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This paper presents large-eddy simulations with atmospheric chemistry of four large point sources world-wide, focusing on the evaluation of NOx (NO + NO2) emissions with the TROPOspheric Monitoring Instrument (TROPOMI). We implemented a condensed chemistry scheme to investigate how the emitted NOx (95 % as NO) is converted to NO2 in the plume. To use NOx as a proxy for CO2 emission, information about its atmospheric lifetime and the fraction of NOx present as NO2 is required. We find that the chemical evolution of the plumes depends strongly on the amount of NOx that is emitted, as well as on wind speed and direction. For large NOx emissions, the chemistry is pushed in a high-NOx chemical regime over a length of almost 100 km downwind of the stack location. Other plumes with lower NOx emissions show a fast transition to an intermediate-NOx chemical regime, with short NOx lifetimes. Simulated NO2 columns mostly agree within 20 % with TROPOMI, signalling that the emissions used in the model were approximately correct. However, variability in the simulations is large, making a one-to-one comparison difficult. We find that temporal wind speed variations should be accounted for in emission estimation methods. Moreover, results indicate that common assumptions about the NO2 lifetime (≈ 4 h) and NOx:NO2 ratios (≈ 1.3) in simplified methods that estimate emissions from NO2 satellite data need revision.

Nitrogen oxides (NOx = NO + NO2) are air pollutants which are co-emitted with CO2 during high-temperature combustion processes. Monitoring NOx emissions is crucial for assessing air quality and for providing proxy estimates of CO2 emissions. Satellite observations, such as those from the TROPOspheric Monitoring Instrument (TROPOMI) on board the Sentinel-5P satellite, provide global coverage at high temporal resolution. However, satellites measure only NO2, necessitating a conversion to NOx. Previous studies have applied a constant NO2-to-NOx conversion factor. In this paper, we develop a more realistic model for NO2-to-NOx conversion and apply it to TROPOMI data of 2020 and 2021. To achieve this, we analysed plume-resolving simulations from the MicroHH large-eddy simulation model with chemistry for the Bełchatów (PL), Jänschwalde (DE), Matimba (ZA) and Medupi (ZA) power plants, as well as a metallurgical plant in Lipetsk (RU). We used the cross-sectional flux method to calculate NO, NO2 and NOx line densities from simulated NO and NO2 columns and derived NO2-to-NOx conversion factors as a function of the time since emission. Since the method of converting NO2 to NOx presented in this paper assumes steady-state conditions and that the conversion factors can be modelled by a negative exponential function, we validated the conversion factors using the same MicroHH data. Finally, we applied the derived conversion factors to TROPOMI NO2 observations of the same sources. The validation of the NO2-to-NOx conversion factors shows that they can account for the NOx chemistry in plumes, in particular for the conversion between NO and NO2 near the source and for the chemical loss of NOx further downstream. When applying these time-since-emission-dependent conversion factors, biases in NOx emissions estimated from TROPOMI NO2 images are greatly reduced from between −50 % and −42 % to between only −9.5 % and −0.5 % in comparison with reported emissions. Single-overpass estimates can be quantified with an uncertainty of 20 %–27 %, while annual NOx emission estimates have uncertainties in the range of 4 %–21 % but are highly dependent on the number of successful retrievals. Although more simulations covering a wider range of meteorological and trace gas background conditions will be needed to generalise the approach, this study marks an important step towards a consistent, uniform, high-resolution and near-real-time estimation of NOx emissions – especially with regard to upcoming NO2-monitoring satellites such as Sentinel-4, Sentinel-5 and CO2M.

The present study evaluates the microstructural features, mechanical properties, and wear characteristics of the newly developed hybrid composite of A356/ZrO2/Al2O3/SiC produced by compo-casting at 605±5 °C, 600 rpm for 15 minutes with less than 30% solid fraction in which Bi and Sn were added separately to the matrix before introducing reinforcements. FESEM micrographs and corresponding EDS illustrated the successful incorporation of particles in the matrix. Fine particles of ZrO2 were observed close to the coarse Al2O3, and SiC particles, along with Bi and Sn elements, were detected at the eutectic evolution region. The A356+Bi/Al2O3+ZrO2+SiC hybrid composite exhibited the lowest specific wear rate (1.642 ×10-7cm3/Nm) and friction coefficient (0.31) under applied loads of 5, 10, and 20 N, in line with the highest hardness (73.4 HBN). Analysis of the worn surfaces revealed that the wear mechanism is mostly adhesive in all synthesized composites, which changed to the combination of adhesive and abrasive mode in the case containing Bi and SiC. Inserting Bi not only leads to the refinement of eutectic Si but also enhances the adhesion between the matrix/particles and improves lubricity. This, in turn, reduces the wear rate and coefficient of friction, ultimately improving the performance of the hybrid composite.

Carbonyl sulfide (COS) is a promising tracer for the estimation of terrestrial ecosystem gross primary production (GPP). However, understanding its non-GPP-related sources and sinks, e.g., anthropogenic sources and soil sources and sinks, is also critical to the success of the approach. Here we infer the regional sources and sinks of COS using continuous in situ mole fraction profile measurements of COS along the 60 m tall Lutjewad tower (1 m a.s.l.; 53∘24′ N, 6∘21′ E) in the Netherlands. To identify potential sources that caused the observed enhancements of COS mole fractions at Lutjewad, both discrete flask samples and in situ measurements in the province of Groningen were made from a mobile van using a quantum cascade laser spectrometer (QCLS). We also simulated the COS mole fractions at Lutjewad using the Stochastic Time-Inverted Lagrangian Transport (STILT) model combined with emission inventories and plant uptake fluxes. We determined the nighttime COS fluxes to be -3.0±2.6 pmol m−2 s−1 using the radon-tracer correlation approach and Lutjewad observations. Furthermore, we identified and quantified several COS sources, including biodigesters, sugar production facilities and silicon carbide production facilities in the province of Groningen. Moreover, the simulation results show that the observed COS enhancements can be partially explained by known industrial sources of COS and CS2, in particular from the Ruhr Valley (51.5∘ N, 7.2∘ E) and Antwerp (51.2∘ N, 4.4∘ E) areas. The contribution of likely missing anthropogenic sources of COS and CS2 in the inventory may be significant. The impact of the identified sources in the province of Groningen is estimated to be negligible in terms of the observed COS enhancements. However, in specific conditions, these sources may influence the measurements in Lutjewad. These results are valuable for improving our understanding of the sources and sinks of COS, contributing to the use of COS as a tracer for GPP.

Despite the consensus on the overall downward trend in Amazon forest loss in the previous decade, estimates of yearly carbon emissions from deforestation still vary widely. Estimated carbon emissions are currently often based on data from local logging activity reports, changes in remotely sensed biomass, and remote detection of fire hotspots and burned area. Here, we use 16 years of satellite-derived carbon monoxide (CO) columns to constrain fire CO emissions from the Amazon Basin between 2003 and 2018. Through data assimilation, we produce 3 d average maps of fire CO emissions over the Amazon, which we verified to be consistent with a long-term monitoring programme of aircraft CO profiles over five sites in the Amazon. Our new product independently confirms a long-term decrease of 54 % in deforestation-related CO emissions over the study period. Interannual variability is large, with known anomalously dry years showing a more than 4-fold increase in basin-wide fire emissions relative to wet years. At the level of individual Brazilian states, we find that both soil moisture anomalies and human ignitions determine fire activity, suggesting that future carbon release from fires depends on drought intensity as much as on continued forest protection. Our study shows that the atmospheric composition perspective on deforestation is a valuable additional monitoring instrument that complements existing bottom-up and remote sensing methods for land-use change. Extension of such a perspective to an operational framework is timely considering the observed increased fire intensity in the Amazon Basin between 2019 and 2021.

This study uses large-eddy simulations (LESs) to evaluate two widely used observational techniques that estimate point source emissions. We evaluate the use of car measurements perpendicular to the wind direction and the commonly used Other Test Method 33A (OTM 33A). The LES study simulates a plume from a point source released into a stationary, homogeneous, and neutral atmospheric surface layer over flat terrain. This choice is motivated by our ambition to validate the observational methods under controlled conditions where they are expected to perform well since the sources of uncertainties are minimized. Three plumes with different release heights were sampled in a manner that mimics sampling according to car transects and the stationary OTM 33A. Subsequently, source strength estimates are compared to the true source strength used in the simulation. Standard deviations of the estimated source strengths decay proportionally to the inverse of the square root of the number of averaged transects, showing statistical independence of individual samples. The analysis shows that for the car transect measurements at least 15 repeated measurement series need to be averaged to obtain a source strength within 40 % of the true source strength. For the OTM 33A analysis, which recommends measurements within 200 m of the source, the estimates of source strengths have similar values close to the source, which is caused by insufficient dispersion of the plume by turbulent mixing close to the source. Additionally, the derived source strength is substantially overestimated with OTM 33A. This overestimation is driven by the proposed OTM 33A dispersion coefficients, which are too large for this specific case. This suggests that the conditions under which the OTM 33A dispersion constants were derived were likely influenced by motions with length scales beyond the scale of the surface layer. Lastly, our simulations indicate that, due to wind-shear effects, the position of the time-averaged centerline of the plumes may differ from the plume emission height. This mismatch can be an additional source of error if a Gaussian plume model (GPM) is used to interpret the measurement. In the case of the car transect measurements, a correct source estimate then requires an adjustment of the source height in the GPM.

This study demonstrates the ability of large-eddy simulation (LES) forced by a large-scale model to reproduce plume dispersion in an actual field campaign. Our aim is to bring together field observations taken under non-ideal conditions and LES to show that this combination can help to derive point-source strengths from sparse observations. We analyze results from a single-day case study based on data collected near an oil well during the ROMEO campaign (ROmanian Methane Emissions from Oil and gas) that took place in October 2019. We set up our LES using boundary conditions derived from the meteorological reanalysis ERA5 and released a point source in line with the configuration in the field. The weather conditions produced by the LES show close agreement with field observations, although the observed wind field showed complex features due to the absence of synoptic forcing. In order to align the plume direction with field observations, we created a second simulation experiment with manipulated wind fields that better resemble the observations. Using these LESs, the estimated source strengths agree well with the emitted artificial tracer gas plume, indicating the suitability of LES to infer source strengths from observations under complex conditions. To further harvest the added value of LES, higher-order statistical moments of the simulated plume were analyzed. Here, we found good agreement with plumes from previous LES and laboratory experiments in channel flows. We derived a length scale of plume mixing from the boundary layer height, the mean wind speed and convective velocity scale. It was demonstrated that this length scale represents the distance from the source at which the predominant plume behavior transfers from meandering dispersion to relative dispersion.

The uptake of carbonyl sulfide (COS) by terrestrial plants is linked to photosynthetic uptake of CO2 as these gases partly share the same uptake pathway. Applying COS as a photosynthesis tracer in models requires an accurate representation of biosphere COS fluxes, but these models have not been extensively evaluated against field observations of COS fluxes. In this paper, the COS flux as simulated by the Simple Biosphere Model, version 4 (SiB4), is updated with the latest mechanistic insights and evaluated with site observations from different biomes: one evergreen needleleaf forest, two deciduous broadleaf forests, three grasslands, and two crop fields spread over Europe and North America. We improved SiB4 in several ways to improve its representation of COS. To account for the effect of atmospheric COS mole fractions on COS biosphere uptake, we replaced the fixed atmospheric COS mole fraction boundary condition originally used in SiB4 with spatially and temporally varying COS mole fraction fields. Seasonal amplitudes of COS mole fractions are ∼50–200 ppt at the investigated sites with a minimum mole fraction in the late growing season. Incorporating seasonal variability into the model reduces COS uptake rates in the late growing season, allowing better agreement with observations. We also replaced the empirical soil COS uptake model in SiB4 with a mechanistic model that represents both uptake and production of COS in soils, which improves the match with observations over agricultural fields and fertilized grassland soils. The improved version of SiB4 was capable of simulating the diurnal and seasonal variation in COS fluxes in the boreal, temperate, and Mediterranean region. Nonetheless, the daytime vegetation COS flux is underestimated on average by 8±27 %, albeit with large variability across sites. On a global scale, our model modifications decreased the modeled COS terrestrial biosphere sink from 922 Gg S yr−1 in the original SiB4 to 753 Gg S yr−1 in the updated version. The largest decrease in fluxes was driven by lower atmospheric COS mole fractions over regions with high productivity, which highlights the importance of accounting for variations in atmospheric COS mole fractions. The change to a different soil model, on the other hand, had a relatively small effect on the global biosphere COS sink. The secondary role of the modeled soil component in the global COS budget supports the use of COS as a global photosynthesis tracer. A more accurate representation of COS uptake in SiB4 should allow for improved application of atmospheric COS as a tracer of local- to global-scale terrestrial photosynthesis.

Large-eddy simulation (LES) models are an excellent tool to improve our understanding of aerosol–cloud interactions (ACI). We introduce a prognostic aerosol scheme with multiple aerosol species in the Dutch Atmospheric Large-Eddy Simulation model (DALES), especially focused on simulating the impact of cloud microphysical processes on the aerosol population. The numerical treatment of aerosol activation is a crucial element for simulating both cloud and aerosol characteristics. Two methods are implemented and discussed: an explicit activation scheme based on κ-Köhler theory and a more classic approach using updraught strength. Sample model simulations are based on the Rain in Shallow Cumulus over the Ocean (RICO) campaign, characterized by rapidly precipitating warm-phase shallow cumulus clouds. We find that in this pristine ocean environment virtually all aerosol mass in cloud droplets is the result of the activation process, while in-cloud scavenging is relatively inefficient. Despite the rapid formation of precipitation, most of the in-cloud aerosol mass is returned to the atmosphere by cloud evaporation. The strength of aerosol processing through subsequent cloud cycles is found to be particularly sensitive to the activation scheme and resulting cloud characteristics. However, the precipitation processes are considerably less sensitive. Scavenging by precipitation is the dominant source for in-rain aerosol mass. About half of the in-rain aerosol reaches the surface, while the rest is released by evaporation of falling precipitation. The effect of cloud microphysics on the average aerosol size depends on the balance between the evaporation of clouds and rain and ultimate removal by precipitation. Analysis of typical aerosol size associated with the different microphysical processes shows that aerosols resuspended by cloud evaporation have a radius that is only 5 % to 10 % larger than the originally activated aerosols. In contrast, aerosols released by evaporating precipitation are an order of magnitude larger.

The TROPOspheric Monitoring Instrument (TROPOMI), launched 13 October 2017, has been measuring carbon monoxide (CO) concentrations in the Earth's atmosphere since early November 2017. In the first measurements, TROPOMI was able to measure CO concentrations of the high-pollution event in India of November 2017. In this paper, we studied the extent of the pollution in India, comparing the TROPOMI CO with modeled data from the Weather Research and Forecasting model (WRF) to identify the most important sources contributing to the high pollution, both at ground level and in the total column. We investigated the period 11–19 November 2017. We found that residential and commercial combustion was a much more important source of CO pollution than the post-monsoon crop burning during this period, which is in contrast to what media suggested and some studies on aerosol emissions found. Also, the high pollution was not limited to Delhi and its direct neighborhood but the accumulation of pollution extended over the whole Indo-Gangetic Plain (IGP) due to the unfavorable weather conditions in combination with extensive emissions. From the TROPOMI data and WRF simulations, we observed a buildup of CO during 11–14 November and a decline in CO after 15 November. The meteorological conditions, characterized by low wind speeds and shallow atmospheric boundary layers, were most likely the primary explanation for the temporal accumulation and subsequent dispersion of regionally emitted CO in the atmosphere. This emphasizes the important role of atmospheric dynamics in determining the air quality conditions at ground level and in the total column. Due to its rapidly growing population and economy, India is expected to encounter similar pollution events more often in future post-monsoon and winter seasons unless significant policy measures are taken to reduce residential and commercial emissions.

The hydroxyl radical (OH) is the main atmospheric oxidant and the primary sink of the greenhouse gas CH4. In an attempt to constrain atmospheric levels of OH, two recent studies combined a tropospheric two-box model with hemispheric-mean observations of methyl chloroform (MCF) and CH4. These studies reached different conclusions concerning the most likely explanation of the renewed CH4 growth rate, which reflects the uncertain and underdetermined nature of the problem. Here, we investigated how the use of a tropospheric two-box model can affect the derived constraints on OH due to simplifying assumptions inherent to a two-box model. To this end, we derived species- and time-dependent quantities from a full 3-D transport model to drive two-box model simulations. Furthermore, we quantified differences between the 3-D simulated tropospheric burden and the burden seen by the surface measurement network of the National Oceanic and Atmospheric Administration (NOAA). Compared to commonly used parameters in two-box models, we found significant deviations in the magnitude and time-dependence of the interhemispheric exchange rate, exposure to OH, and stratospheric loss rate. For MCF these deviations can be large due to changes in the balance of its sources and sinks over time. We also found that changes in the yearly averaged tropospheric burden of CH4 and MCF can be obtained within 0.96 ppb yr−1 and 0.14 % yr−1 by the NOAA surface network, but that substantial systematic biases exist in the interhemispheric mixing ratio gradients that are input to two-box model inversions. To investigate the impact of the identified biases on constraints on OH, we accounted for these biases in a two-box model inversion of MCF and CH4. We found that the sensitivity of interannual OH anomalies to the biases is modest (1 %–2 %), relative to the uncertainties on derived OH (3 %–4 %). However, in an inversion where we implemented all four bias corrections simultaneously, we found a shift to a positive trend in OH concentrations over the 1994–2015 period, compared to the standard inversion. Moreover, the absolute magnitude of derived global mean OH, and by extent, that of global CH4 emissions, was affected much more strongly by the bias corrections than their anomalies (∼10 %). Through our analysis, we identified and quantified limitations in the two-box model approach as well as an opportunity for full 3-D simulations to address these limitations. However, we also found that this derivation is an extensive and species-dependent exercise and that the biases were not always entirely resolvable. In future attempts to improve constraints on the atmospheric oxidative capacity through the use of simple models, a crucial first step is to consider and account for biases similar to those we have identified for the two-box model.

The interactions between biogenic volatile organic compounds (BVOCs), like isoprene and monoterpenes, and anthropogenic emissions of nitrogen and sulfur oxides lead to high concentrations of secondary organic aerosol (SOA) in the southeastern United States. To improve our understanding of SOA formation, we study the diurnal evolution of SOA in a land–atmosphere coupling context based on comprehensive surface and upper air observations from a characteristic day during the 2013 Southern Oxidant and Aerosol Study (SOAS) campaign. We use a mixed layer model (MXLCH-SOA) that is updated with new chemical pathways and an interactive land surface scheme that describes both biogeochemical and biogeophysical couplings between the land surface and the atmospheric boundary layer (ABL) to gain insight into the drivers of the daytime evolution of biogenic SOA. MXLCH-SOA reproduces observed BVOC and surface heat fluxes, gas-phase chemistry, and ABL dynamics well, with the exception of isoprene and monoterpene mixing ratios measured close to the land surface. This is likely due to the fact that these species do not have uniform profiles throughout the atmospheric surface layer due to their fast reaction with OH and incomplete mixing near the surface. The flat daytime evolution of the SOA concentration is caused by the dampening of the increase due to locally formed SOA by entrainment of SOA-depleted air from the residual layer. SOA formation from isoprene through the intermediate species isoprene epoxydiols (IEPOXs) and isoprene hydroxyhydroperoxides (ISOPOOHs) is in good agreement with the observations, with a mean isoprene SOA yield of 1.8 %. However, SOA from monoterpenes, oxidised by OH and O3, dominates the locally produced SOA (69 %), with a mean monoterpene SOA yield of 10.7 %. Isoprene SOA is produced primarily through OH oxidation via ISOPOOH and IEPOX (31 %). Entrainment of aged SOA from the residual layer likely contributes to the observed more oxidised oxygenated organic aerosol (MO-OOA) factor. A sensitivity analysis of the coupled land surface–boundary layer–SOA formation system to changing temperatures reveals that SOA concentrations are buffered under increasing temperatures: a rise in BVOC emissions is offset by decreases in OH concentrations and the efficiency with which SVOCs partition into the aerosol phase.

This paper presents the first results of an age-of-air (AoA) inter-comparison of six global transport models. Following a protocol, three global circulation models and three chemistry transport models simulated five tracers with boundary conditions that grow linearly in time. This allows for an evaluation of the AoA and transport times associated with inter-hemispheric transport, vertical mixing in the troposphere, transport to and in the stratosphere, and transport of air masses between land and ocean. Since AoA is not a directly measurable quantity in the atmosphere, simulations of 222Rn and SF6 were also performed. We focus this first analysis on averages over the period 2000–2010, taken from longer simulations covering the period 1988–2014. We find that two models, NIES and TOMCAT, show substantially slower vertical mixing in the troposphere compared to other models (LMDZ, TM5, EMAC, and ACTM). However, while the TOMCAT model, as used here, has slow transport between the hemispheres and between the atmosphere over land and ocean, the NIES model shows efficient horizontal mixing and a smaller latitudinal gradient in SF6 compared to the other models and observations. We find consistent differences between models concerning vertical mixing of the troposphere, expressed as AoA differences and modelled 222Rn gradients between 950 and 500 hPa. All models agree, however, on an interesting asymmetry in inter-hemispheric mixing, with faster transport from the Northern Hemisphere surface to the Southern Hemisphere than vice versa. This is attributed to a rectifier effect caused by a stronger seasonal cycle in boundary layer venting over Northern Hemispheric land masses, and possibly to a related asymmetric position of the intertropical convergence zone. The calculated AoA in the mid–upper stratosphere varies considerably among the models (4–7 years). Finally, we find that the inter-model differences are generally larger than differences in AoA that result from using the same model with a different resolution or convective parameterisation. Taken together, the AoA model inter-comparison provides a useful addition to traditional approaches to evaluate transport timescales. Results highlight that inter-model differences associated with resolved transport (advection, reanalysis data, nudging) and parameterised transport (convection, boundary layer mixing) are still large and require further analysis. For this purpose, all model output and analysis software are available.

The representation of aerosol–cloud interaction in global climate models (GCMs) remains a large source of uncertainty in climate projections. Due to its complexity, precipitation evaporation is either ignored or taken into account in a simplified manner in GCMs. This research explores various ways to treat aerosol resuspension and determines the possible impact of precipitation evaporation and subsequent aerosol resuspension on global aerosol burdens and distribution. The representation of aerosol wet deposition by large-scale precipitation in the EC-Earth model has been improved by utilising additional precipitation-related 3-D fields from the dynamical core, the Integrated Forecasting System (IFS) general circulation model, in the chemistry and aerosol module Tracer Model, version 5 (TM5). A simple approach of scaling aerosol release with evaporated precipitation fraction leads to an increase in the global aerosol burden (+7.8 to +15 % for different aerosol species). However, when taking into account the different sizes and evaporation rate of raindrops following Gong et al. (2006), the release of aerosols is strongly reduced, and the total aerosol burden decreases by −3.0 to −8.5 %. Moreover, inclusion of cloud processing based on observations by Mitra et al. (1992) transforms scavenged small aerosol to coarse particles, which enhances removal by sedimentation and hence leads to a −10 to −11 % lower aerosol burden. Finally, when these two effects are combined, the global aerosol burden decreases by −11 to −19 %. Compared to the Moderate Resolution Imaging Spectroradiometer (MODIS) satellite observations, aerosol optical depth (AOD) is generally underestimated in most parts of the world in all configurations of the TM5 model and although the representation is now physically more realistic, global AOD shows no large improvements in spatial patterns. Similarly, the agreement of the vertical profile with Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) satellite measurements does not improve significantly. We show, however, that aerosol resuspension has a considerable impact on the modelled aerosol distribution and needs to be taken into account.

The growth of mega-cities leads to air quality problems directly affecting the citizens. Satellite measurements are becoming of higher quality and quantity, which leads to more accurate satellite retrievals of enhanced air pollutant concentrations over large cities. In this paper, we compare and discuss both an existing and a new method for estimating urban-scale trends in CO emissions using multi-year retrievals from the MOPITT satellite instrument. The first method is mainly based on satellite data, and has the advantage of fewer assumptions, but also comes with uncertainties and limitations as shown in this paper. To improve the reliability of urban-to-regional scale emission trend estimation, we simulate MOPITT retrievals using the Weather Research and Forecast model with chemistry core (WRF-Chem). The difference between model and retrieval is used to optimize CO emissions in WRF-Chem, focusing on the city of Madrid, Spain. This method has the advantage over the existing method in that it allows both a trend analysis of CO concentrations and a quantification of CO emissions. Our analysis confirms that MOPITT is capable of detecting CO enhancements over Madrid, although significant differences remain between the yearly averaged model output and satellite measurements (R2 = 0.75) over the city. After optimization, we find Madrid CO emissions to be lower by 48 % for 2002 and by 17 % for 2006 compared with the EdgarV4.2 emission inventory. The MOPITT-derived emission adjustments lead to better agreement with the European emission inventory TNO-MAC-III for both years. This suggests that the downward trend in CO emissions over Madrid is overestimated in EdgarV4.2 and more realistically represented in TNO-MACC-III. However, our satellite and model based emission estimates have large uncertainties, around 20 % for 2002 and 50 % for 2006.

Air mass factor (AMF) calculation is the largest source of uncertainty in NO2 and HCHO satellite retrievals in situations with enhanced trace gas concentrations in the lower troposphere. Structural uncertainty arises when different retrieval methodologies are applied within the scientific community to the same satellite observations. Here, we address the issue of AMF structural uncertainty via a detailed comparison of AMF calculation methods that are structurally different between seven retrieval groups for measurements from the Ozone Monitoring Instrument (OMI). We estimate the escalation of structural uncertainty in every sub-step of the AMF calculation process. This goes beyond the algorithm uncertainty estimates provided in state-of-the-art retrievals, which address the theoretical propagation of uncertainties for one particular retrieval algorithm only. We find that top-of-atmosphere reflectances simulated by four radiative transfer models (RTMs) (DAK, McArtim, SCIATRAN and VLIDORT) agree within 1.5 %. We find that different retrieval groups agree well in the calculations of altitude resolved AMFs from different RTMs (to within 3 %), and in the tropospheric AMFs (to within 6 %) as long as identical ancillary data (surface albedo, terrain height, cloud parameters and trace gas profile) and cloud and aerosol correction procedures are being used. Structural uncertainty increases sharply when retrieval groups use their preference for ancillary data, cloud and aerosol correction. On average, we estimate the AMF structural uncertainty to be 42 % over polluted regions and 31 % over unpolluted regions, mostly driven by substantial differences in the a priori trace gas profiles, surface albedo and cloud parameters. Sensitivity studies for one particular algorithm indicate that different cloud correction approaches result in substantial AMF differences in polluted conditions (5 to 40 % depending on cloud fraction and cloud pressure, and 11 % on average) even for low cloud fractions (2 and HCHO retrievals.

The aim of this paper is to present an overview of inverse modeling methods that have been developed over the years for estimating the global sources and sinks of CH4. It provides insight into how techniques and estimates have evolved over time and what the remaining shortcomings are. As such, it serves a didactical purpose of introducing apprentices to the field, but it also takes stock of developments so far and reflects on promising new directions. The main focus is on methodological aspects that are particularly relevant for CH4, such as its atmospheric oxidation, the use of methane isotopologues, and specific challenges in atmospheric transport modeling of CH4. The use of satellite retrievals receives special attention as it is an active field of methodological development, with special requirements on the sampling of the model and the treatment of data uncertainty. Regional scale flux estimation and attribution is still a grand challenge, which calls for new methods capable of combining information from multiple data streams of different measured parameters. A process model representation of sources and sinks in atmospheric transport inversion schemes allows the integrated use of such data. These new developments are needed not only to improve our understanding of the main processes driving the observed global trend but also to support international efforts to reduce greenhouse gas emissions.

We evaluate the capability of the global atmospheric transport model TM5 to simulate the boundary layer dynamics and associated variability of trace gases close to the surface, using radon (222Rn). Focusing on the European scale, we compare the boundary layer height (BLH) in the TM5 model with observations from the National Oceanic and Atmospheric Admnistration (NOAA) Integrated Global Radiosonde Archive (IGRA) and also with ceilometer and lidar (light detection and ranging) BLH retrievals at two stations. Furthermore, we compare TM5 simulations of 222Rn activity concentrations, using a novel, process-based 222Rn flux map over Europe (Karstens et al., 2015), with harmonised 222Rn measurements at 10 stations. The TM5 model reproduces relatively well the daytime BLH (within 10–20 % for most of the stations), except for coastal sites, for which differences are usually larger due to model representation errors. During night, however, TM5 overestimates the shallow nocturnal BLHs, especially for the very low observed BLHs ( The 222Rn activity concentration simulations based on the new 222Rn flux map show significant improvements especially regarding the average seasonal variability, compared to simulations using constant 222Rn fluxes. Nevertheless, the (relative) differences between simulated and observed daytime minimum 222Rn activity concentrations are larger for several stations (on the order of 50 %) than the (relative) differences between simulated and observed BLH at noon. Although the nocturnal BLH is often higher in the model than observed, simulated 222Rn nighttime maxima are actually larger at several continental stations. This counterintuitive behaviour points to potential deficiencies of TM5 to correctly simulate the vertical gradients within the nocturnal boundary layer, limitations of the 222Rn flux map, or issues related to the definition of the nocturnal BLH. At several stations the simulated decrease of 222Rn activity concentrations in the morning is faster than observed. In addition, simulated vertical 222Rn activity concentration gradients at Cabauw decrease faster than observations during the morning transition period, and are in general lower than observed gradients during daytime. Although these effects may be partially due to the slow response time of the radon detectors, they clearly point to too fast vertical mixing in the TM5 boundary layer during daytime. Furthermore, the capability of the TM5 model to simulate the diurnal BLH cycle is limited by the current coarse temporal resolution (3 h/6 h) of the TM5 input meteorology.

This study investigates the constraint provided by greenhouse gas measurements from space on surface fluxes. Imperfect knowledge of the light path through the atmosphere, arising from scattering by clouds and aerosols, can create biases in column measurements retrieved from space. To minimize the impact of such biases, ratios of total column retrieved CH4 and CO2 (Xratio) have been used. We apply the ratio inversion method described in Pandey et al. (2015) to retrievals from the Greenhouse Gases Observing SATellite (GOSAT). The ratio inversion method uses the measured Xratio as a weak constraint on CO2 fluxes. In contrast, the more common approach of inverting proxy CH4 retrievals (Frankenberg et al., 2005) prescribes atmospheric CO2 fields and optimizes only CH4 fluxes. The TM5–4DVAR (Tracer Transport Model version 5–variational data assimilation system) inverse modeling system is used to simultaneously optimize the fluxes of CH4 and CO2 for 2009 and 2010. The results are compared to proxy inversions using model-derived CO2 mixing ratios (XCO2model) from CarbonTracker and the Monitoring Atmospheric Composition and Climate (MACC) Reanalysis CO2 product. The performance of the inverse models is evaluated using measurements from three aircraft measurement projects. Xratio and XCO2model are compared with TCCON retrievals to quantify the relative importance of errors in these components of the proxy XCH4 retrieval (XCH4proxy). We find that the retrieval errors in Xratio (mean = 0.61 %) are generally larger than the errors in XCO2model (mean = 0.24 and 0.01 % for CarbonTracker and MACC, respectively). On the annual timescale, the CH4 fluxes from the different satellite inversions are generally in agreement with each other, suggesting that errors in XCO2model do not limit the overall accuracy of the CH4 flux estimates. On the seasonal timescale, however, larger differences are found due to uncertainties in XCO2model, particularly over Australia and in the tropics. The ratio method stays closer to the a priori CH4 flux in these regions, because it is capable of simultaneously adjusting the CO2 fluxes. Over tropical South America, comparison to independent measurements shows that CO2 fields derived from the ratio method are less realistic than those used in the proxy method. However, the CH4 fluxes are more realistic, because the impact of unaccounted systematic uncertainties is more evenly distributed between CO2 and CH4. The ratio inversion estimates an enhanced CO2 release from tropical South America during the dry season of 2010, which is in accordance with the findings of Gatti et al. (2014) and Van der Laan et al. (2015). The performance of the ratio method is encouraging, because despite the added nonlinearity due to the assimilation of Xratio and the significant increase in the degree of freedom by optimizing CO2 fluxes, still consistent results are obtained with respect to other CH4 inversions.

Oceans are a net source of molecular hydrogen (H2) to the atmosphere. The production of marine H2 is assumed to be mainly biological by N2 fixation, but photochemical pathways are also discussed. We present measurements of mole fraction and isotopic composition of dissolved and atmospheric H2 from the southern and northern Atlantic between 2008 and 2010. In total almost 400 samples were taken during 5 cruises along a transect between Punta Arenas (Chile) and Bremerhaven (Germany), as well as at the coast of Mauritania.The isotopic source signatures of dissolved H2 extracted from surface water are highly deuterium-depleted and correlate negatively with temperature, showing δD values of (−629 ± 54) ‰ for water temperatures at (27 ± 3) °C and (−249 ± 88) ‰ below (19 ± 1) °C. The results for warmer water masses are consistent with the biological production of H2. This is the first time that marine H2 excess has been directly attributed to biological production by isotope measurements. However, the isotope values obtained in the colder water masses indicate that beside possible biological production, a significant different source should be considered.The atmospheric measurements show distinct differences between both hemispheres as well as between seasons. Results from the global chemistry transport model TM5 reproduce the measured H2 mole fractions and isotopic composition well. The climatological global oceanic emissions from the GEMS database are in line with our data and previously published flux calculations. The good agreement between measurements and model results demonstrates that both the magnitude and the isotopic signature of the main components of the marine H2 cycle are in general adequately represented in current atmospheric models despite a proposed source different from biological production or a substantial underestimation of nitrogen fixation by several authors.

The CH4 growth rate in the atmosphere showed large variations after the Pinatubo eruption in June 1991. A decrease of more than 10 ppb yr−1 in the growth rate over the course of 1992 was reported, and a partial recovery in the following year. Although several reasons have been proposed to explain the evolution of CH4 after the eruption, their contributions to the observed variations are not yet resolved. CH4 is removed from the atmosphere by the reaction with tropospheric OH, which in turn is produced by O3 photolysis under UV radiation. The CH4 removal after the Pinatubo eruption might have been affected by changes in tropospheric UV levels due to the presence of stratospheric SO2 and sulfate aerosols, and due to enhanced ozone depletion on Pinatubo aerosols. The perturbed climate after the eruption also altered both sources and sinks of atmospheric CH4. Furthermore, CH4 concentrations were influenced by other factors of natural variability in that period, such as El Niño–Southern Oscillation (ENSO) and biomass burning events. Emissions of CO, NOX and non-methane volatile organic compounds (NMVOCs) also affected CH4 concentrations indirectly by influencing tropospheric OH levels.Potential drivers of CH4 variability are investigated using the TM5 global chemistry model. The contribution that each driver had to the global CH4 variability during the period 1990 to 1995 is quantified. We find that a decrease of 8–10 ppb yr−1 CH4 is explained by a combination of the above processes. However, the timing of the minimum growth rate is found 6&nash;9 months later than observed. The long-term decrease in CH4 growth rate over the period 1990 to 1995 is well captured and can be attributed to an increase in OH concentrations over this time period. Potential uncertainties in our modelled CH4 growth rate include emissions of CH4 from wetlands, biomass burning emissions of CH4 and other compounds, biogenic NMVOC and the sensitivity of OH to NMVOC emission changes. Two inventories are used for CH4 emissions from wetlands, ORCHIDEE and LPJ, to investigate the role of uncertainties in these emissions. Although the higher climate sensitivity of ORCHIDEE improves the simulated CH4 growth rate change after Pinatubo, none of the two inventories properly captures the observed CH4 variability in this period.

We present a method for assimilating total column CH4 : CO2 ratio measurements from satellites for inverse modeling of CH4 and CO2 fluxes using the variational approach. Unlike conventional approaches, in which retrieved CH4 : CO2 are multiplied by model-derived total column CO2 and only the resulting CH4 is assimilated, our method assimilates the ratio of CH4 and CO2 directly and is therefore called the ratio method. It is a dual tracer inversion, in which surface fluxes of CH4 and CO2 are optimized simultaneously. The optimization of CO2 fluxes turns the hard constraint of prescribing model-derived CO2 fields into a weak constraint on CO2, which allows us to account for uncertainties in CO2. The method has been successfully tested in a synthetic inversion setup. We show that the ratio method is able to reproduce assumed true CH4 and CO2 fluxes starting from a prior, which is derived by perturbing the true fluxes randomly. We compare the performance of the ratio method with that of the traditional proxy approach and the use of only surface measurements for estimating CH4 fluxes. Our results confirm that the optimized CH4 fluxes are sensitive to the treatment of CO2, and that hard constraints on CO2 may significantly compromise results that are obtained for CH4. We find that the relative performance of ratio and proxy methods have a regional dependence. The ratio method performs better than the proxy method in regions where the CO2 fluxes are most uncertain. However, both ratio and proxy methods perform better than the surface-measurement-only inversion, confirming the potential of spaceborne measurements for accurately determining fluxes of CH4 and other greenhouse gases (GHGs).

This study investigates the use of total column CH4 (XCH4) retrievals from the SCIAMACHY satellite instrument for quantifying large-scale emissions of methane. A unique data set from SCIAMACHY is available spanning almost a decade of measurements, covering a period when the global CH4 growth rate showed a marked transition from stable to increasing mixing ratios. The TM5 4DVAR inverse modelling system has been used to infer CH4 emissions from a combination of satellite and surface measurements for the period 2003–2010. In contrast to earlier inverse modelling studies, the SCIAMACHY retrievals have been corrected for systematic errors using the TCCON network of ground-based Fourier transform spectrometers. The aim is to further investigate the role of bias correction of satellite data in inversions. Methods for bias correction are discussed, and the sensitivity of the optimized emissions to alternative bias correction functions is quantified. It is found that the use of SCIAMACHY retrievals in TM5 4DVAR increases the estimated inter-annual variability of large-scale fluxes by 22% compared with the use of only surface observations. The difference in global methane emissions between 2-year periods before and after July 2006 is estimated at 27–35 Tg yr−1. The use of SCIAMACHY retrievals causes a shift in the emissions from the extra-tropics to the tropics of 50 ± 25 Tg yr−1. The large uncertainty in this value arises from the uncertainty in the bias correction functions. Using measurements from the HIPPO and BARCA aircraft campaigns, we show that systematic errors in the SCIAMACHY measurements are a main factor limiting the performance of the inversions. To further constrain tropical emissions of methane using current and future satellite missions, extended validation capabilities in the tropics are of critical importance.

A modelling experiment has been conceived to assess the impact of transport model errors on methane emissions estimated in an atmospheric inversion system. Synthetic methane observations, obtained from 10 different model outputs from the international TransCom-CH4 model inter-comparison exercise, are combined with a prior scenario of methane emissions and sinks, and integrated into the three-component PYVAR-LMDZ-SACS (PYthon VARiational-Laboratoire de Météorologie Dynamique model with Zooming capability-Simplified Atmospheric Chemistry System) inversion system to produce 10 different methane emission estimates at the global scale for the year 2005. The same methane sinks, emissions and initial conditions have been applied to produce the 10 synthetic observation datasets. The same inversion set-up (statistical errors, prior emissions, inverse procedure) is then applied to derive flux estimates by inverse modelling. Consequently, only differences in the modelling of atmospheric transport may cause differences in the estimated fluxes. In our framework, we show that transport model errors lead to a discrepancy of 27 Tg yr−1 at the global scale, representing 5% of total methane emissions. At continental and annual scales, transport model errors are proportionally larger than at the global scale, with errors ranging from 36 Tg yr−1 in North America to 7 Tg yr−1 in Boreal Eurasia (from 23 to 48%, respectively). At the model grid-scale, the spread of inverse estimates can reach 150% of the prior flux. Therefore, transport model errors contribute significantly to overall uncertainties in emission estimates by inverse modelling, especially when small spatial scales are examined. Sensitivity tests have been carried out to estimate the impact of the measurement network and the advantage of higher horizontal resolution in transport models. The large differences found between methane flux estimates inferred in these different configurations highly question the consistency of transport model errors in current inverse systems. Future inversions should include more accurately prescribed observation covariances matrices in order to limit the impact of transport model errors on estimated methane fluxes.

The fires around Moscow in July and August 2010 emitted a large amount of pollutants to the atmosphere. Here we estimate the carbon monoxide (CO) source strength of the Moscow fires in July and August by using the TM5-4DVAR system in combination with CO column observations of the Infrared Atmospheric Sounding Interferometer (IASI). It is shown that the IASI observations provide a strong constraint on the total emissions needed in the model. Irrespective of the prior emissions used, the optimised CO fire emission estimates from mid-July to mid-August 2010 amount to approximately 24 Tg CO. This estimate depends only weakly (< 15%) on the assumed diurnal variations and injection height of the emissions. However, the estimated emissions might depend on unaccounted model uncertainties such as vertical transport. Our emission estimate of 22–27 Tg CO during roughly one month of intense burning is less than suggested by another recent study, but substantially larger than predicted by the bottom-up inventories. This latter discrepancy suggests that bottom-up emission estimates for extreme peat burning events require improvements.

A modified cumulus convection parametrisation scheme is presented. This scheme computes the mass of air transported upward in a cumulus cell using conservation of moisture and a detailed distribution of convective precipitation provided by a reanalysis dataset. The representation of vertical transport within the scheme includes entrainment and detrainment processes in convective updrafts and downdrafts. Output from the proposed parametrisation scheme is employed in the National Institute for Environmental Studies (NIES) global chemical transport model driven by JRA-25/JCDAS reanalysis. The simulated convective precipitation rate and mass fluxes are compared with observations and reanalysis data. A simulation of the short-lived tracer 222Rn is used to further evaluate the performance of the cumulus convection scheme. Simulated distributions of 222Rn are evaluated against observations at the surface and in the free troposphere, and compared with output from models that participated in the TransCom-CH4 Transport Model Intercomparison. From this comparison, we demonstrate that the proposed convective scheme in general is consistent with observed and modeled results.

The global methane (CH4) growth rate showed large variations after the eruption of Mount Pinatubo in June 1991. Both sources and sinks of tropospheric CH4 were altered following the eruption, by feedback processes between climate and tropospheric photochemistry. Such processes include Ultra Violet (UV) radiative changes due to the presence of volcanic sulfur dioxide (SO2) and sulphate aerosols in the stratosphere, and due to stratospheric ozone depletion. Changes in temperature and water vapour in the following years caused changes in tropospheric chemistry, as well as in natural emissions. We present a sensitivity study that investigates the relative effects that these processes had on tropospheric CH4 concentrations, using a simple one-dimensional chemistry model representative for the global tropospheric column. To infer the changes in UV radiative fluxes, the chemistry model is coupled to a radiative transfer model. We find that the overall effect of natural processes after the eruption on the CH4 growth rate is dominated by the reduction in CH4 lifetime due to stratospheric ozone depletion. However, all the other processes are found to have non-negligible effects, and should therefore be taken into account in order to obtain a good estimate of CH4 concentrations after Pinatubo. We find that the overall effect was a small initial increase in the CH4 growth rate after the eruption, followed by a decrease of about 7 ppb yr−1 by mid-1993. When changes in anthropogenic emissions are employed according to emission inventories, an additional decrease of about 5 ppb yr−1 in the CH4 growth rate is obtained between the years 1991 and 1993. The results using the simplified single column model are in good qualitative agreement with observed changes in the CH4 growth rate. Further analysis, taking into account changes in the dynamics of the atmosphere, variations in emissions from biomass burning, and in biogenic emissions of non-methane volatile organic compounds (NMVOC), requires the use of a full three-dimensional model.

A chemistry-transport model (CTM) intercomparison experiment (TransCom-CH4) has been designed to investigate the roles of surface emissions, transport and chemical loss in simulating the global methane distribution. Model simulations were conducted using twelve models and four model variants and results were archived for the period of 1990–2007. All but one model transports were driven by reanalysis products from 3 different meteorological agencies. The transport and removal of CH4 in six different emission scenarios were simulated, with net global emissions of 513 ± 9 and 514 ± 14 Tg CH4 yr−1 for the 1990s and 2000s, respectively. Additionally, sulfur hexafluoride (SF6) was simulated to check the interhemispheric transport, radon (222Rn) to check the subgrid scale transport, and methyl chloroform (CH3CCl3) to check the chemical removal by the tropospheric hydroxyl radical (OH). The results are compared to monthly or annual mean time series of CH4, SF6 and CH3CCl3 measurements from 8 selected background sites, and to satellite observations of CH4 in the upper troposphere and stratosphere. Most models adequately capture the vertical gradients in the stratosphere, the average long-term trends, seasonal cycles, interannual variations (IAVs) and interhemispheric (IH) gradients at the surface sites for SF6, CH3CCl3 and CH4. The vertical gradients of all tracers between the surface and the upper troposphere are consistent within the models, revealing vertical transport differences between models. An average IH exchange time of 1.39 ± 0.18 yr is derived from SF6 time series. Sensitivity simulations suggest that the estimated trends in exchange time, over the period of 1996–2007, are caused by a change of SF6 emissions towards the tropics. Using six sets of emission scenarios, we show that the decadal average CH4 growth rate likely reached equilibrium in the early 2000s due to the flattening of anthropogenic emission growth since the late 1990s. Up to 60% of the IAVs in the observed CH4 concentrations can be explained by accounting for the IAVs in emissions, from biomass burning and wetlands, as well as meteorology in the forward models. The modeled CH4 budget is shown to depend strongly on the troposphere-stratosphere exchange rate and thus on the model's vertical grid structure and circulation in the lower stratosphere. The 15-model median CH4 and CH3CCl3 atmospheric lifetimes are estimated to be 9.99 ± 0.08 and 4.61 ± 0.13 yr, respectively, with little IAV due to transport and temperature.

We describe the setup and first results of an inverse modelling system for atmospheric N2O, based on a four-dimensional variational (4DVAR) technique and the atmospheric transport zoom model TM5. We focus in this study on the European domain, utilizing a comprehensive set of quasi-continuous measurements over Europe, complemented by N2O measurements from the Earth System Research Laboratory of the National Oceanic and Atmospheric Administration (NOAA/ESRL) cooperative global air sampling network. Despite ongoing measurement comparisons among networks parallel measurements at a limited number of stations show that significant offsets exist among the different laboratories. Since the spatial gradients of N2O mixing ratios are of the same order of magnitude as these biases, the direct use of these biased datasets would lead to significant errors in the derived emissions. Therefore, in order to also use measurements with unknown offsets, a new bias correction scheme has been implemented within the TM5-4DVAR inverse modelling system, thus allowing the simultaneous assimilation of observations from different networks. The N2O bias corrections determined in the TM5-4DVAR system agree within ~0.1 ppb (dry-air mole fraction) with the bias derived from the measurements at monitoring stations where parallel NOAA discrete air samples are available. The N2O emissions derived for the northwest European and east European countries for 2006 show good agreement with the bottom-up emission inventories reported to the United Nations Framework Convention on Climate Change (UNFCCC). Moreover, the inverse model can significantly narrow the uncertainty range reported in N2O emission inventories for these countries, while the lack of measurements does not allow to reduce the uncertainties of emission estimates in southern Europe. Several sensitivity experiments were performed to test the robustness of the results. It is shown that also inversions without detailed a priori spatio-temporal emission distributions are capable to reproduce major regional emission patterns within the footprint of the existing atmospheric network, demonstrating the strong constraints of the atmospheric observations on the derived emissions.

We present a comprehensive description and benchmark evaluation of the tropospheric chemistry version of the global chemistry transport model TM5 (Tracer Model 5, version TM5-chem-v3.0). A full description is given concerning the photochemical mechanism, the interaction with aerosol, the treatment of the stratosphere, the wet and dry deposition parameterizations, and the applied emissions. We evaluate the model against a suite of ground-based, satellite, and aircraft measurements of components critical for understanding global photochemistry for the year 2006. The model exhibits a realistic oxidative capacity at a global scale. The methane lifetime is ~8.9 years with an associated lifetime of methyl chloroform of 5.86 years, which is similar to that derived using an optimized hydroxyl radical field. The seasonal cycle in observed carbon monoxide (CO) is well simulated at different regions across the globe. In the Northern Hemisphere CO concentrations are underestimated by about 20 ppbv in spring and 10 ppbv in summer, which is related to missing chemistry and underestimated emissions from higher hydrocarbons, as well as to uncertainties in the seasonal variation of CO emissions. The model also captures the spatial and seasonal variation in formaldehyde tropospheric columns as observed by SCIAMACHY. Positive model biases over the Amazon and eastern United States point to uncertainties in the isoprene emissions as well as its chemical breakdown. Simulated tropospheric nitrogen dioxide columns correspond well to observations from the Ozone Monitoring Instrument in terms of its seasonal and spatial variability (with a global spatial correlation coefficient of 0.89), but TM5 fields are lower by 25–40%. This is consistent with earlier studies pointing to a high bias of 0–30% in the OMI retrievals, but uncertainties in the emission inventories have probably also contributed to the discrepancy. TM5 tropospheric nitrogen dioxide profiles are in good agreement (within ~0.1 ppbv) with in situ aircraft observations from the INTEX-B campaign over (the Gulf of) Mexico. The model reproduces the spatial and seasonal variation in background surface ozone concentrations and tropospheric ozone profiles from the World Ozone and Ultraviolet Radiation Data Centre to within 10 ppbv, but at several tropical stations the model tends to underestimate ozone in the free troposphere. The presented model results benchmark the TM5 tropospheric chemistry version, which is currently in use in several international cooperation activities, and upon which future model improvements will take place.

Our understanding of the global black carbon (BC) cycle is essentially qualitative due to uncertainties in our knowledge of its properties. This work investigates two source of uncertainties in modelling black carbon: those due to the use of different schemes for BC ageing and its removal rate in the global Transport-Chemistry model TM5 and those due to the uncertainties in the definition and quantification of the observations, which propagate through to both the emission inventories, and the measurements used for the model evaluation. The schemes for the atmospheric processing of black carbon that have been tested with the model are (i) a simple approach considering BC as bulk aerosol and a simple treatment of the removal with fixed 70% of in-cloud black carbon concentrations scavenged by clouds and removed when rain is present and (ii) a more complete description of microphysical ageing within an aerosol dynamics model, where removal is coupled to the microphysical properties of the aerosol, which results in a global average of 40% in-cloud black carbon that is scavenged in clouds and subsequently removed by rain, thus resulting in a longer atmospheric lifetime. This difference is reflected in comparisons between both sets of modelled results and the measurements. Close to the sources, both anthropogenic and vegetation fire source regions, the model results do not differ significantly, indicating that the emissions are the prevailing mechanism determining the concentrations and the choice of the aerosol scheme does not influence the levels. In more remote areas such as oceanic and polar regions the differences can be orders of magnitude, due to the differences between the two schemes. The more complete description reproduces the seasonal trend of the black carbon observations in those areas, although not always the magnitude of the signal, while the more simplified approach underestimates black carbon concentrations by orders of magnitude. The sensitivity to wet scavenging has been tested by varying in-cloud and below-cloud removal. BC lifetime increases by 10% when large scale and convective scale precipitation removal efficiency are reduced by 30%, while the variation is very small when below-cloud scavenging is zero. Since the emission inventories are representative of elemental carbon-like substance, the model output should be compared to elemental carbon measurements and if known, the ratio of black carbon to elemental carbon mass should be taken into account when the model is compared with black carbon observations.

Inverse modeling is widely employed to provide "top-down" emission estimates using atmospheric measurements. Here, we analyze the dependence of derived CH4 emissions on the sampling frequency and density of the observational surface network, using the TM5-4DVAR inverse modeling system and synthetic observations. This sensitivity study focuses on Europe. The synthetic observations are created by TM5 forward model simulations. The inversions of these synthetic observations are performed using virtually no knowledge on the a priori spatial and temporal distribution of emissions, i.e. the emissions are derived mainly from the atmospheric signal detected by the measurement network. Using the European network of stations for which continuous or weekly flask measurements are available for 2001, the synthetic experiments can retrieve the "true" annual total emissions for single countries such as France within 20%, and for all North West European countries together within ~5%. However, larger deviations are obtained for South and East European countries due to the scarcity of stations in the measurement network. Upgrading flask sites to stations with continuous measurements leads to an improvement for central Europe in emission estimates. For realistic emission estimates over the whole European domain, however, a major extension of the number of stations in the existing network is required. We demonstrate the potential of an extended network of a total of ~60 European stations to provide realistic emission estimates over the whole European domain.

We evaluate black carbon (BC) model predictions from the AeroCom model intercomparison project by considering the diversity among year 2000 model simulations and comparing model predictions with available measurements. These model-measurement intercomparisons include BC surface and aircraft concentrations, aerosol absorption optical depth (AAOD) retrievals from AERONET and Ozone Monitoring Instrument (OMI) and BC column estimations based on AERONET. In regions other than Asia, most models are biased high compared to surface concentration measurements. However compared with (column) AAOD or BC burden retreivals, the models are generally biased low. The average ratio of model to retrieved AAOD is less than 0.7 in South American and 0.6 in African biomass burning regions; both of these regions lack surface concentration measurements. In Asia the average model to observed ratio is 0.7 for AAOD and 0.5 for BC surface concentrations. Compared with aircraft measurements over the Americas at latitudes between 0 and 50N, the average model is a factor of 8 larger than observed, and most models exceed the measured BC standard deviation in the mid to upper troposphere. At higher latitudes the average model to aircraft BC ratio is 0.4 and models underestimate the observed BC loading in the lower and middle troposphere associated with springtime Arctic haze. Low model bias for AAOD but overestimation of surface and upper atmospheric BC concentrations at lower latitudes suggests that most models are underestimating BC absorption and should improve estimates for refractive index, particle size, and optical effects of BC coating. Retrieval uncertainties and/or differences with model diagnostic treatment may also contribute to the model-measurement disparity. Largest AeroCom model diversity occurred in northern Eurasia and the remote Arctic, regions influenced by anthropogenic sources. Changing emissions, aging, removal, or optical properties within a single model generated a smaller change in model predictions than the range represented by the full set of AeroCom models. Upper tropospheric concentrations of BC mass from the aircraft measurements are suggested to provide a unique new benchmark to test scavenging and vertical dispersion of BC in global models.

Large-scale hydrological modelling has become increasingly wide-spread during the last decade. An annual workshop series on large-scale hydrological modelling has provided, since 1997, a forum to the German-speaking community for discussing recent developments and achievements in this research area. In this paper we present the findings from the 2007 workshop which focused on advances and visions in large-scale hydrological modelling. We identify the state of the art, difficulties and research perspectives with respect to the themes "sensitivity of model results", "integrated modelling" and "coupling of processes in hydrosphere, atmosphere and biosphere". Some achievements in large-scale hydrological modelling during the last ten years are presented together with a selection of remaining challenges for the future.

The effects of unified aerosol sources on global aerosol fields simulated by different models are examined in this paper. We compare results from two AeroCom experiments, one with different (ExpA) and one with unified emissions, injection heights, and particle sizes at the source (ExpB). Surprisingly, harmonization of aerosol sources has only a small impact on the simulated inter-model diversity of the global aerosol burden, and consequently global optical properties, as the results are largely controlled by model-specific transport, removal, chemistry (leading to the formation of secondary aerosols) and parameterizations of aerosol microphysics (e.g., the split between deposition pathways) and to a lesser extent by the spatial and temporal distributions of the (precursor) emissions. The burdens of black carbon and especially sea salt become more coherent in ExpB only, because the large ExpA diversities for these two species were caused by a few outliers. The experiment also showed that despite prescribing emission fluxes and size distributions, ambiguities in the implementation in individual models can lead to substantial differences. These results indicate the need for a better understanding of aerosol life cycles at process level (including spatial dispersal and interaction with meteorological parameters) in order to obtain more reliable results from global aerosol simulations. This is particularly important as such model results are used to assess the consequences of specific air pollution abatement strategies.

The AeroCom exercise diagnoses multi-component aerosol modules in global modeling. In an initial assessment simulated global distributions for mass and mid-visible aerosol optical thickness (aot) were compared among 20 different modules. Model diversity was also explored in the context of previous comparisons. For the component combined aot general agreement has improved for the annual global mean. At 0.11 to 0.14, simulated aot values are at the lower end of global averages suggested by remote sensing from ground (AERONET ca. 0.135) and space (satellite composite ca. 0.15). More detailed comparisons, however, reveal that larger differences in regional distribution and significant differences in compositional mixture remain. Of particular concern are large model diversities for contributions by dust and carbonaceous aerosol, because they lead to significant uncertainty in aerosol absorption (aab). Since aot and aab, both, influence the aerosol impact on the radiative energy-balance, the aerosol (direct) forcing uncertainty in modeling is larger than differences in aot might suggest. New diagnostic approaches are proposed to trace model differences in terms of aerosol processing and transport: These include the prescription of common input (e.g. amount, size and injection of aerosol component emissions) and the use of observational capabilities from ground (e.g. measurements networks) or space (e.g. correlations between aerosol and clouds).

Simulation results of global aerosol models have been assembled in the framework of the AeroCom intercomparison exercise. In this paper, we analyze the life cycles of dust, sea salt, sulfate, black carbon and particulate organic matter as simulated by sixteen global aerosol models. The differences among the results (model diversities) for sources and sinks, burdens, particle sizes, water uptakes, and spatial dispersals have been established. These diversities have large consequences for the calculated radiative forcing and the aerosol concentrations at the surface. Processes and parameters are identified which deserve further research. The AeroCom all-models-average emissions are dominated by the mass of sea salt (SS), followed by dust (DU), sulfate (SO4), particulate organic matter (POM), and finally black carbon (BC). Interactive parameterizations of the emissions and contrasting particles sizes of SS and DU lead generally to higher diversities of these species, and for total aerosol. The lower diversity of the emissions of the fine aerosols, BC, POM, and SO4, is due to the use of similar emission inventories, and does therefore not necessarily indicate a better understanding of their sources. The diversity of SO4-sources is mainly caused by the disagreement on depositional loss of precursor gases and on chemical production. The diversities of the emissions are passed on to the burdens, but the latter are also strongly affected by the model-specific treatments of transport and aerosol processes. The burdens of dry masses decrease from largest to smallest: DU, SS, SO4, POM, and BC. The all-models-average residence time is shortest for SS with about half a day, followed by SO4 and DU with four days, and POM and BC with six and seven days, respectively. The wet deposition rate is controlled by the solubility and increases from DU, BC, POM to SO4 and SS. It is the dominant sink for SO4, BC, and POM, and contributes about one third to the total removal of SS and DU species. For SS and DU we find high diversities for the removal rate coefficients and deposition pathways. Models do neither agree on the split between wet and dry deposition, nor on that between sedimentation and other dry deposition processes. We diagnose an extremely high diversity for the uptake of ambient water vapor that influences the particle size and thus the sink rate coefficients. Furthermore, we find little agreement among the model results for the partitioning of wet removal into scavenging by convective and stratiform rain. Large differences exist for aerosol dispersal both in the vertical and in the horizontal direction. In some models, a minimum of total aerosol concentration is simulated at the surface. Aerosol dispersal is most pronounced for SO4 and BC and lowest for SS. Diversities are higher for meridional than for vertical dispersal, they are similar for the individual species and highest for SS and DU. For these two components we do not find a correlation between vertical and meridional aerosol dispersal. In addition the degree of dispersals of SS and DU is not related to their residence times. SO4, BC, and POM, however, show increased meridional dispersal in models with larger vertical dispersal, and dispersal is larger for longer simulated residence times.

The sensitivity to two different emission inventories, injection altitude and temporal variations of anthropogenic emissions in aerosol modelling is studied, using the two way nested global transport chemistry model TM5 focussing on Europe in June and December 2000. The simulations of gas and aerosol concentrations and aerosol optical depth (AOD) with the EMEP and AEROCOM emission inventories are compared with EMEP gas and aerosol surface based measurements, AERONET sun photometers retrievals and MODIS satellite data. For the aerosol precursor gases SO2 and NOx in both months the model results calculated with the EMEP inventory agree better (overestimated by a factor 1.3 for both SO2 and NOx) with the EMEP measurements than the simulation with the AEROCOM inventory (overestimated by a factor 2.4 and 1.9, respectively). Besides the differences in total emissions between the two inventories, an important role is also played by the vertical distribution of SO2 and NOx emissions in understanding the differences between the EMEP and AEROCOM inventories. In December NOx and SO2 from both simulations agree within 50% with observations. In June SO4= evaluated with the EMEP emission inventory agrees slightly better with surface observations than the AEROCOM simulation, whereas in December the use of both inventories results in an underestimate of SO4 with a factor 2. Nitrate aerosol measured in summer is not reliable, however in December nitrate aerosol calculations with the EMEP and AEROCOM emissions agree with 30%, and 60%, respectively with the filter measurements. Differences are caused by the total emissions and the temporal distribution of the aerosol precursor gases NOx and NH3. Despite these differences, we show that the column integrated AOD is less sensitive to the underlying emission inventories. Calculated AOD values with both emission inventories underestimate the observed AERONET AOD values by 20–30%, whereas a case study using MODIS data shows a high spatial agreement. Our evaluation of the role of temporal distribution of anthropogenic emissions on aerosol calculations shows that the daily and weekly temporal distributions of the emissions are only important for NOx, NH3 and aerosol nitrate. However, for all aerosol species SO4=, NH4+, POM, BC, as well as for AOD, the seasonal temporal variations used in the emission inventory are important. Our study shows the value of including at least seasonal information on anthropogenic emissions, although from a comparison with a range of measurements it is often difficult to firmly identify the superiority of specific emission inventories, since other modelling uncertainties, e.g. related to transport, aerosol removal, water uptake, and model resolution, play a dominant role.

To elucidate human induced changes of aerosol load and composition in the atmosphere, a coupled aerosol and gas-phase chemistry transport model of the troposphere and lower stratosphere has been used. The present 3-D modeling study focuses on aerosol chemical composition change since preindustrial times considering the secondary organic aerosol formation together with all other main aerosol components including nitrate. In particular, we evaluate non-sea-salt sulfate (nss-SO4=), ammonium (NH4+), nitrate (NO3−), black carbon (BC), sea-salt, dust, primary and secondary organics (POA and SOA) with a focus on the importance of secondary organic aerosols. Our calculations show that the aerosol optical depth (AOD) has increased by about 21% since preindustrial times. This enhancement of AOD is attributed to a rise in the atmospheric load of BC, nss-SO4=, NO3, POA and SOA by factors of 3.3, 2.6, 2.7, 2.3 and 1.2, respectively, whereas we assumed that the natural dust and sea-salt sources remained constant. The nowadays increase in carbonaceous aerosol loading is dampened by a 34–42% faster conversion of hydrophobic to hydrophilic carbonaceous aerosol leading to higher removal rates. These changes between the various aerosol components resulted in significant modifications of the aerosol chemical composition. The relative importance of the various aerosol components is critical for the aerosol climatic effect, since atmospheric aerosols behave differently when their chemical composition changes. According to this study, the aerosol composition changed significantly over the different continents and with height since preindustrial times. The presence of anthropogenically emitted primary particles in the atmosphere facilitates the condensation of the semi-volatile species that form SOA onto the aerosol phase, particularly in the boundary layer. The SOA burden that is dominated by the natural component has increased by 24% while its contribution to the AOD has increased by 11%. The increase in oxidant levels and preexisting aerosol mass since preindustrial times is the reason of the burden change, since emissions have not changed significantly. The computed aerosol composition changes translate into about 2.5 times more water associated with non sea-salt aerosol. Additionally, aerosols contain 2.7 times more inorganic components nowadays than during the preindustrial times. We find that the increase in emissions of inorganic aerosol precursors is much larger than the corresponding aerosol increase, reflecting a non-linear atmospheric response.

This paper describes the global chemistry Transport Model, version 5 (TM5) which allows two-way nested zooming. The model is used for global studies which require high resolution regionally but can work on a coarser resolution globally. The zoom algorithm introduces refinement in both space and time in some predefined regions. Boundary conditions of the zoom region are provided by a coarser parent grid and the results of the zoom area are communicated back to the parent. A case study using 222Rn measurements that were taken during the MINOS campaign reveals the advantages of local zooming. As a next step, it is investigated to what extent simulated concentrations over Europe are influenced by using an additional zoom domain over North America. An artificial ozone-like tracer is introduced with a lifetime of twenty days and simplified non-linear chemistry. The concentration differences at Mace Head (Ireland) are generally smaller than 10%, much smaller than the effects of the resolution enhancement over Europe. Thus, coarsening of resolution at some distance of a sampling station seems allowed. However, it is also noted that the budgets of the tracers change considerably due to resolution dependencies of, for instance, vertical transport. Due to the two-way nested algorithm, TM5 offers a consistent tool to study the effects of grid refinement on global atmospheric chemistry issues like intercontinental transport of air pollution.

A synthesis inversion based on the atmospheric zoom model TM5 is used to derive top-down estimates of CH4 emissions from individual European countries for the year 2001. We employ a model zoom over Europe with 1° × 1° resolution that is two-way nested into the global model domain (with resolution of 6° × 4°. This approach ensures consistent boundary conditions for the zoom domain and thus European top-down estimates consistent with global CH4 observations. The TM5 model, driven by ECMWF analyses, simulates synoptic scale events at most European and global sites fairly well, and the use of high-frequency observations allows exploiting the information content of individual synoptic events. A detailed source attribution is presented for a comprehensive set of 56 monitoring sites, assigning the atmospheric signal to the emissions of individual European countries and larger global regions. The available observational data put significant constraints on emissions from different regions. Within Europe, in particular several Western European countries are well constrained. The inversion results suggest up to 50-90% higher anthropogenic CH4 emissions in 2001 for Germany, France and UK compared to reported UNFCCC values (EEA, 2003). A recent revision of the German inventory, however, resulted in an increase of reported CH4 emissions by 68.5% (EEA, 2004), being now in very good agreement with our top-down estimate. The top-down estimate for Finland is distinctly smaller than the a priori estimate, suggesting much smaller CH4 emissions from Finnish wetlands than derived from the bottom-up inventory. The EU-15 totals are relatively close to UNFCCC values (within 4-30%) and appear very robust for different inversion scenarios.

During the Mediterranean Intensive Oxidant Study MINOS in August 2001, 87 air samples were collected at the ground-based station Finokalia (35°19'N, 25°40'E) on the north coast of Crete and subsequently analysed by GC-MS. The analysis includes various hydrocarbons, organo-halogens, HCFCs and CFCs. These compounds have a wide variety of sources and sinks and a large range of atmospheric lifetimes. We evaluated the characteristics of the sampling site in terms of proximity to individual sources by plotting the measured variability of these species against lifetime. The resulting linear relationship suggests that the sampling site is representative of intermediate conditions between a remote site and one that is in the vicinity of a wide variety of sources. Our analysis of air mass origin and chemical ratios also shows that several distinct anthropogenic sources influenced the atmospheric composition over Crete. Propane observations are compared to a global model to assess the fossil fuel related emission inventory. Although the model reproduces the general pattern of the propane variations, the model mixing ratios are systematically too low by a factor of 1.5 to 3, probably due to an underestimation of the propane emissions from east European countries in the underlying global database EDGAR. Another important finding was that methyl chloroform, a compound banned under the Montreal protocol, showed significant enhancements from background, which were well correlated with CFC-113. This suggests continued use and emission of methyl chloroform by one or more European countries. We also discuss the observed variations of methyl bromide and suggest that the significant peak observed on 12 August 2001 reflects heavy agricultural use as a soil fumigant in Italy.

We have used a 3D chemistry transport model to evaluate the transport of HF and CH4 in the stratosphere during the Arctic winter of 1999/2000. Several model experiments were carried out with the use of a zoom algorithm to investigate the effect of different horizontal resolutions. Balloon-borne and satellite-borne observations of HF and CH4 were used to test the model. In addition, air mass descent rates within the polar vortex were calculated and compared to observations. Outside the vortex the model results agree well with the observations, but inside the vortex the model underestimates the observed vertical gradient in HF and CH4, even when the highest available resolution (1º x 1º) is applied. The calculated diabatic descent rates agree with observations above potential temperature levels of 450 K. These model results suggest that too strong mixing through the vortex edge could be a plausible cause for the model discrepancies, associated with the calculated mass fluxes, although other reasons are also discussed. Based on our model experiments we conclude that a global 6º x 9º resolution is too coarse to represent the polar vortex, whereas the higher resolutions, 3º x 2º and 1º x 1º, yield similar results, even with a 6º x 9º resolution in the tropical region.

The trend and interannual variability of methane sources are derived from multi-annual simulations of tropospheric photochemistry using a 3-D global chemistry-transport model. Our semi-inverse analysis uses the fifteen years (1979--1993) re-analysis of ECMWF meteorological data and annually varying emissions including photo-chemistry, in conjunction with observed CH4 concentration distributions and trends derived from the NOAA-CMDL surface stations. Dividing the world in four zonal regions (45--90 N, 0--45 N, 0--45 S, 45--90 S) we find good agreement in each region between (top-down) calculated emission trends from model simulations and (bottom-up) estimated anthropogenic emission trends based on the EDGAR global anthropogenic emission database, which amounts for the period 1979--1993 2.7 Tg CH4 yr-1. Also the top-down determined total global methane emission compares well with the total of the bottom-up estimates. We use the difference between the bottom-up and top-down determined emission trends to calculate residual emissions. These residual emissions represent the inter-annual variability of the methane emissions. Simulations have been performed in which the year-to-year meteorology, the emissions of ozone precursor gases, and the stratospheric ozone column distribution are either varied, or kept constant. In studies of methane trends it is most important to include the trends and variability of the oxidant fields. The analyses reveals that the variability of the emissions is of the order of 8Tg CH4 yr-1, and likely related to wetland emissions and/or biomass burning.

A new method has been developed that provides mass-conserving wind fields for global chemistry-transport models. In previous global Eulerian modeling studies a mass-imbalance was found between the model mass transport and the surface pressure tendencies. Several methods have been suggested to correct for this imbalance, but so far no satisfactory solution has been found. Our new method solves these problems by using the wind fields in a spherical harmonical form (divergence and vorticity) by mimicing the physics of the weather forecast model as closely as possible. A 3-D chemistry-transport model was used to show that the calculated ozone fields with the new processing method agree remarkably better with ozone observations in the upper troposphere and lower stratosphere. In addition, the calculated age of air in the lower stratosphere show better agreement with observations, although the air remains still too young in the extra-tropical stratosphere.

We have compared the 14-year record of satellite derived tropical tropospheric ozone columns (TTOC) from the NIMBUS--7 Total Ozone Mapping Spectrometer (TOMS) to TTOC calculated by achemistry-transport model (CTM). An objective measure of error, based on the zonal distribution of TTOC in the tropics, is applied to perform this comparison systematically. In addition, the sensitivity of the model to several key processes in the tropics is quantified to select directions for future improvements. The comparisons indicate a widespread, systematic (20%) discrepancy over the tropical Atlantic Ocean, which maximizes during austral Spring. Although independent evidence from ozonesondes shows that some of the disagreement is due to satellite overestimate of TTOC, the Atlantic mismatch is largely due to a misrepresentation of seasonally recurring processes in the model. Only minor differences between the model and observations over the Pacific occur, mostly due to interannual variability not captured by the model. Although chemical processes determine the TTOC extent, dynamical processes dominate the TTOC distribution, as the use of actual meteorology pertaining to the year of observations always leads to a better agreement with TTOC observations than using a random year or a climatology. The modeled TTOC is remarkably insensitive to many model parameters due to efficient feedbacks in the ozone budget. Nevertheless, the simulations would profit from an improved biomass burning calendar, as well as from an increase in NOx abundances in free tropospheric biomass burning plumes. The model showed the largest response to lightning NOx emissions, but systematic improvements could not be found. The use of multi-year satellite derived tropospheric data to systematically test and improve a CTM is a promising new addition to existing methods of model validation, and is a first step to integrating tropospheric satellite observations into global ozone modeling studies. Conversely, the CTM may suggest improvements to evolving satellite retrievals for tropospheric ozone.

No abstract available.

LNG can be stored either in flat bottom storage tanks or pressurized storage tanks such as bullets or spheres. Safety levels of atmospheric storage tanks are classified by codes as "single containment", "double containment" and "full containment". For spherical and bullet tanks an analogical definition by codes is missing and containment philosophies for atmospheric storage cannot be applied to pressurized storage. Therefore a new definition is proposed to describe the safety levels of pressurized tank types and flat-bottom tank types consistently. It is supposed to use the definitions single, double and full integrity instead of single, double and full containment in order not to mix up definitions. The integrity level a storage tank has been assigned to gives a direct link to the consequences that would have to be taken into account in case the primary container fails totally. The advantage of these new containment definitions is having available a normalized basis for the comparison of different tanks fulfilling similar requirements on safety design. It is expected, that the integrity level of the LNG storage vessel has influence on the risk to external population. To evaluate this influence, the risk to external population caused by the different LNG storage alternatives has been calculated by means of a quantitative risk assessment. These calculations show, that in general the risk to external population is the higher the lower the integrity level of the LNG storage. Therefore it can be concluded that high integrity solutions should be chosen where exposure of third party population is high. This should be considered when selecting the tank type (i.e. integrity level) with regard to the distance to populated areas as well as the population density.

No abstract available.