, namely 17 ozone-depleting substances, 11 hydrofluorocarbons (HFCs), 9 perfluorocarbons (PFCs), sulfur hexafluoride (SF6), nitrogen trifluoride (NF3) and sulfuryl fluoride (SO2F2). In addition, we provide three equivalence species that aggregate concentrations of GHGs other than CO2, CH4 and N2O, weighted by their radiative forcing efficiencies. For the year 1850, which is used for pre-industrial control runs, we estimate annual global-mean surface concentrations of CO2 at 284.3ppm, CH4 at 808.2ppb and N2O at 273.0ppb. The data are available at https://esgf-node.llnl.gov/search/input4mips/ and http://www.climatecollege.unimelb.edu.au/cmip6. While the minimum CMIP6 recommendation is to use the global- and annual-mean time series, modelling groups can also choose our monthly and latitudinally resolved concentrations, which imply a stronger radiative forcing in the Northern Hemisphere winter (due to the latitudinal gradient and seasonality).

2020, Allen, Robert J., Turnock, Steven, Nabat, Pierre, Neubauer, David, Lohmann, Ulrike, Olivié, Dirk, Oshima, Naga, Michou, Martine, Wu, Tongwen, Zhang, Jie, Takemura, Toshihiko, Schulz, Michael, Tsigaridis, Kostas, Bauer, Susanne E., Emmons, Louisa, Horowitz, Larry, Naik, Vaishali, van Noije, Twan, Bergman, Tommi, Lamarque, Jean-Francois, Zanis, Prodromos, Tegen, Ina, Westervelt, Daniel M., Le Sager, Philippe, Good, Peter, Shim, Sungbo, O’Connor, Fiona, Akritidis, Dimitris, Georgoulias, Aristeidis K., Deushi, Makoto, Sentman, Lori T., John, Jasmin G., Fujimori, Shinichiro, Collins, William J.

It is important to understand how future environmental policies will impact both climate change and air pollution. Although targeting near-term climate forcers (NTCFs), defined here as aerosols, tropospheric ozone, and precursor gases, should improve air quality, NTCF reductions will also impact climate. Prior assessments of the impact of NTCF mitigation on air quality and climate have been limited. This is related to the idealized nature of some prior studies, simplified treatment of aerosols and chemically reactive gases, as well as a lack of a sufficiently large number of models to quantify model diversity and robust responses. Here, we quantify the 2015-2055 climate and air quality effects of non-methane NTCFs using nine state-of-the-art chemistry-climate model simulations conducted for the Aerosol and Chemistry Model Intercomparison Project (AerChemMIP). Simulations are driven by two future scenarios featuring similar increases in greenhouse gases (GHGs) but with weak (SSP3-7.0) versus strong (SSP3-7.0-lowNTCF) levels of air quality control measures. As SSP3-7.0 lacks climate policy and has the highest levels of NTCFs, our results (e.g., surface warming) represent an upper bound. Unsurprisingly, we find significant improvements in air quality under NTCF mitigation (strong versus weak air quality controls). Surface fine particulate matter (PM2:5) and ozone (O3) decrease by 2:20:32 ugm3 and 4:60:88 ppb, respectively (changes quoted here are for the entire 2015-2055 time period; uncertainty represents the 95% confidence interval), over global land surfaces, with larger reductions in some regions including south and southeast Asia. Non-methane NTCF mitigation, however, leads to additional climate change due to the removal of aerosol which causes a net warming effect, including global mean surface temperature and precipitation increases of 0:250:12K and 0:030:012mmd1, respectively. Similarly, increases in extreme weather indices, including the hottest and wettest days, also occur. Regionally, the largest warming and wetting occurs over Asia, including central and north Asia (0:660:20K and 0:030:02mmd1), south Asia (0:470:16K and 0:170:09mmd1), and east Asia (0:460:20K and 0:150:06mmd1). Relatively large warming and wetting of the Arctic also occur at 0:590:36K and 0:040:02mmd1, respectively. Similar surface warming occurs in model simulations with aerosol-only mitigation, implying weak cooling due to ozone reductions. Our findings suggest that future policies that aggressively target non-methane NTCF reductions will improve air quality but will lead to additional surface warming, particularly in Asia and the Arctic. Policies that address other NTCFs including methane, as well as carbon dioxide emissions, must also be adopted to meet climate mitigation goals. © Author(s) 2020. This work is distributed under the Creative Commons Attribution 4.0 License.

2019, Schmack, Roman, Friedrich, Alexandra, Kondratenko, Evgenii V., Polte, Jörg, Werwatz, Axel, Kraehnert, Ralph

Decades of catalysis research have created vast amounts of experimental data. Within these data, new insights into property-performance correlations are hidden. However, the incomplete nature and undefined structure of the data has so far prevented comprehensive knowledge extraction. We propose a meta-analysis method that identifies correlations between a catalyst’s physico-chemical properties and its performance in a particular reaction. The method unites literature data with textbook knowledge and statistical tools. Starting from a researcher’s chemical intuition, a hypothesis is formulated and tested against the data for statistical significance. Iterative hypothesis refinement yields simple, robust and interpretable chemical models. The derived insights can guide new fundamental research and the discovery of improved catalysts. We demonstrate and validate the method for the oxidative coupling of methane (OCM). The final model indicates that only well-performing catalysts provide under reaction conditions two independent functionalities, i.e. a thermodynamically stable carbonate and a thermally stable oxide support.

2016, Junghans, Katrin, Ghiassi, Kamran B., Samoylova, Nataliya A., Deng, Qingming, Rosenkranz, Marco, Olmstead, Marylin M., Balch, Alan L., Popov, Alexey A.

The formation of endohedral metallofullerenes (EMFs) in an electric arc is reported for the mixed‐metal Sc–Ti system utilizing methane as a reactive gas. Comparison of these results with those from the Sc/CH4 and Ti/CH4 systems as well as syntheses without methane revealed a strong mutual influence of all key components on the product distribution. Whereas a methane atmosphere alone suppresses the formation of empty cage fullerenes, the Ti/CH4 system forms mainly empty cage fullerenes. In contrast, the main fullerene products in the Sc/CH4 system are Sc4C2@C80 (the most abundant EMF from this synthesis), Sc3C2@C80, isomers of Sc2C2@C82, and the family Sc2C2 n (2 n=74, 76, 82, 86, 90, etc.), as well as Sc3CH@C80. The Sc–Ti/CH4 system produces the mixed‐metal Sc2TiC@C2 n (2 n=68, 78, 80) and Sc2TiC2@C2 n (2 n=80) clusterfullerene families. The molecular structures of the new, transition‐metal‐containing endohedral fullerenes, Sc2TiC@Ih‐C80, Sc2TiC@D5h‐C80, and Sc2TiC2@Ih‐C80, were characterized by NMR spectroscopy. The structure of Sc2TiC@Ih‐C80 was also determined by single‐crystal X‐ray diffraction, which demonstrated the presence of a short Ti=C double bond. Both Sc2TiC‐ and Sc2TiC2‐containing clusterfullerenes have Ti‐localized LUMOs. Encapsulation of the redox‐active Ti ion inside the fullerene cage enables analysis of the cluster–cage strain in the endohedral fullerenes through electrochemical measurements.