Slow feedbacks resulting from strongly enhanced atmospheric methane mixing ratios in a chemistry-climate model with mixed-layer ocean

In a previous study the quasi-instantaneous chemical impacts (rapid adjustments) of strongly enhanced methane (CH4) mixing ratios have been analysed. However, to quantify the influence of the respective slow climate feedbacks on the chemical composition it is necessary to include the radiation-driven temperature feedback. Therefore, we perform sensitivity simulations with doubled and quintupled present-day (year 2010) CH4 mixing ratios with the chemistry-climate model EMAC (European Centre for Medium-Range Weather Forecasts, Hamburg version - Modular Earth Submodel System (ECHAM/MESSy) Atmospheric Chemistry) and include in a novel set-up a mixedlayer ocean model to account for tropospheric warming. Strong increases in CH4 lead to a reduction in the hydroxyl radical in the troposphere, thereby extending the CH4 lifetime. Slow climate feedbacks counteract this reduction in the hydroxyl radical through increases in tropospheric water vapour and ozone, thereby dampening the extension of CH4 lifetime in comparison with the quasi-instantaneous response. Changes in the stratospheric circulation evolve clearly with the warming of the troposphere. The Brewer-Dobson circulation strengthens, affecting the response of trace gases, such as ozone, water vapour and CH4 in the stratosphere, and also causing stratospheric temperature changes. In the middle and upper stratosphere, the increase in stratospheric water vapour is reduced with respect to the quasi-instantaneous response. We find that this difference cannot be explained by the response of the cold point and the associated water vapour entry values but by a weaker strengthening of the in situ source of water vapour through CH4 oxidation. However, in the lower stratosphere water vapour increases more strongly when tropospheric warming is accounted for, enlarging its overall radiative impact. The response of the stratosphere adjusted temperatures driven by slow climate feedbacks is dominated by these increases in stratospheric water vapour as well as strongly decreased ozone mixing ratios above the tropical tropopause, which result from enhanced tropical upwelling. While rapid radiative adjustments from ozone and stratospheric water vapour make an essential contribution to the effective CH4 radiative forcing, the radiative impact of the respective slow feedbacks is rather moderate. In line with this, the climate sensitivity from CH4 changes in this chemistry-climate model set-up is not significantly different from the climate sensitivity in carbon-dioxide-driven simulations, provided that the CH4 effective radiative forcing includes the rapid adjustments from ozone and stratospheric water vapour changes

Model simulations of atmospheric methane (1997-2016) and their evaluation using NOAA and AGAGE surface and IAGOS-CARIBIC aircraft observations

Methane (CH4) is an important greenhouse gas, and its atmospheric budget is determined by interacting sources and sinks in a dynamic global environment. Methane observations indicate that after almost a decade of stagnation, from 2006, a sudden and continuing global mixing ratio increase took place. We applied a general circulation model to simulate the global atmospheric budget, variability, and trends of methane for the period 1997–2016. Using interannually constant CH4 a priori emissions from 11 biogenic and fossil source categories, the model results are compared with observations from 17 Advanced Global Atmospheric Gases Experiment (AGAGE) and National Oceanic and Atmospheric Administration (NOAA) surface stations and intercontinental Civil Aircraft for the Regular observation of the atmosphere Based on an Instrumented Container (CARIBIC) flights, with > 4800 CH4 samples, gathered on > 320 flights in the upper troposphere and lowermost stratosphere. Based on a simple optimization procedure, methane emission categories have been scaled to reduce discrepancies with the observational data for the period 1997–2006. With this approach, the all-station mean dry air mole fraction of 1780 nmol mol−1 could be improved from an a priori root mean square deviation (RMSD) of 1.31 % to just 0.61 %, associated with a coefficient of determination (R2) of 0.79. The simulated a priori interhemispheric difference of 143.12 nmol mol−1 was improved to 131.28 nmol mol−1, which matched the observations quite well (130.82 nmol mol−1). Analogously, aircraft measurements were reproduced well, with a global RMSD of 1.1 % for the measurements before 2007, with even better results on a regional level (e.g., over India, with an RMSD of 0.98 % and R2=0.65). With regard to emission optimization, this implied a 30.2 Tg CH4 yr−1 reduction in predominantly fossil-fuel-related emissions and a 28.7 Tg CH4 yr−1 increase of biogenic sources. With the same methodology, the CH4 growth that started in 2007 and continued almost linearly through 2013 was investigated, exploring the contributions by four potential causes, namely biogenic emissions from tropical wetlands, from agriculture including ruminant animals, and from rice cultivation, and anthropogenic emissions (fossil fuel sources, e.g., shale gas fracking) in North America. The optimization procedure adopted in this work showed that an increase in emissions from shale gas (7.67 Tg yr−1), rice cultivation (7.15 Tg yr−1), and tropical wetlands (0.58 Tg yr−1) for the period 2006–2013 leads to an optimal agreement (i.e., lowest RMSD) between model results and observations

High brightness red emitting polymer beads for immunoassays: Comparison between trifluoroacetylacetonates of Europium

Efficiently luminescing spherical polymer particles (beads) in the nanoscale regime of up to approximately 250 nm have become very valuable tools in bioanalytical assays. Eu3+- complexes imbedded in polymethacrylate and polystyrene in particular proved to be extraordinarily useful in sensitive immunochemical and multi-analyte assays, and histo- and cytochemistry. Their obvious advantages derive from both, the possibility to realize very high ratios of emitter complexes to target molecules, and the intrinsically long decay times of the Eu3+-complexes, which allows an almost complete discrimination against bothersome autofluorescence via time-gated measuring techniques; the narrow line emission in conjunction with large apparent Stokes shifts are additional benefits with regard to spectral separation of excitation and emission with optical filters. Last but not least, a reasonable strategy to couple the beads to the analytes is mandatory. We have thus screened a variety of complexes and ancillary ligands; the four most promising candidates evaluated and compared to each other were β-diketonates (trifluoroacetylacetonates, R-CO-CH-CO-CF3, R = - thienyl, -phenyl, -naphthyl and -phenanthryl); highest solubilities in polystyrene were obtained with trioctylphosphine co-ligands. All beads had overall quantum yields in excess of 80% as dried powders and lifetimes well beyond 600 µs. Core-shell particles were devised for the conjugation to model proteins (Avidine, Neutravidine). Their applicability was tested in biotinylated titer plates using time gated measurements and a Lateral Flow Assay as practical examples

Methane chemistry in a nutshell - the new submodels CH4 (v1.0) and TRSYNC (v1.0) in MESSy (v2.54.0)

Climate projections including chemical feedbacks rely on state-of-the-art chemistry-climate models (CCMs). Of particular importance is the role of methane (CH4) for the budget of stratospheric water vapour (SWV), which has an important climate impact. However, simulations with CCMs are, due to the large number of involved chemical species, computationally demanding, which limits the simulation of sensitivity studies. To allow for sensitivity studies and ensemble simulations with a reduced demand for computational resources, we introduce a simplified approach to simulate the core of methane chemistry in form of the new Modular Earth Submodel System (MESSy) submodel CH4. It involves an atmospheric chemistry mechanism reduced to the sink reactions of CH4 with predefined fields of the hydroxyl radical (OH), excited oxygen (O(1D)), and chlorine (Cl), as well as photolysis and the reaction products limited to water vapour (H2O). This chemical production of H2O is optionally fed back onto the specific humidity (q) of the connected general circulation model (GCM), to account for the impact onto SWV and its effect on radiation and stratospheric dynamics. The submodel CH4 is further capable of simulating the four most prevalent CH4 isotopologues for carbon and hydrogen (CH4 and CH3D, as well as 12CH4 and 13CH4). Furthermore, the production of deuterated water vapour (HDO) is, similar to the production of H2O in the CH4 oxidation, optionally passed back to the isotopological hydrological cycle simulated by the submodel H2OISO, using the newly developed auxiliary submodel TRSYNC. Moreover, the simulation of a user-defined number of diagnostic CH4 age and emission classes is possible, the output of which can be used for offline inverse optimization techniques. The presented approach combines the most important chemical hydrological feedback including the isotopic signatures with the advantages concerning the computational simplicity of a GCM, in comparison to a full-featured CCM

Estimating the impact of the radiative feedback from atmospheric methane on climate sensitivity

Methane (CH4), the second most important greenhouse gas directly emitted by human activity, is removed from the atmosphere via chemical degradation. In this study we assess the radiative feedback from atmospheric CH4 resulting from changes in its chemical sink, which is mainly the oxidation with the hydroxyl radical (OH) and, which is influenced by temperature and the chemical composition of the atmosphere. We present results from numerical simulations with the chemistry-climate model EMAC perturbed by either CO2 or CH4 increase. The essential innovation in the simulation set-up is the use of CH4 emission fluxes instead of prescribed CH4 concentrations at the lower boundary. This means that changes in the chemical sink can feed back on the atmospheric CH4 concentration without constraints. For both forcing agents, CO2 and CH4, we explore so called rapid radiative adjustments in simulations with prescribed sea surface temperatures, as well as slow radiative feedbacks and the climate sensitivity in respective simulations using an interactive oceanic mixed layer. To quantify individual physical and chemical radiative adjustments and feedbacks we use the partial radiative perturbation method in offline simulations with a radiative transfer model consistent with the one used in the online simulations. First results show a negative feedback of atmospheric CH4 in a warming and moistening troposphere. As water vapour is a precursor of OH, increased humidity leads to increasing OH mixing ratios. This leads in turn to a shortening of the CH4 lifetime and a reduction of the CH4 mixing ratios accordingly. This decrease in CH4 also affects the response of tropospheric ozone (O3) leading to a less pronounced increase of O3 in the tropical upper troposphere compared to previous studies of the O3 response following a CO2 perturbation (Dietmüller et al., 2014;Nowack et al., 2015;Marsh et al., 2016)

Investigation of strongly enhanced methane Part II: Slow climate feedbacks.

Methane (CH4) is the second most important anthropogenic greenhouse gas and its atmospheric abundance is rising rapidly at the moment (e.g. Nisbet et al., 2019). We assess the effects of doubled and fivefold present-day (2010) CH4 lower boundary mixing ratios on the basis of sensitivity simulations with the chemistry-climate model EMAC. As a follow-up on Winterstein et al. (2019) we investigate slow adjustments by applying a mixed layer ocean (MLO) model instead of prescribed oceanic conditions. In the simulations with prescribed oceanic conditions, tropospheric temperature changes are largely suppressed, while with MLO tropospheric temperatures adjust to the forcing. In the present study we compare the changes in the MLO sensitivity simulations to the sensitivity simulations with prescribed oceanic conditions (Winterstein et al., 2019). Comparing the responses of these two sets of sensitivity simulations separates rapid adjustments and the effects of slow climate feedbacks associated with tropospheric warming. The chemical interactions in the stratosphere in the MLO set-up (slow adjustments) compare in general well with the results of Winterstein et al. (2019) (rapid adjustments). The increase of stratospheric water vapor is albeit 5 % (15 %) points weaker in the MLO doubling (fivefolding) experiment compared to the doubling (fivefolding) experiment with prescribed oceanic conditions in line with a weaker increase of stratospheric OH. Stronger O3 decrease and CH4 increase in the lowermost tropical stratosphere in the MLO sensitivity simulations compared to the sensitivity simulations with prescribed oceanic conditions indicate a more distinct strengthening of tropical up-welling due to tropospheric warming in the MLO set-up. The MLO simulations also show evidence of a strengthening of the Brewer-Dobson Circulation. When separating the quasi-instantaneous chemically induced O3 response from the O3 response pattern in the MLO set-up, the O3 response to slow climate feedbacks remains. This pattern is consistent with the O3 response to slow climate feedbacks induced by increases of CO2. This first of its kind study shows the climatic impact of strongly enhanced CH4 mixing ratios and how the slow climate response of tropospheric warming potentially damp instantaneous chemical feedbacks

Model simulations of atmospheric methane (1997--2016) and their evaluation using NOAA and AGAGE surface and IAGOS-CARIBIC aircraft observations

Methane (CH4) is an important greenhouse gas, and its atmospheric budget is determined by interacting sources and sinks in a dynamic global environment. Methane observations indicate that after almost a decade of stagnation, from 2006, a sudden and continuing global mixing ratio increase took place. We applied a general circulation model to simulate the global atmospheric budget, variability, and trends of methane for the period 1997–2016. Using interannually constant CH4 a priori emissions from 11 biogenic and fossil source categories, the model results are compared with observations from 17 Advanced Global Atmospheric Gases Experiment (AGAGE) and National Oceanic and Atmospheric Administration (NOAA) surface stations and intercontinental Civil Aircraft for the Regular observation of the atmosphere Based on an Instrumented Container (CARIBIC) flights, with > 4800 CH4 samples, gathered on > 320 flights in the upper troposphere and lowermost stratosphere. Based on a simple optimization procedure, methane emission categories have been scaled to reduce discrepancies with the observational data for the period 1997–2006. With this approach, the all-station mean dry air mole fraction of 1780 nmol mol−1 could be improved from an a priori root mean square deviation (RMSD) of 1.31 % to just 0.61 %, associated with a coefficient of determination (R2) of 0.79. The simulated a priori interhemispheric difference of 143.12 nmol mol−1 was improved to 131.28 nmol mol−1, which matched the observations quite well (130.82 nmol mol−1). Analogously, aircraft measurements were reproduced well, with a global RMSD of 1.1 % for the measurements before 2007, with even better results on a regional level (e.g., over India, with an RMSD of 0.98 % and R2=0.65). With regard to emission optimization, this implied a 30.2 Tg CH4 yr−1 reduction in predominantly fossil-fuel-related emissions and a 28.7 Tg CH4 yr−1 increase of biogenic sources. With the same methodology, the CH4 growth that started in 2007 and continued almost linearly through 2013 was investigated, exploring the contributions by four potential causes, namely biogenic emissions from tropical wetlands, from agriculture including ruminant animals, and from rice cultivation, and anthropogenic emissions (fossil fuel sources, e.g., shale gas fracking) in North America. The optimization procedure adopted in this work showed that an increase in emissions from shale gas (7.67 Tg yr−1), rice cultivation (7.15 Tg yr−1), and tropical wetlands (0.58 Tg yr−1) for the period 2006–2013 leads to an optimal agreement (i.e., lowest RMSD) between model results and observations

Effects of Strongly Enhanced Atmospheric Methane Concentrations in a Chemistry-Climate Model: Rapid Adjustments and Slow Feedbacks

Methane (CH4) is the second most important anthropogenic greenhouse gas. Besides its direct radiative impact it induces chemical feedbacks relevant for climate and air quality. We assess the effects of doubled and fivefold present-day (year 2010) CH4 lower boundary mixing ratios on the basis of sensitivity simulations with the chemistry-climate model EMAC. We investigate rapid adjustments and slow feedbacks, and their radiative impacts, by applying prescribed oceanic conditions and a mixed layer ocean (MLO) model, respectively. In the present study we compare the changes in the MLO sensitivity simulations to the experiments with prescribed oceanic conditions (Winterstein et al., 2019). In the troposphere the increased CH4 mixing ratios cause enhanced depletion of the hydroxyl radical (OH), which further results in a prolonged CH4 lifetime. Slow feedbacks, however, dampen the lifetime increase in comparison to the rapid adjustments. OH precursors (water vapour and ozone (O3)) are more strongly increased in the MLO experiments and offset the reduction of OH. The chemical feedbacks in the stratosphere include increases of stratospheric water vapour (SWV) mixing ratios on the order of 50 % for doubled CH4, and 250 % for fivefold CH4. In the middle and upper stratosphere the increase of SWV is weaker in the experiments that include slow feedbacks. This is linked to a weaker increase of stratospheric OH and a likewise weaker strengthening of the CH4 oxidation. In the lower stratosphere slow feedbacks lead to a more pronounced increase of SWV compared to rapid adjustments enlarging its overall radiative impact. The MLO simulations show further evidence of the strengthening of the Brewer-Dobson circulation. The rapid radiative adjustments from O3 and SWV contribute significantly to the CH4 effective radiative forcing, whereas the radiative impact of the respective slow feedbacks is rather moderate. In accordance with this, the climate sensitivity from CH4 changes in this chemistry-climate model set-up is not significantly different from the climate sensitivity in CO2-driven simulations, provided that the rapid adjustments from O3 and SWV changes are included in the CH4 effective radiative forcing

DataSheet1_High brightness red emitting polymer beads for immunoassays: Comparison between trifluoroacetylacetonates of Europium.pdf

Efficiently luminescing spherical polymer particles (beads) in the nanoscale regime of up to approximately 250 nm have become very valuable tools in bioanalytical assays. Eu3+- complexes imbedded in polymethacrylate and polystyrene in particular proved to be extraordinarily useful in sensitive immunochemical and multi-analyte assays, and histo- and cytochemistry. Their obvious advantages derive from both, the possibility to realize very high ratios of emitter complexes to target molecules, and the intrinsically long decay times of the Eu3+-complexes, which allows an almost complete discrimination against bothersome autofluorescence via time-gated measuring techniques; the narrow line emission in conjunction with large apparent Stokes shifts are additional benefits with regard to spectral separation of excitation and emission with optical filters. Last but not least, a reasonable strategy to couple the beads to the analytes is mandatory. We have thus screened a variety of complexes and ancillary ligands; the four most promising candidates evaluated and compared to each other were β-diketonates (trifluoroacetylacetonates, R-CO-CH-CO-CF3, R = - thienyl, -phenyl, -naphthyl and -phenanthryl); highest solubilities in polystyrene were obtained with trioctylphosphine co-ligands. All beads had overall quantum yields in excess of 80% as dried powders and lifetimes well beyond 600 µs. Core-shell particles were devised for the conjugation to model proteins (Avidine, Neutravidine). Their applicability was tested in biotinylated titer plates using time gated measurements and a Lateral Flow Assay as practical examples.</p