Refine
Year of publication
Document Type
- Article (593) (remove)
Has Fulltext
- yes (593)
Is part of the Bibliography
- no (593)
Keywords
- climate change (11)
- Climate change (5)
- Atmospheric chemistry (4)
- Geochemistry (4)
- loess (4)
- Biogeochemistry (3)
- COSMO-CLM (3)
- Klimawandel (3)
- Palaeoclimate (3)
- Salinity (3)
Institute
- Geowissenschaften (593) (remove)
The SAWNUC (Sulphuric Acid Water NUCleation) microphysical aerosol nucleation model is used to study the effect of reactor walls on the interpretation of nucleation experiments with respect to nucleation theory. This work shows that loss processes, such as wall losses, influence the interpretation of nucleation experiments, especially at low growth rates and short lifetimes of freshly nucleated particles. In these cases the power dependency of the formation rates, determined at a certain particle size, with respect to H2SO4 does not correspond to the approximate number of H2SO4 molecules in the critical cluster as expected by the first nucleation theorem. Observed ∂log(J)/∂log([H2SO4]) therefore can vary widely for identical nucleation conditions but different sink terms.
We investigate the contribution of oceanic methyl iodide (CH3I) to the stratospheric iodine budget. Based on CH3I measurements from three tropical ship campaigns and the Lagrangian transport model FLEXPART, we provide a detailed analysis of CH3I transport from the ocean surface to the cold point in the upper tropical tropopause layer (TTL). While average oceanic emissions differ by less than 50% from campaign to campaign, the measurements show much stronger variations within each campaign. A positive correlation between the oceanic CH3I emissions and the efficiency of CH3I troposphere–stratosphere transport has been identified for some cruise sections. The mechanism of strong horizontal surface winds triggering large emissions on the one hand and being associated with tropical convective systems, such as developing typhoons, on the other hand, could explain the identified correlations. As a result of the simultaneous occurrence of large CH3I emissions and strong vertical uplift, localized maximum mixing ratios of 0.6 ppt CH3I at the cold point have been determined for observed peak emissions during the SHIVA (Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere)-Sonne research vessel campaign in the coastal western Pacific. The other two campaigns give considerably smaller maxima of 0.1 ppt CH3I in the open western Pacific and 0.03 ppt in the coastal eastern Atlantic. In order to assess the representativeness of the large local mixing ratios, we use climatological emission scenarios to derive global upper air estimates of CH3I abundances. The model results are compared with available upper air measurements, including data from the recent ATTREX and HIPPO2 aircraft campaigns. In the eastern Pacific region, the location of the available measurement campaigns in the upper TTL, the comparisons give a good agreement, indicating that around 0.01 to 0.02 ppt of CH3I enter the stratosphere. However, other tropical regions that are subject to stronger convective activity show larger CH3I entrainment, e.g., 0.08 ppt in the western Pacific. Overall our model results give a tropical contribution of 0.04 ppt CH3I to the stratospheric iodine budget. The strong variations in the geographical distribution of CH3I entrainment suggest that currently available upper air measurements are not representative of global estimates and further campaigns will be necessary in order to better understand the CH3I contribution to stratospheric iodine.
As part of the CLACE-6 campaign we performed size-resolved CCN measurements for a~supersaturation range of S = 0.079 % to 0.66% at the high-alpine research station Jungfraujoch, Switzerland, in March~2007. The derived effective hygroscopicity parameter κ describing the influence of particle composition on CCN activity was on average 0.23–0.30 for Aitken (50–100 nm) and 0.32–0.43 for accumulation mode particles (100–200 nm). The campaign average value of κ = 0.3 is similar to the average value of κ for other continental locations. When air masses came from southeasterly directions crossing the Po Valley in Italy, particles were much more hygroscopic (κ ≈ 0.42) due to large sulfate mass fractions. The κ values obtained at S = 0.079 % exhibited a good negative correlation with the organic mass fractions derived from PM1 aerosol mass spectrometer (AMS) measurements. Applying a simple mixing rule the organic and inorganic mass fractions observed by the AMS could be used to reproduce the temporal fluctuations of the hygroscopicity of accumulation mode particles quite well.
We show how during a cloud event the aerosol particles were activated as cloud droplets and then removed from the air by precipitation leaving behind only a small amount of accumulation mode particles consisting mainly of weakly CCN-active particles, most likely externally mixed unprocessed soot particles.
During the campaign we had the opportunity to directly compare two DMT CCN counters for a certain time. The total CCN concentration (NCCN,tot) obtained by the two instruments at equal supersaturations agreed well for both possible operating modes: detecting NCCN,tot directly by sampling the polydisperse aerosol with the CCNC, or indirectly by combining size-resolved measurements of the activated fraction with parallel measurements of the particle size distribution (e.g., by SMPS). However, some supersaturation setpoints differed between the two CCNCs by as much as 20% after applying the instrument calibrations, which resulted in differences of the corresponding NCCN,tot of up to 50%. This emphasizes that it is extremely important to carefully calibrate the supersaturation of the instrument, especially at low S.
The link between atmospheric radicals and newly formed particles at a spruce forest site in Germany
(2013)
It has been claimed for more than a century that atmospheric new particle formation is primarily influenced by the presence of sulphuric acid. However, the activation process of sulphuric acid related clusters into detectable particles is still an unresolved topic. In this study we focus on the PARADE campaign measurements conducted during August/September 2011 at Mt. Kleiner Feldberg in central Germany. During this campaign a set of radicals, organic and inorganic compounds and oxidants and aerosol properties were measured or calculated. We compared a range of organic and inorganic nucleation theories, evaluating their ability to simulate measured particle formation rates at 3 nm in diameter (J3) for a variety of different conditions. Nucleation mechanisms involving only sulphuric acid tentatively captured the observed noon-time daily maximum in J3, but displayed an increasing difference to J3 measurements during the rest of the diurnal cycle. Including large organic radicals, i.e. organic peroxy radicals (RO2) deriving from monoterpenes and their oxidation products in the nucleation mechanism improved the correlation between observed and simulated J3. This supports a recently proposed empirical relationship for new particle formation that has been used in global models. However, the best match between theory and measurements for the site of interest was found for an activation process based on large organic peroxy radicals and stabilized Criegee intermediates (sCI). This novel laboratory derived algorithm simulated the daily pattern and intensity of J3 observed in the ambient data. In this algorithm organic derived radicals are involved in activation and growth and link the formation rate of smallest aerosol particles with OH during daytime and NO3 during nighttime. Because of the RO2s lifetime is controlled by HO2 and NO we conclude that peroxy radicals and NO seem to play an important role for ambient radical chemistry not only with respect to oxidation capacity but also for the activation process of new particle formation. This is supposed to have significant impact of atmospheric radical species on aerosol chemistry and should to be taken into account when studying the impact of new particles in climate feedback cycles.
This study presents a comprehensive and critical assessment of the meteorological conditions and atmospheric flow during the Lagrangian-type "Hill Cap Cloud Thuringia 2010" experiment (HCCT-2010). HCCT-2010 was performed in September and October 2010 at Mt. Schmücke in the Thuringian forest, Germany, applying three measurements sites (upwind, in-cloud, downwind) to study physical and chemical aerosol-cloud-interactions. A Lagrangian-type hill cap cloud experiment requires suitable cloud and particularly connected airflow conditions, i.e. representative air masses at the different measurement sites. Therefore, the present study aimed at the identification of time periods during the 6-weeks duration of the campaign, where such conditions were fulfilled and which can be used in further data examinations.
The following topics were studied in detail: (i) the general synoptic weather situations including the mesoscale flow conditions by means of a classification of advected air masses and calculation of non-dimensional flow parameters (e.g. Froude number), (ii) local meteorological conditions, including synoptic front passages, the presence of orographic or frontal cloudiness, cloud base heights and vertical stratification, and (iii) local flow conditions by means of statistical analyses using the quasi-inert trace gas ozone and selected size bins of particle number size distributions as well as SF6 tracer experiments in the campaign area. A comprehensive analyses using statistical measures such as the COD (Coefficient Of Divergence) and cross-correlation have been carried out for the first time in the context of a Lagrangian-type hill cap cloud experiment. Suitable criteria for the aimed statistical analyses were thus developed and applied in the present study to characterise the local flow connectivity in detail.
The comprehensive examination resulted in a total of 14 so-called "Full Cloud Events" (FCE), which are shown to conform to the Lagrange-type experimental philosophy of HCCT-2010. In addition, 15 so-called "Non-Cloud Events" (NCEs) could be established, which can be used as reference cases as they provide similarly suitable flow conditions but no cloud at the summit site. Orographic cloudiness was identified for approx. one third of the FCE periods, while about two thirds were associated to synoptic fronts. The statistical flow analyses indicate the existence of a strong link between the sites during the events, particularly under constant south-westerly flow conditions, high wind speeds and slightly stable stratification. The COD analyses using continuously measured concentrations of ozone and the 49 nm diameter particle bin revealed particularly for COD values below 0.1 very consistent time series, i.e. closely linked air masses between the different sites. The cross-correlation analysis revealed under connected flow conditions typical overflow times of about 15 to 30 min between the two valley sites. Additionally, the performed SF6 tracer experiments during the campaign clearly demonstrate that under appropriate meteorological conditions a Lagrangian-type approach is valid and that the connected flow validation procedure developed in this work is suitable for identifying such conditions. Finally, an overall evaluation of the identified FCEs is presented, which provides the basis for subsequent investigations of the measured chemical and physical data during HCCT-2010.
Nucleation of aerosol particles from trace atmospheric vapours is thought to provide up to half of global cloud condensation nuclei. Aerosols can cause a net cooling of climate by scattering sunlight and by leading to smaller but more numerous cloud droplets, which makes clouds brighter and extends their lifetimes. Atmospheric aerosols derived from human activities are thought to have compensated for a large fraction of the warming caused by greenhouse gases. However, despite its importance for climate, atmospheric nucleation is poorly understood. Recently, it has been shown that sulphuric acid and ammonia cannot explain particle formation rates observed in the lower atmosphere. It is thought that amines may enhance nucleation, but until now there has been no direct evidence for amine ternary nucleation under atmospheric conditions. Here we use the CLOUD (Cosmics Leaving Outdoor Droplets) chamber at CERN and find that dimethylamine above three parts per trillion by volume can enhance particle formation rates more than 1,000-fold compared with ammonia, sufficient to account for the particle formation rates observed in the atmosphere. Molecular analysis of the clusters reveals that the faster nucleation is explained by a base-stabilization mechanism involving acid–amine pairs, which strongly decrease evaporation. The ion-induced contribution is generally small, reflecting the high stability of sulphuric acid–dimethylamine clusters and indicating that galactic cosmic rays exert only a small influence on their formation, except at low overall formation rates. Our experimental measurements are well reproduced by a dynamical model based on quantum chemical calculations of binding energies of molecular clusters, without any fitted parameters. These results show that, in regions of the atmosphere near amine sources, both amines and sulphur dioxide should be considered when assessing the impact of anthropogenic activities on particle formation.
Sulphuric acid, ammonia, amines, and oxidised organics play a crucial role in nanoparticle formation in the atmosphere. In this study, we investigate the composition of nucleated nanoparticles formed from these compounds in the CLOUD (Cosmics Leaving Outdoor Droplets) chamber experiments at CERN (Centre européen pour la recherche nucléaire). The investigation was carried out via analysis of the particle hygroscopicity, ethanol affinity, oxidation state, and ion composition. Hygroscopicity was studied by a hygroscopic tandem differential mobility analyser and a cloud condensation nuclei counter, ethanol affinity by an organic differential mobility analyser and particle oxidation level by a high-resolution time-of-flight aerosol mass spectrometer. The ion composition was studied by an atmospheric pressure interface time-of-flight mass spectrometer. The volume fraction of the organics in the particles during their growth from sizes of a few nanometers to tens of nanometers was derived from measured hygroscopicity assuming the Zdanovskii–Stokes–Robinson relationship, and compared to values gained from the spectrometers. The ZSR-relationship was also applied to obtain the measured ethanol affinities during the particle growth, which were used to derive the volume fractions of sulphuric acid and the other inorganics (e.g. ammonium salts). In the presence of sulphuric acid and ammonia, particles with a mobility diameter of 150 nm were chemically neutralised to ammonium sulphate. In the presence of oxidation products of pinanediol, the organic volume fraction of freshly nucleated particles increased from 0.4 to ~0.9, with an increase in diameter from 2 to 63 nm. Conversely, the sulphuric acid volume fraction decreased from 0.6 to 0.1 when the particle diameter increased from 2 to 50 nm. The results provide information on the composition of nucleated aerosol particles during their growth in the presence of various combinations of sulphuric acid, ammonia, dimethylamine and organic oxidation products.
The international research project RECONCILE has addressed central questions regarding polar ozone depletion, with the objective to quantify some of the most relevant yet still uncertain physical and chemical processes and thereby improve prognostic modelling capabilities to realistically predict the response of the ozone layer to climate change. This overview paper outlines the scope and the general approach of RECONCILE, and it provides a summary of observations and modelling in 2010 and 2011 that have generated an in many respects unprecedented dataset to study processes in the Arctic winter stratosphere. Principally, it summarises important outcomes of RECONCILE including (i) better constraints and enhanced consistency on the set of parameters governing catalytic ozone destruction cycles, (ii) a better understanding of the role of cold binary aerosols in heterogeneous chlorine activation, (iii) an improved scheme of polar stratospheric cloud (PSC) processes that includes heterogeneous nucleation of nitric acid trihydrate (NAT) and ice on non-volatile background aerosol leading to better model parameterisations with respect to denitrification, and (iv) long transient simulations with a chemistry-climate model (CCM) updated based on the results of RECONCILE that better reproduce past ozone trends in Antarctica and are deemed to produce more reliable predictions of future ozone trends. The process studies and the global simulations conducted in RECONCILE show that in the Arctic, ozone depletion uncertainties in the chemical and microphysical processes are now clearly smaller than the sensitivity to dynamic variability.
The International Halocarbons in Air Comparison Experiment (IHALACE) was conducted to document relationships between calibration scales among various laboratories that measure atmospheric greenhouse and ozone depleting gases. Six stainless steel cylinders containing natural and modified natural air samples were circulated among 19 laboratories. Results from this experiment reveal relatively good agreement among commonly used calibration scales for a number of trace gases present in the unpolluted atmosphere at pmol mol−1 (parts per trillion) levels, such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). Some scale relationships were found to be consistent with those derived from bi-lateral experiments or from analysis of atmospheric data, while others revealed discrepancies. The transfer of calibration scales among laboratories was found to be problematic in many cases, meaning that measurements tied to a common scale may not, in fact, be compatible. These results reveal substantial improvements in calibration over previous comparisons. However there is room for improvement in communication and coordination of calibration activities with respect to the measurement of halogenated and related trace gases.
Numerous reactive volatile organic compounds (VOCs) are emitted into the atmosphere by vegetation. Most biogenic VOCs are highly reactive towards the atmosphere's most important oxidant, the hydroxyl (OH) radical. One way to investigate the chemical interplay between biosphere and atmosphere is through the measurement of total OH reactivity, the total loss rate of OH radicals. This study presents the first determination of total OH reactivity emission rates (measurements via the comparative reactivity method) based on a branch cuvette enclosure system mounted on a Norway spruce (Picea abies) throughout spring, summer and autumn 2011. In parallel VOC emission rates were monitored by a second proton-transfer-reaction mass spectrometer (PTR-MS), and total ozone (O3) loss rates were obtained inside the cuvette. Total OH reactivity emission rates were in general temperature and light dependent, showing strong diel cycles with highest values during daytime. Monoterpene emissions contributed most, accounting for 56–69% of the measured total OH reactivity flux in spring and early summer. However, during late summer and autumn the monoterpene contribution decreased to 11–16%. At this time, a large missing fraction of the total OH reactivity emission rate (70–84%) was found when compared to the VOC budget measured by PTR-MS. Total OH reactivity and missing total OH reactivity emission rates reached maximum values in late summer corresponding to the period of highest temperature. Total O3 loss rates within the closed cuvette showed similar diel profiles and comparable seasonality to the total OH reactivity fluxes.
Total OH reactivity fluxes were also compared to emissions from needle storage pools predicted by a temperature-only-dependent algorithm. Deviations of total OH reactivity fluxes from the temperature-only-dependent emission algorithm were observed for occasions of mechanical and heat stress. While for mechanical stress, induced by strong wind, measured VOCs could explain total OH reactivity emissions, during heat stress they could not. The temperature-driven algorithm matched the diel variation of total OH reactivity emission rates much better in spring than in summer, indicating a different production and emission scheme for summer and early autumn. During these times, unmeasured and possibly unknown primary biogenic emissions contributed significantly to the observed total OH reactivity flux.
has been demonstrated in climate models that both the Indian and East Asian summer monsoons (ISM and EASM) are strengthened by the uplift of the entire Asian orography or Tibetan Plateau (TP) (i.e. bulk mountain uplift). Such an effect is widely perceived as the major mechanism contributing to the evolution of Asian summer monsoons in the Neogene. However, geological evidence suggests more diachronous growth of the Asian orography (i.e. regional mountain uplift) than bulk mountain uplift. This demands a re-evaluation of the relation between mountain uplift and the Asian monsoon in the geological periods. In this study, sensitivity experiments considering the diachronous growth of different parts of the Asian orography are performed using the regional climate model COSMO-CLM to investigate their effects on the Asian summer monsoons. The results show that, different from the bulk mountain uplift, the regional mountain uplift can lead to an asynchronous development of the ISM and EASM. While the ISM is primarily intensified by the thermal insulation (mechanical blocking) effect of the southern TP (Zagros Mountains), the EASM is mainly enhanced by the surface sensible heating of the central, northern and eastern TP. Such elevated surface heating can induce a low-level cyclonic anomaly around the TP that reduces the ISM by suppressing the lower tropospheric monsoon vorticity, but promotes the EASM by strengthening the warm advection from the south of the TP that sustains the monsoon convection. Our findings provide new insights to the evolution of the Asian summer monsoons and their interaction with the tectonic changes in the Neogene.
Spatial interpolation of rain gauge data is important in forcing of hydrological simulations or evaluation of weather predictions, for example. This paper investigates the application of statistical distance, like one minus common variance of observation time series, between data sites instead of geographical distance in interpolation. Here, as a typical representative of interpolation methods the inverse distance weighting interpolation is applied and the test data is daily precipitation observed in Austria. Choosing statistical distance instead of geographical distance in interpolation of available coarse network observations to sites of a denser network, which is not reporting for the interpolation date, yields more robust interpolation results. The most distinct performance enhancement is in or close to mountainous terrain. Therefore, application of statistical distance in the inverse distance weighting interpolation or in similar methods can parsimoniously densify the currently available observation network. Additionally, the success further motivates search for conceptual rain-orography interaction models as components of spatial rain interpolation algorithms in mountainous terrain.
Spatial interpolation of rain gauge data is important in forcing of hydrological simulations or evaluation of weather predictions, for example. The spatial density of available data sites is often changing with time. This paper investigates the application of statistical distance, like one minus common variance of time series, between data sites instead of geographical distance in interpolation. Here, as a typical representative of interpolation methods the inverse distance weighting interpolation is applied and the test data is daily precipitation observed in Austria. Choosing statistical distance instead of geographical distance in interpolation of an actually available coarse observation network yields more robust interpolation results at sites of a denser network with actually lacking observations. The performance enhancement is in or close to mountainous terrain. This has the potential to parsimoniously densify the currently available observation network. Additionally, the success further motivates search for conceptual rain-orography interaction models as components of spatial rain interpolation algorithms in mountainous terrain.
In this study, two different methods were applied to derive daily and monthly sunshine duration based on high-resolution satellite products provided by the European Organisation for the Exploitation of Meteorological Satellites (EUMETSAT) Satellite Application Facility on Climate Monitoring using data from Meteosat Second Generation (MSG) SEVIRI (Spinning Enhanced Visible and Infrared Imager). The satellite products were either hourly cloud type or hourly surface incoming direct radiation. The satellite sunshine duration estimates were not found to be significantly different using the native 15-minute temporal resolution of SEVIRI. The satellite-based sunshine duration products give additional spatial information over the European continent compared with equivalent in situ-based products. An evaluation of the satellite sunshine duration by product intercomparison and against station measurements was carried out to determine their accuracy. The satellite data were found to be within ±1 h/day compared to high-quality Baseline Surface Radiation Network or surface synoptic observations (SYNOP) station measurements. The satellite-based products differ more over the oceans than over land, mainly because of the treatment of fractional clouds in the cloud type-based sunshine duration product. This paper presents the methods used to derive the satellite sunshine duration products and the performance of the different retrievals. The main benefits and disadvantages compared to station-based products are also discussed.
The current study tested the assumption that floristic and functional diversity patterns are negatively related to soil nitrogen content. We analyzed 20 plots with soil N-contents ranging from 0.63% to 1.06% in a deciduous forest near Munich (Germany). To describe species adaptation strategies to different nitrogen availabilities, we used a plant functional type (PFT) approach. Each identified PFT represents one realized adaptation strategy to the current environment. These were correlated, next to plant species richness and evenness, to soil nitrogen contents. We found that N-efficient species were typical for low soil nitrogen contents, while N-requiring species occur at high N-contents. In contrast to our initial hypotheses, floristic and functional diversity measures (number of PFTs) were positively related to nitrogen content in the soil. Every functional group has its own adaptation to the prevailing environmental conditions; in consequence, these functional groups can co-exist but do not out-compete one another. The increased number of functional groups at high N-contents leads to increased species richness. Hence, for explaining diversity patterns we need to consider species groups representing different adaptations to the current environmental conditions. Such co-existing ecological strategies may even overcome the importance of competition in their effect on biodiversity.
This article presents an environmental remote sensing application using a UAV that is specifically aimed at reducing the data gap between field scale and satellite scale in soil erosion monitoring in Morocco. A fixed-wing aircraft type Sirius I (MAVinci, Germany) equipped with a digital system camera (Panasonic) is employed. UAV surveys are conducted over different study sites with varying extents and flying heights in order to provide both very high resolution site-specific data and lower-resolution overviews, thus fully exploiting the large potential of the chosen UAV for multi-scale mapping purposes. Depending on the scale and area coverage, two different approaches for georeferencing are used, based on high-precision GCPs or the UAV’s log file with exterior orientation values respectively. The photogrammetric image processing enables the creation of Digital Terrain Models (DTMs) and ortho-image mosaics with very high resolution on a sub-decimetre level. The created data products were used for quantifying gully and badland erosion in 2D and 3D as well as for the analysis of the surrounding areas and landscape development for larger extents.
Reduction of greenhouse gas (GHG) emissions to minimize climate change requires very significant societal effort. To motivate this effort, it is important to clarify the benefits of avoided emissions. To this end, we analysed the impact of four emissions scenarios on future renewable groundwater resources, which range from 1600 GtCO2 during the 21st century (RCP2.6) to 7300 GtCO2 (RCP8.5). Climate modelling uncertainty was taken into account by applying the bias-corrected output of a small ensemble of five CMIP5 global climate models (GCM) as provided by the ISI-MIP effort to the global hydrological model WaterGAP. Despite significant climate model uncertainty, the benefits of avoided emissions with respect to renewable groundwater resources (i.e. groundwater recharge (GWR)) are obvious. The percentage of projected global population (SSP2 population scenario) suffering from a significant decrease of GWR of more than 10% by the 2080s as compared to 1971–2000 decreases from 38% (GCM range 27–50%) for RCP8.5 to 24% (11–39%) for RCP2.6. The population fraction that is spared from any significant GWR change would increase from 29% to 47% if emissions were restricted to RCP2.6. Increases of GWR are more likely to occur in areas with below average population density, while GWR decreases of more than 30% affect especially (semi)arid regions, across all GCMs. Considering change of renewable groundwater resources as a function of mean global temperature (GMT) rise, the land area that is affected by GWR decreases of more than 30% and 70% increases linearly with global warming from 0 to 3 ° C. For each degree of GMT rise, an additional 4% of the global land area (except Greenland and Antarctica) is affected by a GWR decrease of more than 30%, and an additional 1% is affected by a decrease of more than 70%.
Environmental change impacts on the C- and N-cycle of European forests: a model comparison study
(2013)
Forests are important components of the greenhouse gas balance of Europe. There is considerable uncertainty about how predicted changes to climate and nitrogen deposition will perturb the carbon and nitrogen cycles of European forests and thereby alter forest growth, carbon sequestration and N2O emission. The present study aimed to quantify the carbon and nitrogen balance, including the exchange of greenhouse gases, of European forests over the period 2010–2030, with a particular emphasis on the spatial variability of change. The analysis was carried out for two tree species: European beech and Scots pine. For this purpose, four different dynamic models were used: BASFOR, DailyDayCent, INTEGRATOR and Landscape-DNDC. These models span a range from semi-empirical to complex mechanistic. Comparison of these models allowed assessment of the extent to which model predictions depended on differences in model inputs and structure. We found a European average carbon sink of 0.160 ± 0.020 kgC m−2 yr−1 (pine) and 0.138 ± 0.062 kgC m−2 yr−1 (beech) and N2O source of 0.285 ± 0.125 kgN ha−1 yr−1 (pine) and 0.575 ± 0.105 kgN ha−1 yr−1 (beech). The European average greenhouse gas potential of the carbon sink was 18 (pine) and 8 (beech) times that of the N2O source. Carbon sequestration was larger in the trees than in the soil. Carbon sequestration and forest growth were largest in central Europe and lowest in northern Sweden and Finland, N. Poland and S. Spain. No single driver was found to dominate change across Europe. Forests were found to be most sensitive to change in environmental drivers where the drivers were limiting growth, where changes were particularly large or where changes acted in concert. The models disagreed as to which environmental changes were most significant for the geographical variation in forest growth and as to which tree species showed the largest rate of carbon sequestration. Pine and beech forests were found to have differing sensitivities to environmental change, in particular the response to changes in nitrogen and precipitation, with beech forest more vulnerable to drought. There was considerable uncertainty about the geographical location of N2O emissions. Two of the models BASFOR and LandscapeDNDC had largest emissions in central Europe where nitrogen deposition and soil nitrogen were largest, whereas the two other models identified different regions with large N2O emission. N2O emissions were found to be larger from beech than pine forests and were found to be particularly sensitive to forest growth.
Forests are important components of the greenhouse gas balance of Europe. There is considerable uncertainty about how predicted changes to climate and nitrogen deposition will perturb the carbon and nitrogen cycles of European forests and thereby alter forest growth, carbon sequestration and N2O emission. The present study aimed to quantify the carbon and nitrogen balance, including the exchange of greenhouse gases, of European forests over the period 2010–2030, with a particular emphasis on the spatial variability of change. The analysis was carried out for two tree species: European beech and Scots pine. For this purpose, four different dynamic models were used: BASFOR, DailyDayCent, INTEGRATOR and Landscape-DNDC. These models span a range from semi-empirical to complex mechanistic. Comparison of these models allowed assessment of the extent to which model predictions depended on differences in model inputs and structure. We found a European average carbon sink of 0.160 ± 0.020 kgC m−2 yr−1 (pine) and 0.138 ± 0.062 kgC m−2 yr−1 (beech) and N2O source of 0.285 ± 0.125 kgN ha−1 yr−1 (pine) and 0.575 ± 0.105 kgN ha−1 yr−1 (beech). The European average greenhouse gas potential of the carbon source was 18 (pine) and 8 (beech) times that of the N2O source. Carbon sequestration was larger in the trees than in the soil. Carbon sequestration and forest growth were largest in central Europe and lowest in northern Sweden and Finland, N. Poland and S. Spain. No single driver was found to dominate change across Europe. Forests were found to be most sensitive to change in environmental drivers where the drivers were limiting growth, where changes were particularly large or where changes acted in concert. The models disagreed as to which environmental changes were most significant for the geographical variation in forest growth and as to which tree species showed the largest rate of carbon sequestration. Pine and beech forests were found to have differing sensitivities to environmental change, in particular the response to changes in nitrogen and precipitation, with beech forest more vulnerable to drought. There was considerable uncertainty about the geographical location of N2O emissions. Two of the models BASFOR and LandscapeDNDC had largest emissions in central Europe where nitrogen deposition and soil nitrogen were largest whereas the two other models identified different regions with large N2O emission. N2O emissions were found to be larger from beech than pine forests and were found to be particularly sensitive to forest growth.
When studying new particle formation, the uncertainty in determining the "true" nucleation rate is considerably reduced when using Condensation Particle Counters (CPCs) capable of measuring concentrations of aerosol particles at sizes close to or even at the critical cluster size (1–2 nm). Recently CPCs, able to reliably detect particles below 2 nm in size and even close to 1 nm became available. The corrections needed to calculate nucleation rates are substantially reduced compared to scaling the observed formation rate to the nucleation rate at the critical cluster size. However, this improved instrumentation requires a careful characterization of their cut-off size and the shape of the detection efficiency curve because relatively small shifts in the cut-off size can translate into larger relative errors when measuring particles close to the cut-off size.
Here we describe the development of two continuous flow CPCs using diethylene glycol (DEG) as the working fluid. The design is based on two TSI 3776 counters. Several sets of measurements to characterize their performance at different temperature settings were carried out. Furthermore two mixing-type Particle Size Magnifiers (PSM) A09 from Airmodus were characterized in parallel. One PSM was operated at the highest mixing ratio (1 L min−1 saturator flow), and the other was operated in a scanning mode, where the mixing ratios are changed periodically, resulting in a range of cut-off sizes. Different test aerosols were generated using a nano-Differential Mobility Analyzer (nano-DMA) or a high resolution DMA, to obtain detection efficiency curves for all four CPCs. One calibration setup included a high resolution mass spectrometer (APi-TOF) for the determination of the chemical composition of the generated clusters. The lowest cut-off sizes were achieved with negatively charged ammonium sulphate clusters, resulting in cut-offs of 1.4 nm for the laminar flow CPCs and 1.2 and 1.1 nm for the PSMs. A comparison of one of the laminar-flow CPCs and one of the PSMs measuring ambient and laboratory air showed good agreement between the instruments.
The SAWNUC microphysical aerosol nucleation model is used to study the effect of reactor walls on the interpretation of nucleation experiments with respect to nucleation theory. This work shows that loss processes, such as wall losses, influence the interpretation of nucleation experiments, especially at low growth rates and short lifetime of freshly nucleated particles. In these cases the power dependency of the formation rates, determined at a certain particle size, with respect to H2SO4 does not correspond to the approximate number of H2SO4 molecules in the critical cluster as expected by the first nucleation theorem. Observed ∂log(J)/∂log([H2SO4]) therefore can vary widely for identical nucleation conditions but different sink terms.
We investigate the contribution of oceanic methyl iodide (CH3I) to the stratospheric iodine budget. Based on CH3I measurements during three tropical ship campaigns and the Lagrangian transport model FLEXPART we provide a detailed analysis of CH3I transport from the ocean surface to the cold point in the upper tropical tropopause layer (TTL). While average oceanic emissions differ by less than 50% from campaign to campaign, the measurements show much stronger variations within each campaign. A positive correlation between the oceanic CH3I emissions and the efficiency of CH3I troposphere–stratosphere transport has been identified for some cruise sections. The mechanism of strong horizontal surface winds triggering large emissions on the one hand and being associated with tropical convective systems, such as developing typhoons, on the other hand, could explain the identified correlations. As a result of the simultaneous occurrence of large CH3I emissions and strong vertical uplift, localized maximum mixing ratios of 0.6 ppt CH3I at the cold point have been determined for observed peak emissions during the SHIVA-Sonne campaign in the coastal West Pacific. The other two campaigns give considerable smaller maxima of 0.1 ppt CH3I for the TransBrom campaign in the open West Pacific and 0.03 ppt for emissions from the coastal East Atlantic during the DRIVE campaign. In order to assess the representativeness of the large local mixing ratios we use climatological emission scenarios to derive global upper air estimates of CH3I abundances. The model results are compared to available upper air measurements including data from the recent ATTREX and HIPPO2 aircraft campaigns. In the East Pacific region, the location of the available measurement campaigns in the upper TTL, the comparisons give a good agreement indicating that around 0.01 to 0.02 ppt of CH3I enter the stratosphere. However, other tropical regions, which are subject to stronger convective activity show larger CH3I entrainment, e.g., 0.08 ppt in the West Pacific. The strong variations in the geographical distribution of CH3I entrainment suggest that currently available upper air measurements are not representative of global estimates and further campaigns will be necessary in order to better understand the CH3I contribution to stratospheric iodine.
In the original manuscript, Figs. 7–16 included fonts which were not correctly embedded in the file. As such, unless certain propriety software (ArcGIS) is installed on the viewing platform, the figures will appear corrupted. In this Corrigendum, Figs. 7–16 and their captions are reproduced with the fonts correctly embedded. Please find the correct figures below.
The late Miocene palaeorecord provides evidence for a warmer and wetter climate than that of today, and there is uncertainty in the palaeo-CO2 record of at least 200 ppm. We present results from fully coupled atmosphere-ocean-vegetation simulations for the late Miocene that examine the relative roles of palaeogeography (topography and ice sheet geometry) and CO2 concentration in the determination of late Miocene climate through comprehensive terrestrial model-data comparisons. Assuming that these data accurately reflect the late Miocene climate, and that the late Miocene palaeogeographic reconstruction used in the model is robust, then results indicate that:
1. Both palaeogeography and atmospheric CO2 contribute to the proxy-derived precipitation differences between the late Miocene and modern reference climates. However these contributions exibit synergy and so do not add linearly.
2. The vast majority of the proxy-derived temperature differences between the late Miocene and modern reference climates can only be accounted for if we assume a palaeo-CO2 concentration towards the higher end of the range of estimates.
The Late Miocene (∼11.6–5.3 Ma) palaeorecord provides evidence for a warmer and wetter climate than that of today and there is uncertainty in the palaeo-CO2 record of at least 150 ppmv. We present results from fully coupled atmosphere-ocean-vegetation simulations for the Late Miocene that examine the relative roles of palaeogeography (topography and ice sheet geometry) and CO2 concentration in the determination of Late Miocene climate through comprehensive terrestrial model-data comparisons. Assuming that the data accurately reflects the Late Miocene climate, and that the Late Miocene palaeogeographic reconstruction used in the model is robust, then results indicate that the proxy-derived precipitation differences between the Late Miocene and modern can be largely accounted for by the palaeogeographic changes alone. However, the proxy-derived temperatures differences between the Late Miocene and modern can only begin to be accounted for if we assume a palaeo-CO2 concentration towards the higher end of the range of estimates.
Water footprints have been proposed as sustainability indicators, relating the consumption of goods like food to the amount of water necessary for their production and the impacts of that water use in the source regions. We have further developed the existing water footprint methodology by globally resolving virtual water flows and import and source regions at 5 arc minutes spatial resolution, and by assessing local impacts of export production. Applying this method to three exemplary cities, Berlin, Delhi and Lagos, we find major differences in amounts, composition, and origin of green and blue virtual water imports, due to differences in diets, trade integration and crop water productivities in the source regions. While almost all of Delhi's and Lagos' virtual water imports are of domestic origin, Berlin on average imports from more than 4000 km distance, in particular soy (livestock feed), coffee and cocoa. While 42% of Delhi's virtual water imports are blue water based, the fractions for Berlin and Lagos are 2% and 0.5%, respectively, roughly equal to local drinking water abstractions of these cities. Some of the external source regions of Berlin's virtual water imports appear to be critically water scarce and/or food insecure. However for deriving recommendations on sustainable consumption and trade, further analysis of context-specific costs and benefits associated with export production will be required.
Estimates of the recovery time of stratospheric ozone heavily rely on the exact knowledge of the processes that lead to the decomposition of the relevant halogenated source gases. Crucial parameters in this context are Fractional Release Factors (FRFs) as well as stratospheric lifetimes and Ozone Depletion Potentials (ODPs). We here present data from the analysis of air samples collected between 2009 and 2011 on board research aircraft flying in the mid- and high latitudinal stratosphere and infer the above-mentioned parameters for ten major source gases:CFCl3 (CFC-11), CF2Cl2 (CFC-12), CF2ClCFCl2(CFC-113), CCl4 (carbon tetrachloride),CH3CCl3 (methyl chloroform), CHF2Cl (HCFC-22), CH3CFCl2 (HCFC-141b), CH3CF2Cl (HCFC-142b), CF2ClBr (H-1211), and CF3Br (H-1301). The inferred correlations of their FRFs with mean ages of air reveal less decomposition as compared to previous studies for most compounds. When using the calculated set of FRFs to infer equivalent stratospheric chlorine we find a reduction of more than 20% as compared to the values inferred in the most recent Scientific Assessment of Ozone Depletion by the World Meteorological Organisation (WMO, 2011). We also note that FRFs and their correlations with mean age are not generally time-independent as often assumed. The stratospheric lifetimes were calculated relative to that of CFC-11. Within our uncertainties the inferred ratios between lifetimes agree with those between stratospheric lifetimes from recent WMO reports except for CFC-11, CFC-12 and CH3CCl3. Finally we calculate lower ODPs than WMO for six out of ten compounds with changes most pronounced for the three HCFCs. Collectively these newly calculated values may have important implications for the severity and recovery time of stratospheric ozone loss.
Estimates of the recovery time of stratospheric ozone heavily rely on the exact knowledge of the processes that lead to the decomposition of the relevant halogenated source gases. Crucial parameters in this context are fractional release factors (FRFs) as well as stratospheric lifetimes and ozone depletion potentials (ODPs). We here present data from the analysis of air samples collected between 2009 and 2011 on board research aircraft flying in the mid- and high-latitude stratosphere and infer the above-mentioned parameters for ten major source gases: CFCl3 (CFC-11), CF2Cl2 (CFC-12), CF2ClCFCl2 (CFC-113), CCl4 (carbon tetrachloride), CH3CCl3 (methyl chloroform), CHF2Cl (HCFC-22), CH3CFCl2 (HCFC-141b), CH3CF2Cl (HCFC-142b), CF2ClBr (H-1211), and CF3Br (H-1301). The inferred correlations of their FRFs with mean ages of air reveal less decomposition as compared to previous studies for most compounds. When using the calculated set of FRFs to infer equivalent stratospheric chlorine, we find a reduction of more than 20% as compared to the values inferred in the most recent Scientific Assessment of Ozone Depletion by the World Meteorological Organisation (WMO, 2011). We also note that FRFs and their correlations with mean age are not generally time-independent as often assumed. The stratospheric lifetimes were calculated relative to that of CFC-11. Within our uncertainties the ratios between stratospheric lifetimes inferred here agree with the values in recent WMO reports except for CFC-11, CFC-12 and CH3CCl3. Finally, we calculate lower ODPs than recommended by WMO for six out of ten compounds, with changes most pronounced for the three HCFCs. Collectively these newly calculated values may have important implications for the severity and recovery time of stratospheric ozone loss.
Whereas fossil evidence indicates extensive treeless vegetation and diverse grazing megafauna in Europe and northern Asia during the last glacial, experiments combining vegetation models and climate models have to-date simulated widespread persistence of trees. Resolving this conflict is key to understanding both last glacial ecosystems and extinction of most of the mega-herbivores. Using a dynamic vegetation model (DVM) we explored the implications of the differing climatic conditions generated by a general circulation model (GCM) in “normal” and “hosing” experiments. Whilst the former approximate interstadial conditions, the latter, designed to mimic Heinrich Events, approximate stadial conditions. The “hosing” experiments gave simulated European vegetation much closer in composition to that inferred from fossil evidence than did the “normal” experiments. Given the short duration of interstadials, and the rate at which forest cover expanded during the late-glacial and early Holocene, our results demonstrate the importance of millennial variability in determining the character of last glacial ecosystems.
Since the 1980s, advances in wastewater treatment technology have led to considerably improved surface water quality in the urban areas of many high income countries. However, trace concentrations of organic wastewater-associated contaminants may still pose a key environmental hazard impairing the ecological quality of surface waters. To identify key impact factors, we analyzed the effects of a wide range of anthropogenic and environmental variables on the aquatic macroinvertebrate community. We assessed ecological water quality at 26 sampling sites in four urban German lowland river systems with a 0–100% load of state-of-the-art biological activated sludge treated wastewater. The chemical analysis suite comprised 12 organic contaminants (five phosphor organic flame retardants, two musk fragrances, bisphenol A, nonylphenol, octylphenol, diethyltoluamide, terbutryn), 16 polycyclic aromatic hydrocarbons, and 12 heavy metals. Non-metric multidimensional scaling identified organic contaminants that are mainly wastewater-associated (i.e., phosphor organic flame retardants, musk fragrances, and diethyltoluamide) as a major impact variable on macroinvertebrate species composition. The structural degradation of streams was also identified as a significant factor. Multiple linear regression models revealed a significant impact of organic contaminants on invertebrate populations, in particular on Ephemeroptera, Plecoptera, and Trichoptera species. Spearman rank correlation analyses confirmed wastewater-associated organic contaminants as the most significant variable negatively impacting the biodiversity of sensitive macroinvertebrate species. In addition to increased aquatic pollution with organic contaminants, a greater wastewater fraction was accompanied by a slight decrease in oxygen concentration and an increase in salinity. This study highlights the importance of reducing the wastewater-associated impact on surface waters. For aquatic ecosystems in urban areas this would lead to: (i) improvement of the ecological integrity, (ii) reduction of biodiversity loss, and (iii) faster achievement of objectives of legislative requirements, e.g., the European Water Framework Directive.
Subvisible cirrus clouds (SVCs) may contribute to dehydration close to the tropical tropopause. The higher and colder SVCs and the larger their ice crystals, the more likely they represent the last efficient point of contact of the gas phase with the ice phase and, hence, the last dehydrating step, before the air enters the stratosphere. The first simultaneous in situ and remote sensing measurements of SVCs were taken during the APE-THESEO campaign in the western Indian ocean in February/March 1999. The observed clouds, termed Ultrathin Tropical Tropopause Clouds (UTTCs), belong to the geometrically and optically thinnest large-scale clouds in the Earth's atmosphere. Individual UTTCs may exist for many hours as an only 200–300 m thick cloud layer just a few hundred meters below the tropical cold point tropopause, covering up to 105 km2. With temperatures as low as 181 K these clouds are prime representatives for defining the water mixing ratio of air entering the lower stratosphere.
Mechanisms by which subvisible cirrus clouds (SVCs) might contribute to dehydration close to the tropical tropopause are not well understood. Recently Ultrathin Tropical Tropopause Clouds (UTTCs) with optical depths around 10−4 have been detected in the western Indian ocean. These clouds cover thousands of square kilometers as 200–300 m thick distinct and homogeneous layer just below the tropical tropopause. In their condensed phase UTTCs contain only 1–5% of the total water, and essentially no nitric acid. A new cloud stabilization mechanism is required to explain this small fraction of the condensed water content in the clouds and their small vertical thickness. This work suggests a mechanism, which forces the particles into a thin layer, based on upwelling of the air of some mm/s to balance the ice particles, supersaturation with respect to ice above and subsaturation below the UTTC. In situ measurements suggest that these requirements are fulfilled. The basic physical properties of this mechanism are explored by means of a single particle model. Comprehensive 1-D cloud simulations demonstrate this stabilization mechanism to be robust against rapid temperature fluctuations of +/−0.5 K. However, rapid warming (ΔT>2 K) leads to evaporation of the UTTC, while rapid cooling (ΔT<−2 K) leads to destabilization of the particles with the potential for significant dehydration below the cloud.
Balloon-borne measurements of CFC-11 (on flights of the DIRAC in situ gas chromatograph and the DESCARTES grab sampler), ClO and O3 were made during the 1999/2000 winter as part of the SOLVE-THESEO 2000 campaign. Here we present the CFC-11 data from nine flights and compare them first with data from other instruments which flew during the campaign and then with the vertical distributions calculated by the SLIMCAT 3-D CTM. We calculate ozone loss inside the Arctic vortex between late January and early March using the relation between CFC-11 and O3 measured on the flights, the peak ozone loss (1200 ppbv) occurs in the 440–470 K region in early March in reasonable agreement with other published empirical estimates. There is also a good agreement between ozone losses derived from three independent balloon tracer data sets used here. The magnitude and vertical distribution of the loss derived from the measurements is in good agreement with the loss calculated from SLIMCAT over Kiruna for the same days.
Turbulent fluxes of carbonyl sulfide (COS) and carbon disulfide (CS2) were measured over a spruce forest in Central Germany using the relaxed eddy accumulation (REA) technique. A REA sampler was developed and validated using simultaneous measurements of CO2 fluxes by REA and by eddy correlation. REA measurements were conducted during six campaigns covering spring, summer, and fall between 1997 and 1999. Both uptake and emission of COS and CS2 by the forest were observed, with deposition occurring mainly during the sunlit period and emission mainly during the dark period. On the average, however, the forest acts as a sink for both gases. The average fluxes for COS and CS2 are -93 ± 11.7 pmol m -2 s -1 and -18 ± 7.6 pmol m -2 s -1, respectively. The fluxes of both gases appear to be correlated to photosynthetically active radiation and to the CO2 and H2O fluxes, supporting the idea that the air-vegetation exchange of both gases is controlled by stomata. An uptake ratio COS / CO2 of 10 ± 1.7 pmol mmol -1 has been derived from the regression line for the correlation between the COS and CO2 fluxes. This uptake ratio, if representative for the global terrestrial net primary production, would correspond to a sink of 2.3 ± 0.5 Tg COS yr-1.
Measurements of OH, the sum of peroxy radicals (ROx), non-methane hydrocarbons (NMHCs) and various other trace gases were made at the Meteorological Observatory Hohenpeissenberg in June 2000. The data from an intensive measurement period characterised by high solar insolation (18-21 June) are analysed. The maximum midday OH concentration ranged between 4.5 x 106 molecules cm-3 and 7.4 x 106 molecules cm-3. The maximum total ROx mixing ratio increased from about 55 pptv on 18 June to nearly 70 pptv on 20 and 21 June. A total of 64 NMHCs, including isoprene and monoterpenes, were measured every 1 to 6 hours. The oxidation rate of the NMHCs by OH was calculated and reached a total of over 14 x 106 molecules cm-3 s-1 on two days. A simple photostationary state balance model was used to simulate the ambient OH and ROx concentrations with the measured data as input. The model was able to reproduce the main features of the diurnal profiles of both OH and ROx. The model results proved to be most sensitive to assumptions about the mixing ratio of formaldehyde (HCHO), which was included as a proxy for carbonyl compounds, and about the partitioning between HO2 and RO2. The measured OH concentration and ROx mixing ratios were reproduced well by assuming the presence of 3 ppbv HCHO and a ratio HO2/RO2 between 1:1 and 1:2. The most important source of OH, and conversely the greatest sink for ROx, was the recycling of HO2 radicals to OH. This reaction was responsible for the recycling of more than 45 x 106 molecules cm-3 s-1 on two days. The most important sink for OH, and the largest source of ROx, was the oxidation of NMHCs, in particular, of isoprene and the monoterpenes.
A new, two-channel instrument for simultaneous NO3 and N2O5 monitoring was used to make the first comprehensive set of nocturnal NOx measurements (NO, NO2, NO3 and N2O5) at the Taunus Observatory, a rural mountain site (Kleiner Feldberg) in South-western Germany. In May 2008, NO3 and N2O5 mixing ratios were well above the instrumental detection limit (a few ppt) on all nights of the campaign and were characterised by large variability resulting from inhomogeneously distributed sinks. The concentrations of NO3, N2O5 and NO2 were consistent with the equilibrium constant, K2, defining the rates of formation and thermal dissociation of N2O5. A steady-state lifetime analysis showed that nocturnal NOx losses were generally dominated by reaction of NO3 with volatile organic compounds in this forested region, with N2O5 uptake to aerosols of secondary importance. Analysis of a limited dataset obtained at high relative humidity indicated that the loss of N2O5 by reaction with water vapour is less efficient (> factor 3) than derived using laboratory kinetic data. The fraction of NOx present as NO3 and N2O5 reached ≈20% on some nights, with night-time losses of NOx competing with daytime losses.
In this work we present the setup and first tests of our new BIO IN detector. This detector is designed to classify atmospheric ice nuclei (IN) for their biological content. Biological material is identified via its auto-fluorescence (intrinsic fluorescence) after irradiation with UV radiation. Ice nuclei are key substances for precipitation development via the Bergeron–Findeisen process. The level of scientific knowledge regarding origin and climatology (temporal and spatial distribution) of IN is very low. Some biological material is known to be active as IN even at relatively high temperatures of up to –2°C (e.g. pseudomonas syringae bacteria). These biological IN could have a strong influence on the formation of clouds and precipitation. We have designed the new BIO IN sensor to analyze the abundance of IN of biological origin. The instrument will be flown on one of the first missions of the new German research aircraft ''HALO'' (High Altitude and LOng Range).
During the second part of the TROCCINOX campaign that took place in Brazil in early 2005, chemical species were measured on-board of the high altitude research aircraft Geophysica (ozone, water vapor, NO, NOy, CH4 and CO) in the altitude range up to 20 km (or up to 450 K potential temperature), i.e. spanning the TTL region roughly extending between 350 and 420 K.
Analysis of transport across TTL is performed using a new version of the Chemical Lagrangian Model of the Stratosphere (CLaMS). In this new version, the stratospheric model has been extended to the earth surface. Above the tropopause, the isentropic and cross-isentropic advection in CLaMS is driven by ECMWF winds and heating/cooling rates derived from a radiation calculation. Below the tropopause the model smoothly transforms from the isentropic to hybrid-pressure coordinate and, in this way, takes into account the effect of large-scale convective transport as implemented in the ECMWF vertical wind. As with other CLaMS simulations, the irreversible transport, i.e. mixing, is controlled by the local horizontal strain and vertical shear rates.
Stratospheric and tropospheric signatures in the TTL can be seen both in the observation and in the model. The composition of air above ≈350 K is mainly controlled by mixing on a time scale of weeks or even months. Based on CLaMS transport studies where mixing can be completely switched off, we deduce that vertical mixing, mainly driven by the vertical shear in the outflow regions of the large-scale convection and in the vicinity of the subtropical jets, is necessary to understand the upward transport of the tropospheric air from the main convective outflow around 350 K up to the tropical tropopause around 380 K. This mechanism is most effective if the outflow of the mesoscale convective systems interacts with the subtropical jets.
The seasonality of transport and mixing of air into the lowermost stratosphere (LMS) is studied using distributions of mean age of air and a~mass balance approach, based on in-situ observations of SF6 and CO2 during the SPURT (Spurenstofftransport in der Tropopausenregion, trace gas transport in the tropopause region) aircraft campaigns. Combining the information of the mean age of air and the water vapour distributions we demonstrate that the tropospheric air transported into the LMS above the extratropical tropopause layer (ExTL) originates predominantly from the tropical tropopause layer (TTL). The concept of our mass balance is based on simultaneous measurements of the two passive tracers and the assumption that transport into the LMS can be described by age spectra which are superposition of two different modes. Based on this concept we conclude that the stratospheric influence on LMS composition is strongest in April with tropospheric fractions (α1) below 20% and that the strongest tropospheric signatures are found in October with (α1 greater than 80%. Beyond the fractions, our mass balance concept allows to calculate the associated transit times for transport of tropospheric air from the tropics into the LMS. The shortest transit times (<0.3 years) are derived for the summer, continuously increasing up to 0.8 years by the end of spring. These findings suggest that strong quasi-horizontal mixing across the weak subtropical jet from summer to mid of autumn and the considerably shorter residual transport time-scales within the lower branch of the Brewer-Dobson circulation in summer than in winter dominates the tropospheric influence in the LMS until the beginning of next year's summer.
A comprehensive evaluation of seasonal backward trajectories initialized in the Northern Hemisphere lowermost stratosphere (LMS) has been performed to investigate the origin of air parcels and the main mechanisms determining characteristic structures in H2O and CO within the LMS. In particular we explain the fundamental role of the transit time since last tropopause crossing (tTST) for the chemical structure of the LMS as well as the feature of the extra-tropical tropopause transition layer (ExTL) as identified from CO profiles. The distribution of H2O in the background LMS above Θ=320 K and 340 K in northern winter and summer, respectively, is found to be governed mainly by the saturation mixing ratio, which in turn is determined by the Lagrangian Cold Point (LCP) encountered by each trajectory. Most of the backward trajectories from this region in the LMS experienced their LCP in the tropics and sub-tropics. The transit time since crossing the tropopause from the troposphere to the stratosphere (tTST) is independent of the H2O value of the air parcel. TST often occurs 20 days after trajectories have encountered their LCP. CO, on the other hand, depends strongly on tTST due to its finite lifetime. The ExTL as identified from CO measurements is then explained as a layer of air just above the tropopause, which on average encountered TST fairly recently.
his study aims at a detailed characterization of an ultra-fine aerosol particle counting system for operation on board the Russian high altitude research aircraft M-55 "Geophysica" (maximum ceiling of 21 km). The COndensation PArticle counting Systems (COPAS) consists of an aerosol inlet and two dual-channel continuous flow Condensation Particle Counters (CPCs).
The aerosol inlet, adapted for COPAS measurements on board the M-55 "Geophysica", is described concerning aspiration, transmission, and transport losses. The counting efficiencies of the CPCs using the chlorofluorocarbon FC-43 as the working fluid are studied experimentally at two pressure conditions, 300 hPa and 70 hPa. Three COPAS channels are operated with different temperature differences between the saturator and the condenser block yielding smallest detectable particle sizes (dp50 – as 50% detection "cut off" diameters) of 6 nm, 11 nm, and 15 nm, respectively, at ambient pressure of 70 hPa. The fourth COPAS channel is operated with an aerosol heating line (250°C) for a determination of the non-volatile number of particles. The heating line is experimentally proven to volatilize pure H2SO4-H2O particles for a particle diameter (dp) range of 11 nm<dp<200 nm.
Additionally this study includes investigation to exclude auto-nucleation of the working fluid inside the CPCs. An instrumental inter-comparison (cross-correlation) has been performed for several measurement flights and mission flights in the Arctic and the Tropics are discussed. Finally, COPAS measurements are used for an aircraft plume crossing analysis.
During SPURT (Spurenstofftransport in der Tropopausenregion, trace gas transport in the tropopause region) we performed measurements of a wide range of trace gases with different lifetimes and sink/source characteristics in the northern hemispheric upper troposphere (UT) and lowermost stratosphere (LMS). A large number of in-situ instruments were deployed on board a Learjet 35A, flying at altitudes up to 13.7 km, at times reaching to nearly 380 K potential temperature. Eight measurement campaigns (consisting of a total of 36 flights), distributed over all seasons and typically covering latitudes between 35° N and 75° N in the European longitude sector (10° W–20° E), were performed. Here we present an overview of the project, describing the instrumentation, the encountered meteorological situations during the campaigns and the data set available from SPURT. Measurements were obtained for N2O, CH4, CO, CO2, CFC12, H2, SF6, NO, NOy, O3 and H2O. We illustrate the strength of this new data set by showing mean distributions of the mixing ratios of selected trace gases, using a potential temperature – equivalent latitude coordinate system. The observations reveal that the LMS is most stratospheric in character during spring, with the highest mixing ratios of O3 and NOy and the lowest mixing ratios of N2O and SF6. The lowest mixing ratios of NOy and O3 are observed during autumn, together with the highest mixing ratios of N2O and SF6 indicating a strong tropospheric influence. For H2O, however, the maximum concentrations in the LMS are found during summer, suggesting unique (temperature- and convection-controlled) conditions for this molecule during transport across the tropopause. The SPURT data set is presently the most accurate and complete data set for many trace species in the LMS, and its main value is the simultaneous measurement of a suite of trace gases having different lifetimes and physical-chemical histories. It is thus very well suited for studies of atmospheric transport, for model validation, and for investigations of seasonal changes in the UT/LMS, as demonstrated in accompanying and elsewhere published studies.
Active chlorine species play a dominant role in the catalytic destruction of stratospheric ozone in the polar vortices during the late winter and early spring seasons. Recently, the correct understanding of the ClO dimer cycle was challenged by the release of new laboratory absorption cross sections (Pope et al., 2007) yielding significant model underestimates of observed ClO and ozone loss (von Hobe et al., 2007). Under this aspect, Arctic stratospheric limb emission measurements carried out by the balloon version of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS-B) from Kiruna (Sweden) on 11 January 2001 and 20/21 March 2003 have been reanalyzed with regard to the chlorine reservoir species ClONO2 and the active species, ClO and ClOOCl (Cl2O2). New laboratory measurements of IR absorption cross sections of ClOOCl for various temperatures and pressures allowed for the first time the retrieval of ClOOCl mixing ratios from remote sensing measurements. High values of active chlorine (ClOx) of roughly 2.3 ppbv at 20 km were observed by MIPAS-B in the cold mid-winter Arctic vortex on 11 January 2001. While nighttime ClOOCl shows enhanced values of nearly 1.1 ppbv at 20 km, ClONO2 mixing ratios are less than 0.1 ppbv at this altitude. In contrast, high ClONO2 mixing ratios of nearly 2.4 ppbv at 20 km have been observed in the late winter Arctic vortex on 20 March 2003. No significant ClOx amounts are detectable on this date since most of the active chlorine has already recovered to its main reservoir species ClONO2. The observed values of ClOx and ClONO2 are in line with the established chlorine chemistry. The thermal equilibrium constants between the dimer formation and its dissociation, as derived from the balloon measurements, are on the lower side of reported data and in good agreement with values recommended by von Hobe et al. (2007). Calculations with the ECHAM/MESSy Atmospheric Chemistry model (EMAC) using established kinetics show similar chlorine activation and deactivation, compared to the measurements in January 2001 and March 2003, respectively.
Chemical ozone loss in winter 1991–1992 is recalculated based on observations of the HALOE satellite instrument, ER-2 aircraft measurements and balloon data. HALOE satellite observations are shown to be reliable in the lower stratosphere below 400 K, at altitudes where profiles are most likely disturbed by the enhanced sulfate aerosols, as a result of the Mt. Pinatubo eruption in June 1991. Very large chemical ozone loss was observed below 400 K from Kiruna balloon observations between December and March 1992. Additionally, for the two winters after the Mt. Pinatubo eruption, HALOE satellite observations show a stronger extent of chemical ozone loss at lower altitudes compared to other Arctic winter between 1991 and 2003. In stipe of already occurring deactivation of chlorine in March 1992, Mipas-B and LPMA balloon observations indicate still chlorine activation at lower altitudes, consistent with observed chemical ozone loss occurring between February and March and April. Enhanced chemical ozone loss in the Arctic winter 1991–1992 as calculated in earlier studies is corroborated here.
On the observation of mesospheric air inside the arctic stratospheric polar vortex in early 2003
(2005)
During several balloon flights inside the Arctic polar vortex in early 2003, unusual trace gas distributions were observed, which indicate a strong influence of mesospheric air in the stratosphere. The tuneable diode laser (TDL) instrument SPIRALE (Spectroscopie InFrarouge par Absorption de Lasers Embarqués) measured unusually high CO values (up to 600 ppb) on 27 January at about 30 km altitude. The cryosampler BONBON sampled air masses with very high molecular Hydrogen, extremely low SF6 and enhanced CO values on 6 March at about 25 km altitude. Finally, the MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) Fourier Transform Infra-Red (FTIR) spectrometer showed NOy values which are significantly higher than NOy* (the NOy derived from a correlation between N2O and NOy under undisturbed conditions), on 21 and 22 March in a layer centred at 22 km altitude. Thus, the mesospheric air seems to have been present in a layer descending from about 30 km in late January to 25 km altitude in early March and about 22 km altitude on 20 March. We present corroborating evidence from a model study using the KASIMA (KArlsruhe Simulation model of the Middle Atmosphere) model that also shows a layer of mesospheric air, which descended into the stratosphere in November and early December 2002, before the minor warming which occurred in late December 2002 lead to a descent of upper stratospheric air, cutting of a layer in which mesospheric air is present. This layer then descended inside the vortex over the course of the winter. The same feature is found in trajectory calculations, based on a large number of trajectories started in the vicinity of the observations on 6 March. Based on the difference between the mean age derived from SF6 (which has an irreversible mesospheric loss) and from CO2 (whose mesospheric loss is much smaller and reversible) we estimate that the fraction of mesospheric air in the layer observed on 6 March, must have been somewhere between 35% and 100%.
The Match method for quantification of polar chemical ozone loss is investigated mainly with respect to the impact of mixing across the vortex edge onto this estimate. We show for the winter 2002/03 that significant mixing across the vortex edge occurred and was accurately modeled by the Chemical Lagrangian Model of the Stratosphere. Observations of inert tracers and ozone in-situ from HAGAR on the Geophysica aircraft and sondes and also remote from MIPAS on ENVISAT were reproduced well. The model even reproduced a small vortex remnant that was isolated until June 2003 and was observed in-situ by a balloon-borne whole air sampler. We use this CLaMS simulation to quantify the impact of cross vortex edge mixing on the results of the Match method. It is shown that a time integration of the determined vortex average ozone loss rates as performed in Match results in larger ozone loss than the polar vortex average ozone loss in CLaMS. Also, the determination of the Match ozone loss rates can be influenced by mixing. This is especially important below 430 K, where ozone outside the vortex is lower than inside and the vortex boundary is not a strong transport barrier. This effect and further sampling effects cause an offset between vortex average ozone loss rates derived from Match and deduced from CLaMS with an even sampling for the entire vortex. Both, the time-integration of ozone loss and the determination of ozone loss rates for Match are evaluated using the winter 2002/03 CLaMS simulation. These impacts can explain the differences between CLaMS and Match column ozone loss. While the investigated effects somewhat reduce the apparent discrepancy in January ozone loss rates, a discrepancy between simulations and Match remains. However, its contribution to the accumulated ozone loss over the winter is not large.
Strong perturbations of the Arctic stratosphere during the winter 2002/2003 by planetary waves led to enhanced stretching and folding of the vortex. On two occasions the vortex in the lower stratosphere split into two secondary vortices that re-merged after some days. As a result of these strong disturbances the role of transport in and out of the vortex was stronger than usual. An advection and mixing simulation with the Chemical Lagrangian Model of the Stratosphere (CLaMS) utilising a suite of inert tracers tagging the original position of the air masses has been carried out. The results show a variety of synoptic and small scale features in the vicinity of the vortex boundary, especially long filaments peeling off the vortex edge and being slowly mixed into the mid latitude environment. The vortex folding events, followed by re-merging of different parts of the vortex led to strong filamentation of the vortex interior. During January, February, and March 2003 flights of the Russian high-altitude aircraft Geophysica were performed in order to probe the vortex, filaments and in one case the merging zone between the secondary vortices. Comparisons between CLaMS results and observations obtained from the Geophysica flights show in general good agreement.
wo different single particle mass spectrometers were operated in parallel at the Swiss High Alpine Research Station Jungfraujoch (JFJ, 3580 m a.s.l.) during the Cloud and Aerosol Characterization Experiment (CLACE 6) in February and March 2007. During mixed phase cloud events ice crystals from 5 μm up to 20 μm were separated from large ice aggregates, non-activated, interstitial aerosol particles and supercooled droplets using an Ice-Counterflow Virtual Impactor (Ice-CVI). During one cloud period supercooled droplets were additionally sampled and analyzed by changing the Ice-CVI setup. The small ice particles and droplets were evaporated by injection into dry air inside the Ice-CVI. The resulting ice and droplet residues (IR and DR) were analyzed for size and composition by two single particle mass spectrometers: a custom-built Single Particle Laser-Ablation Time-of-Flight Mass Spectrometer (SPLAT) and a commercial Aerosol Time of Flight Mass Spectrometer (ATOFMS, TSI Model 3800). During CLACE 6 the SPLAT instrument characterized 355 individual ice residues that produced a mass spectrum for at least one polarity and the ATOFMS measured 152 particles. The mass spectra were binned in classes, based on the combination of dominating substances, such as mineral dust, sulfate, potassium and elemental carbon or organic material. The derived chemical information from the ice residues is compared to the JFJ ambient aerosol that was sampled while the measurement station was out of clouds (several thousand particles analyzed by SPLAT and ATOFMS) and to the composition of the residues of supercooled cloud droplets (SPLAT: 162 cloud droplet residues analyzed, ATOFMS: 1094). The measurements showed that mineral dust particles were strongly enhanced in the ice particle residues. 57% of the SPLAT spectra from ice residues were dominated by signatures from mineral compounds, and 78% of the ATOFMS spectra. Sulfate and nitrate containing particles were strongly depleted in the ice residues. Sulfate was found to dominate the droplet residues (~90% of the particles). The results from the two different single particle mass spectrometers were generally in agreement. Differences in the results originate from several causes, such as the different wavelength of the desorption and ionisation lasers and different size-dependent particle detection efficiencies.
We present the analysis of the impact of convection on the composition of the tropical tropopause layer region (TTL) in West-Africa during the AMMA-SCOUT campaign. Geophysica M55 aircraft observations of water vapor, ozone, aerosol and CO2 during August 2006 show perturbed values at altitudes ranging from 14 km to 17 km (above the main convective outflow) and satellite data indicates that air detrainment is likely to have originated from convective cloud east of the flights. Simulations of the BOLAM mesoscale model, nudged with infrared radiance temperatures, are used to estimate the convective impact in the upper troposphere and to assess the fraction of air processed by convection. The analysis shows that BOLAM correctly reproduces the location and the vertical structure of convective outflow. Model-aided analysis indicates that convection can influence the composition of the upper troposphere above the level of main outflow for an event of deep convection close to the observation site. Model analysis also shows that deep convection occurring in the entire Sahelian transect (up to 2000 km E of the measurement area) has a non negligible role in determining TTL composition.