Long-term Observations of Atmospheric Halogenated Organic Trace Gases.

CFCs (chlorofluorocarbons) and other strong ozone-depleting halogenated organic trace gases were used in numerous industrial, household and agriculture applications. First atmospheric measurements of CFCs were performed in the 1970s, well ahead of the detection of the ozone hole in the 1980s. The continuous observation of these ozone-depleting substances (ODSs) is crucial for monitoring their global ban within the Montreal Protocol. In addition, also HFCs (fluorinated hydrocarbons) are measured, which were introduced as substitutes of ODSs and are potent greenhouse gases. Since 2000, Empa continuously measures more than 50 halogenated trace gases at the high-Alpine station of Jungfraujoch (3850 m asl) as part of the global AGAGE network (Advanced Global Atmospheric Gases Experiment). Jungfraujoch is the highest location worldwide where such measurements are performed, and the site where several of these compounds were measured in the atmosphere for the first time. The measurements at Jungfraujoch and at other globally well-positioned sites serve as an early warning system, i. e. before potentially harmful halogenated organic substances can accumulate and detrimentally affect the natural environment.

First observations of the fourth generation synthetic halocarbons HFC-1234yf, HFC-1234ze(E), and HCFC-1233zd(E) in the atmosphere.

Halogenated alkenes are a class of anthropogenic substances, which replace ozone-depleting substances and long-lived greenhouse gases in the foam-blowing, refrigeration, and solvent sectors. We report the first multiyear atmospheric measurements of the hydrofluorocarbons HFC-1234yf (2,3,3,3-tetrafluoroprop-1-ene, CF3CF═CH2), and HFC-1234ze(E) (E-1,3,3,3-tetrafluoroprop-1-ene trans-CF3CH═CHF), and the hydrochlorofluorocarbon HCFC-1233zd(E) (E-1-chloro-3,3,3-trifluoroprop-1-ene trans-CF3CH═CHCl) from the high altitude observatory at Jungfraujoch and from urban Dubendorf (Switzerland). When observations started in 2011 HFC-1234yf was undetectable at Jungfraujoch (mole fractions <0.003 ppt, parts-per-trillion, 10(-12)) but since then the percentage of measurements with detectable mole fractions has steadily increased to 4.5% in 2014. By contrast, in 2014 HFC-1234ze(E) was detectable in half of our samples at Jungfraujoch and in all samples at Dubendorf demonstrating the wide use of this compound within the air mass footprints of the stations. Our back trajectory analysis for the Jungfraujoch observations suggests high emission strength of HFC-1234ze(E) in the Belgium/Netherlands region. HCFC-1233zd(E) is present at very low mole fractions (typically <0.03 ppt) at both stations, and features pronounced seasonality and a general absence of pollution events during our 2013-2014 measurements. This is indicative of the presence of significant emissions from source locations outside the footprints of the two stations. Based on a simple one-box model calculation we estimate globally increasing HCFC-1233zd(E) emissions from 0.2 Gg yr(-1) in 2013 to 0.5 Gg yr(-1) for 2014.

A high-resolution monitoring approach of urban CO2 fluxes. Part 2 - surface flux optimisation using eddy covariance observations.

Achieving climate neutrality by 2050 requires ground-breaking technological and methodological advancements in climate change mitigation planning and actions from local to regional scales. Monitoring the cities' CO2 emissions with sufficient detail and accuracy is crucial for guiding sustainable urban transformation. Current methodologies for CO2 emission inventories rely on bottom-up (BU) approaches which do not usually offer information on the spatial or temporal variability of the emissions and present substantial uncertainties. This study develops a novel approach which assimilates direct CO2 flux observations from urban eddy covariance (EC) towers with very high spatiotemporal resolution information from an advanced urban BU surface flux model (Part 1 of this study, Stagakis et al., 2023) within a Bayesian inversion framework. The methodology is applied to the city centre of Basel, Switzerland (3 × 3 km domain), taking advantage of two long-term urban EC sites located 1.6 km apart. The data assimilation provides optimised gridded CO2 flux information individually for each urban surface flux component (i.e. building heating emissions, commercial/industrial emissions, traffic emissions, human respiration emissions, biogenic net exchange) at 20 m resolution and weekly time-step. The results demonstrate that urban EC observations can be consistently used to improve high-resolution BU surface CO2 flux model estimations, providing realistic seasonal variabilities of each flux component. Traffic emissions are determined with the greatest confidence among the five flux components during the inversions. The optimised annual anthropogenic emissions are 14.7 % lower than the prior estimate, the human respiration emissions have decreased by 12.1 %, while the biogenic components transformed from a weak sink to a weak source. The root-mean-square errors (RMSEs) of the weekly comparisons between EC observations and model outputs are consistently reduced. However, a slight underestimation of the total flux, especially in locations with complex CO2 source/sink mixture, is still evident in the optimised fluxes.

Future emissions and atmospheric fate of HFC-1234yf from mobile air conditioners in Europe.

HFC-1234yf (2,3,3,3-tetrafluoropropene) is under discussion for replacing HFC-134a (1,1,1,2-tetrafluoroethane) as a cooling agent in mobile air conditioners (MACs) in the European vehicle fleet. Some HFC-1234yf will be released into the atmosphere, where it is almost completely transformed to the persistent trifluoroacetic acid (TFA). Future emissions of HFC-1234yf after a complete conversion of the European vehicle fleet were assessed. Taking current day leakage rates and predicted vehicle numbers for the year 2020 into account, European total HFC-1234yf emissions from MACs were predicted to range between 11.0 and 19.2 Gg yr(-1). Resulting TFA deposition rates and rainwater concentrations over Europe were assessed with two Lagrangian chemistry transport models. Mean European summer-time TFA mixing ratios of about 0.15 ppt (high emission scenario) will surpass previously measured levels in background air in Germany and Switzerland by more than a factor of 10. Mean deposition rates (wet + dry) of TFA were estimated to be 0.65-0.76 kg km(-2) yr(-1), with a maxium of ∼2.0 kg km(-2) yr(-1) occurring in Northern Italy. About 30-40% of the European HFC-1234yf emissions were deposited as TFA within Europe, while the remaining fraction was exported toward the Atlantic Ocean, Central Asia, Northern, and Tropical Africa. Largest annual mean TFA concentrations in rainwater were simulated over the Mediterranean and Northern Africa, reaching up to 2500 ng L(-1), while maxima over the continent of about 2000 ng L(-1) occurred in the Czech Republic and Southern Germany. These highest annual mean concentrations are at least 60 times lower than previously determined to be a safe level for the most sensitive aquatic life-forms. Rainwater concentrations during individual rain events would still be 1 order of magnitude lower than the no effect level. To verify these results future occasional sampling of TFA in the atmospheric environment should be considered. If future HFC-1234yf emissions surpass amounts used here studies of TFA accumulation in endorheic basins and other sensitive areas should be aspired.

European emissions of halogenated greenhouse gases inferred from atmospheric measurements.

European emissions of nine representative halocarbons (CFC-11, CFC-12, Halon 1211, HCFC-141b, HCFC-142b, HCFC-22, HFC-125, HFC-134a, HFC-152a) are derived for the year 2009 by combining long-term observations in Switzerland, Italy, and Ireland with campaign measurements from Hungary. For the first time, halocarbon emissions over Eastern Europe are assessed by top-down methods, and these results are compared to Western European emissions. The employed inversion method builds on least-squares optimization linking atmospheric observations with calculations from the Lagrangian particle dispersion model FLEXPART. The aggregated halocarbon emissions over the study area are estimated at 125 (106-150) Tg of CO(2) equiv/y, of which the hydrofluorocarbons (HFCs) make up the most important fraction with 41% (31-52%). We find that chlorofluorocarbon (CFC) emissions from banks are still significant and account for 35% (27-43%) of total halocarbon emissions in Europe. The regional differences in per capita emissions are only small for the HFCs, while emissions of CFCs and hydrochlorofluorocarbons (HCFCs) tend to be higher in Western Europe compared to Eastern Europe. In total, the inferred per capita emissions are similar to estimates for China, but 3.5 (2.3-4.5) times lower than for the United States. Our study demonstrates the large benefits of adding a strategically well placed measurement site to the existing European observation network of halocarbons, as it extends the coverage of the inversion domain toward Eastern Europe and helps to better constrain the emissions over Central Europe.

Lagrangian Particle Dispersion Models in the Grey Zone of Turbulence: Adaptations to FLEXPART-COSMO for Simulations at 1 km Grid Resolution.

Lagrangian particle dispersion models (LPDMs) are frequently used for regional-scale inversions of greenhouse gas emissions. However, the turbulence parameterizations used in these models were developed for coarse resolution grids, hence, when moving to the kilometre-scale the validity of these descriptions should be questioned. Here, we analyze the influence of the turbulence parameterization employed in the LPDM FLEXPART-COSMO model. Comparisons of the turbulence kinetic energy between the turbulence schemes of FLEXPART-COSMO and the underlying Eulerian model COSMO suggest that the dispersion in FLEXPART-COSMO suffers from a double-counting of turbulent elements when run at a high resolution of 1 × 1 km 2 . Such turbulent elements are represented in both COSMO, by the resolved grid-scale winds, and FLEXPART, by its stochastic parameterizations. Therefore, we developed a new parametrization for the variations of the winds and the Lagrangian time scales in FLEXPART in order to harmonize the amount of turbulence present in both models. In a case study for a power plant plume, the new scheme results in improved plume representation when compared with in situ flight observations and with a tracer transported in COSMO. Further in-depth validation of the LPDM against methane observations at a tall tower site in Switzerland shows that the model's ability to predict the observed tracer variability and concentration at different heights above ground is considerably enhanced using the updated turbulence description. The high-resolution simulations result in a more realistic and pronounced diurnal cycle of the tracer concentration peaks and overall improved correlation with observations when compared to previously used coarser resolution simulations (at 7 km × 7 km). Our results indicate that the stochastic turbulence schemes of LPDMs, developed in the past for coarse resolution models, should be revisited to include a resolution dependency and resolve only the part of the turbulence spectrum that is a subgrid process at each different mesh size. Although our new scheme is specific to COSMO simulations at 1 × 1 km 2 resolution, the methodology for deriving the scheme can easily be applied to different resolutions and other regional models. Supplementary Information: The online version contains supplementary material available at 10.1007/s10546-022-00728-3.

Global nature run data with realistic high-resolution carbon weather for the year of the Paris Agreement.

The CO2 Human Emissions project has generated realistic high-resolution 9 km global simulations for atmospheric carbon tracers referred to as nature runs to foster carbon-cycle research applications with current and planned satellite missions, as well as the surge of in situ observations. Realistic atmospheric CO2, CH4 and CO fields can provide a reference for assessing the impact of proposed designs of new satellites and in situ networks and to study atmospheric variability of the tracers modulated by the weather. The simulations spanning 2015 are based on the Copernicus Atmosphere Monitoring Service forecasts at the European Centre for Medium Range Weather Forecasts, with improvements in various model components and input data such as anthropogenic emissions, in preparation of a CO2 Monitoring and Verification Support system. The relative contribution of different emissions and natural fluxes towards observed atmospheric variability is diagnosed by additional tagged tracers in the simulations. The evaluation of such high-resolution model simulations can be used to identify model deficiencies and guide further model improvements.

Nanoplastics transport to the remote, high-altitude Alps.

Plastic materials are increasingly produced worldwide with a total estimated production of >8300 million tonnes to date, of which 60% was discarded. In the environment, plastics fragment into smaller particles, e.g. microplastics (size < 5 mm), and further weathering leads to the formation of functionally different contaminants - nanoplastics (size <1 µm). Nanoplastics are believed to have entirely different physical (e.g. transport), chemical (e.g. functional groups at the surface) and biological (passing the cell membrane, toxicity) properties compared to the micro- and macroplastics, yet, their measurement in the environmental samples is seldom available. Here, we present measurements of nanoplastics mass concentration and calculated the deposition at the pristine high-altitude Alpine Sonnblick observatory (3106 MASL), during the 1.5 month campaigh in late winter 2017. The average nanoplastics concentration was 46.5 ng/mL of melted surface snow. The main polymer types of nanoplastics observed for this site were polypropylene (PP) and polyethylene terephthalate (PET). We measured significantly higher concentrations in the dry sampling periods for PET (p < 0.002) but not for PP, which indicates that dry deposition may be the preferential pathway for PET leading to a gradual accumulation on the snow surfaces during dry periods. Air transport modelling indicates regional and long-range transport of nanoplastics, originating preferentially from European urban areas. The mean deposition rate was 42 (+32/-25) kg km-2 year-1. Thus more than 2 × 1011 nanoplastics particles are deposited per square meter of surface snow each week of the observed period, even at this remote location, which raises significant toxicological concerns.

Quantification of methane emissions from UK biogas plants.

The rising number of operational biogas plants in the UK brings a new emissions category to consider for methane monitoring, quantification and reduction. Minimising methane losses from biogas plants to the atmosphere is critical not only because of their contribution of methane to global warming but also with respect to the sustainability of renewable energy production. Mobile greenhouse gas surveys were conducted to detect plumes of methane emissions from the biogas plants in southern England that varied in their size, waste feed input materials and biogas utilization. Gaussian plume modelling was used to estimate total emissions of methane from ten biogas plants based on repeat passes through the plumes. Methane emission rates ranged from 0.1 to 58.7 kg CH4 hr-1, and the percentage of losses relative to the calculated production rate varied between 0.02 and 8.1%. The average emission rate was 15.9 kg CH4 hr-1, and the average loss was 3.7%. In general, methane emission rates from smaller farm biogas plants were higher than from larger food waste biogas plants. We also suggest that biogas methane emissions may account for between 0.4 and 3.8%, with an average being 1.9% of the total methane emissions in the UK excluding the sewage sludge biogas plants.

Simulative and experimental investigations on pressure-induced structural vibrations of a rear muffler.

The periodically blown out exhaust gas of a combustion engine may excite structural vibrations of the exhaust system. In addition to the noise of the orifice, these vibrations contribute to the overall noise radiation of the exhaust system. In this work, the excitation of structural vibrations of a rear muffler via the acoustic path is investigated both in experiments and simulations. In both cases transfer functions from the acoustic pressure at the inlet to the structural deflection on the surface of the rear muffler are determined and compared to each other. For the simulation an FE-FE (finite element) coupling is applied to account for the fluid-structure interaction. To efficiently predict the fluid-structure coupled behavior, a model reduction technique for the finite element method based on the Craig-Bampton method and the Rubin method is presented. In a last step, the sound radiation is evaluated by solving the exterior acoustic problem with the fast multipole boundary element method. For this purpose, the results of the FE computation are used as boundary datum.