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Global cloud and precipitation chemistry and wet deposition: tropospheric model simulations with ECHAM5/MESSy1

The representation of cloud and precipitation chemistry and subsequent wet deposition of trace constituents in global atmospheric chemistry models is associated with large uncertainties. To improve the simulated trace gas distributions we apply the new submodel SCAV, which includes detailed cloud and precipitation chemistry and present results of the atmospheric chemistry general circulation model ECHAM5/MESSy1. A good agreement with observed wet deposition fluxes for species causing acid rain is obtained. The new scheme enables prognostic calculations of the pH of clouds and precipitation, and these results are also in accordance with observations. We address the influence of detailed cloud and precipitation chemistry on trace constituents based on sensitivity simulations. The results confirm previous results from regional scale and box models, and we extend the analysis to the role of aqueous phase chemistry on the global scale. Some species are directly affected through multiphase removal processes, and many also indirectly through changes in oxidant concentrations, which in turn have an impact on the species lifetime. While the overall effect on tropospheric ozone is relatively small (<10%), regional effects on O3 can reach ≈20%, and several important compounds (e.g., H2O2, HCHO) are substantially depleted by clouds and precipitation.
Estimating the NH3:H2SO4 ratio of nucleating clusters in atmospheric conditions using quantum chemical methods

We study the ammonia addition reactions of H2SO4·NH3 molecular clusters containing up to four ammonia and two sulfuric acid molecules using the ab initio method RI-MP2 (Resolution of Identity 2nd order Møller-Plesset perturbation theory). Together with results from previous studies, we use the computed values to estimate an upper limit for the ammonia content of small atmospheric clusters, without having to explicitly include water molecules in the quantum chemical simulations. Our results indicate that the NH3:H2SO4 mole ratio of small molecular clusters in typical atmospheric conditions is probably around 1:2. High ammonia concentrations or low temperatures may lead to the formation of ammonium bisulfate (1:1) clusters, but our results rule out the formation of ammonium sulfate clusters (2:1) anywhere in the atmosphere. A sensitivity analysis indicates that the qualitative conclusions of this study are not affected even by relatively large errors in the calculation of electronic energies or vibrational frequencies.
Aerosol climatology: dependence of the Angstrom exponent on wavelength over four AERONET sites

The Ångström exponent, α, is often used as a qualitative indicator of aerosol particle size. In this study, aerosol optical depth (AOD) and Ångström exponent (α) data were analyzed to obtain information about the adequacy of the simple use of the Ångström exponent for characterizing aerosols, and for exploring possibilities for a more efficient characterization of aerosols. This was made possible by taking advantage of the spectral variation of α, the so-called curvature. The data were taken from four selected AERONET stations, which are representative of four aerosol types, i.e. biomass burning, pollution, desert dust and maritime. Using the least-squares method, the Ångström-α was calculated in the spectral interval 340–870 nm, along with the coefficients α1 and α2 of the second order polynomial fit to the plotted logarithm of AOD versus the logarithm of wavelength, and the second derivative of α. The results show that the spectral curvature can provide important additional information about the different aerosol types, and can be effectively used to discriminate between them, since the fine-mode particles exhibit negative curvature, while the coarse-mode aerosols positive. In addition, the curvature has always to be taken into account in the computations of Ångström exponent values in the spectral intervals 380–440 nm and 675–870 nm, since fine-mode aerosols exhibit larger α675–870 than α380–440 values, and vice-versa for coarse-mode particles. A second-order polynomial fit simulates the spectral dependence of the AODs very well, while the associated constant term varies proportionally to the aerosol type. The correlation between the coefficients α1 and α2 of the second-order polynomial fit and the Ångström exponent α, and the atmospheric turbidity, is further investigated. The obtained results reveal important features, which can be used for better discriminating between different aerosol types.
Contributions of anthropogenic and natural sources of sulfur to SO2, H2SO4(g) and nanoparticle formation

Atmospheric nanoparticles (NPs) are important intermediates in the transition from gas-phase molecules to new aerosols that can activate into cloud droplets. Through increases in the emissions of sulfur-containing gases, human activities have likely increased the number of NPs produced in the atmosphere. To have significant impacts, however, sulfur pollution must be transported away from the surface, where NP formation is inefficient, to higher altitudes. To characterize this anthropogenic influence, tagged tracers are implemented in a global atmospheric transport model. The tagged tracers are used to track the contributions of sulfur from five sources (anthropogenic, oceanic, volcanic, aircraft, and stratospheric) to the gas-phase burdens of SO2 and H2SO4(g), and the rates of forming atmospheric NPs. Because NPs may be produced by a variety of mechanisms, three different aerosol nucleation schemes (binary, ternary and ion-induced) are used in the model calculations. Of the SO2 in the global troposphere, the tagged tracers indicate that about 69% originates from anthropogenic surface emissions, 20% from the oceans and 10% from de-gassing volcanoes. The same sources contribute about 56%, 24% and 19%, respectively, to the global tropospheric H2SO4(g) burden. The anthropogenic contribution for H2SO4(g) is reduced because anthropogenic SO2 produces H2SO4(g) less efficiently than oceanic and volcanic sulfur. Regardless of the underlying nucleation assumptions, the simulations show a pronounced influence of anthropogenic sulfur on atmospheric NP formation, particularly in the Northern Hemisphere. Utilizing the tagged H2SO4(g) contributions, anthropogenic sulfur is estimated to account for roughly 69% of the NP formation in the Northern Hemisphere, 31% in the Southern Hemisphere and 56% across the global troposphere. In the key region of the upper troposphere, anthropogenic and oceanic sulfur both make sizeable contributions to NP formation (54% and 37%, respectively). The tagged tracer contributions suggest that human activities have probably more than doubled the NP production rate in the atmosphere from preindustrial to modern times.
Global peroxyacetyl nitrate (PAN) retrieval in the upper troposphere from limb emission spectra of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS)

We use limb emission spectra of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) onboard the ENVIronmental SATellite (ENVISAT) to derive the first global distribution of peroxyacetyl nitrate (PAN) in the upper troposphere. PAN is generated in tropospheric air masses polluted by fuel combustion or biomass burning and acts as a reservoir and carrier of NOx in the cold free troposphere. PAN exhibits continuum-like broadband structures in the mid-infrared region and was retrieved in a contiguous analysis window covering the wavenumber region 775–800 cm−1. The interfering species CCl4, HCFC-22, H2O, ClONO2, CH3CCl3 and C2H2 were fitted along with PAN, whereas pre-fitted profiles were used to model the contribution of other contaminants like ozone. Sensitivity tests consisting in retrieval without consideration of PAN demonstrated the existence of PAN signatures in MIPAS spectra obtained in polluted air masses. The analysed dataset consists of 10 days between 4 October and 1 December 2003. This period covers the end of the biomass burning season in South America and South and East Africa, in which generally large amounts of pollutants are produced and distributed over wide areas of the southern hemispheric free troposphere. Indeed, elevated PAN amounts of 200–700 pptv were measured in a large plume extending from Brasil over the Southern Atlantic, Central and South Africa, the South Indian Ocean as far as Australia at altitudes between 8 and 16 km. Enhanced PAN values were also found in a much more restricted area between northern subtropical Africa and India. The most significant northern midlatitude PAN signal was detected in an area at 8 km altitude extending from China into the Chinese Sea. The average mid and high latitude PAN amounts found at 8 km were around 125 pptv in the northern, but only between 50 and 75 pptv in the southern hemisphere. The PAN distribution found in the southern hemispheric tropics and subtropics is highly correlated with the jointly fitted acetylene (C2H2), which is another pollutant produced by biomass burning, and agrees reasonably well with the CO plume detected during end of September 2003 at the 275 hPa level (~10 km) by the Measurement of Pollution in the Troposphere (MOPITT) instrument on the Terra satellite. Similar southern hemispheric PAN amounts were also observed by previous airborne measurements performed in September/October 1992 and 1996 above the South Atlantic and the South Pacific, respectively.
Predicting terrestrial 222Rn flux using gamma dose rate as a proxy

222Rn is commonly used as a natural tracer for validating climate models. To improve such models a better source term for 222Rn than currently used is necessary. The aim of this work is to establish a method for mapping this source term by using a commonly measured proxy, the gamma dose rate (GDR). Automatic monitoring of GDR has been networked in 25 European countries by the Institute for Environment and Sustainability at the Joint Research Centre (JRC IES) in Ispra, Italy, using a common data format. We carried out simultaneous measurements of 222Rn flux and GDR at 63 locations in Switzerland, Germany, Finland and Hungary in order to cover a wide range of GDR. Spatial variations in GDR resulted from different radionuclide concentrations in soil forming minerals. A relatively stable fraction (20%) of the total terrestrial GDR originates from the 238U decay series, of which 222Rn is a member. Accordingly, spatial variation in terrestrial GDR was found to describe almost 60% of the spatial variation in 222Rn flux. Furthermore, temporal variation in GDR and 222Rn was found to be correlated. Increasing soil moisture reduces gas diffusivity and the rate of 222Rn flux but it also decreases GDR through increased shielding of photons. Prediction of 222Rn flux through GDR for individual measurement points is imprecise but un-biased. Verification of larger scale prediction showed that estimates of mean 222Rn fluxes were not significantly different from the measured mean values.
Size-segregated fluxes of mineral dust from a desert area of northern China by eddy covariance

Mineral dust emission accounts for a substantial portion of particles present in the troposphere. It is emitted mostly from desert areas, mainly through intense storm episodes. The aim of this work was to quantify size-segregated fluxes of mineral dust particles emitted during storm events occurring in desert areas of northern China (Alashan desert, Inner Mongolia), known to act as one of the strongest sources of mineral dust particles in the Asian continent. Long-range transport of mineral dust emitted in this area is responsible for the high particle concentrations reached in densely populated areas, including the city of Beijing. Based on a theoretical analysis, an eddy covariance system was built to get size-segregated fluxes of mineral dust particles with optical diameters ranging between 0.26 and 7.00 µm. The system was optimised to measure fluxes under intense storm event conditions. It was tested in two sites located in the Chinese portion of the Gobi desert. During the field campaign, an intense wind erosion event, classified as a "weak dust storm", was recorded in one of them. Data obtained during this event indicate that particle number fluxes were dominated by the finer fraction, whereas in terms of mass, coarser particle accounted for the largest portion. It was found that during the storm event, ratios of size-segregated particle mass fluxes remained substantially constant and a simple parameterization of particle emission from total mass fluxes was possible. A strong correlation was also found between particle mass fluxes and the friction velocity. This relationship is extremely useful to investigate mechanisms of particle formation by wind erosion.
Isoprene and monoterpene fluxes from Central Amazonian rainforest inferred from tower-based and airborne measurements, and implications on the atmospheric chemistry and the local carbon budget

We estimated the isoprene and monoterpene source strengths of a pristine tropical forest north of Manaus in the central Amazon Basin using three different micrometeorological flux measurement approaches. During the early dry season campaign of the Cooperative LBA Airborne Regional Experiment (LBA-CLAIRE-2001), a tower-based surface layer gradient (SLG) technique was applied simultaneously with a relaxed eddy accumulation (REA) system. Airborne measurements of vertical profiles within and above the convective boundary layer (CBL) were used to estimate fluxes on a landscape scale by application of the mixed layer gradient (MLG) technique. The mean daytime fluxes of organic carbon measured by REA were 2.1 mg C m−2 h−1 for isoprene, 0.20 mg C m−2 h−1 for α-pinene, and 0.39 mg C m−2 h−1 for the sum of monoterpenes. These values are in reasonable agreement with fluxes determined with the SLG approach, which exhibited a higher scatter, as expected for the complex terrain investigated. The observed VOC fluxes are in good agreement with simulations using a single-column chemistry and climate model (SCM). In contrast, the model-derived mixing ratios of VOCs were by far higher than observed, indicating that chemical processes may not be adequately represented in the model. The observed vertical gradients of isoprene and its primary degradation products methyl vinyl ketone (MVK) and methacrolein (MACR) suggest that the oxidation capacity in the tropical CBL is much higher than previously assumed. A simple chemical kinetics model was used to infer OH radical concentrations from the vertical gradients of (MVK+MACR)/isoprene. The estimated range of OH concentrations during the daytime was 3–8×106 molecules cm−3, i.e., an order of magnitude higher than is estimated for the tropical CBL by current state-of-the-art atmospheric chemistry and transport models. The remarkably high OH concentrations were also supported by results of a simple budget analysis, based on the flux-to-lifetime relationship of isoprene within the CBL. Furthermore, VOC fluxes determined with the airborne MLG approach were only in reasonable agreement with those of the tower-based REA and SLG approaches after correction for chemical decay by OH radicals, applying a best estimate OH concentration of 5.5×106 molecules cm−3. The SCM model calculations support relatively high OH concentration estimates after specifically being constrained by the mixing ratios of chemical constituents observed during the campaign. The relevance of the VOC fluxes for the local carbon budget of the tropical rainforest site during the measurements campaign was assessed by comparison with the concurrent CO2 fluxes, estimated by three different methods (eddy correlation, Lagrangian dispersion, and mass budget approach). Depending on the CO2 flux estimate, 1–6% or more of the carbon gained by net ecosystem productivity appeared to be re-emitted through VOC emissions.
Technical Note: The effect of sensor resolution on the number of cloud-free observations from space

Air quality and surface emission inversions are likely to be focal points for future satellite missions on atmospheric composition. Most important for these applications is sensitivity to the atmospheric composition in the lowest few kilometers of the troposphere. Reduced sensitivity by clouds needs to be minimized. In this study we have quantified the increase in number of useful footprints, i.e. footprints which are sufficient cloud-free, as a function of sensor resolution (footprint area). High resolution (1 km×1 km) MODIS TERRA cloud mask observations are aggregated to lower resolutions. Statistics for different thresholds on cloudiness are applied. For each month in 2004 four days of MODIS data are analyzed. Globally the fraction of cloud-free observations drops from 16% at 100 km2 resolution to only 3% at 10 000 km2 if not a single MODIS observation within a footprint is allowed to be cloudy. If up to 5% or 20% of a footprint is allowed to be cloudy, the fraction of cloud-free observations is 9% or 17%, respectively, at 10 000 km2 resolution. The probability of finding cloud-free observations for different sensor resolutions is also quantified as a function of geolocation and season, showing examples over Europe and northern South America (ITCZ).
Lightning-produced NOx over Brazil during TROCCINOX: airborne measurements in tropical and subtropical thunderstorms and the importance of mesoscale convective systems

During the TROCCINOX field experiments in February–March 2004 and February 2005, airborne in situ measurements of NO, NOy, CO, and O3 mixing ratios and the J(NO2) photolysis rate were carried out in the anvil outflow of thunderstorms over southern Brazil. Both tropical and subtropical thunderstorms were investigated, depending on the location of the South Atlantic convergence zone. Tropical air masses were discriminated from subtropical ones according to the higher equivalent potential temperature (Θe) in the lower and mid troposphere, the higher CO mixing ratio in the mid troposphere, and the lower wind velocity in the upper troposphere within the Bolivian High (north of the subtropical jet stream). During thunderstorm anvil penetrations, typically at 20–40 km horizontal scales, NOx mixing ratios were distinctly enhanced and the absolute mixing ratios varied between 0.2–1.6 nmol mol−1 on average. This enhancement was mainly attributed to NOx production by lightning and partly due to upward transport from the NOx-richer boundary layer. In addition, CO mixing ratios were occasionally enhanced, indicating upward transport from the boundary layer. For the first time, the composition of the anvil outflow from a large, long-lived mesoscale convective system (MCS) advected from northern Argentina and Uruguay was investigated in more detail. Over a horizontal scale of about 400 km, NOx, CO and O3 absolute mixing ratios were significantly enhanced in these air masses in the range of 0.6–1.1, 110–140 and 60–70 nmol mol−1, respectively. Analyses from trace gas correlations and a Lagrangian particle dispersion model indicate that polluted air masses, probably from the Buenos Aires urban area and from biomass burning regions, were uplifted by the MCS. Ozone was distinctly enhanced in the aged MCS outflow, due to photochemical production and entrainment of O3-rich air masses from the upper troposphere – lower stratosphere region. The aged MCS outflow was transported to the north, ascended and circulated, driven by the Bolivian High over the Amazon basin. In the observed case, the O3-rich MCS outflow remained over the continent and did not contribute to the South Atlantic ozone maximum.