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Iodine species in the troposphere are linked to ozone depletion and new particle formation. In this study, a full year of iodine monoxide (IO) columns retrieved from measurements of the SCIAMACHY satellite instrument is presented, coupled with a discussion of their uncertainties and the detection limits. The largest amounts of IO are found near springtime in the Antarctic. A seasonal variation of iodine monoxide in Antarctica is revealed with high values in springtime, slightly less IO in the summer period and again larger amounts in autumn. In winter, no elevated IO levels are found in the areas accessible to satellite measurements. This seasonal cycle is in good agreement with recent ground-based measurements in Antarctica. In the Arctic region, no elevated IO levels were found in the period analysed. This implies that different conditions with respect to iodine release exist in the two Polar Regions. To investigate possible release mechanisms, comparisons of IO columns with those of tropospheric BrO, and ice coverage are described and discussed. Some parallels and interesting differences between IO and BrO temporal and spatial distributions are identified. Overall, the large spatial coverage of satellite retrieved IO data and the availability of a long-term dataset provide new insight about the abundances and distributions of iodine compounds in the troposphere.
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Air ions are characterized on the basis of measurements carried out in a boreal forest at the Hyytiälä SMEAR station, Finland, during the BIOFOR III campaign in spring 1999. The air ions were discriminated as small ions (charged molecular aggregates of the diameter of less than 2.5 nm), intermediate ions (charged aerosol particles of the diameter of 2.5–8 nm), and large ions (charged aerosol particles of the diameter of 8–20 nm). Statistical characteristics of the ion concentrations and the parameters of ion balance in the atmosphere are presented separately for the nucleation event days and non-event days. In the steady state, the ionization rate is balanced with the loss of small ions, which is expressed as the product of the small ion concentration and the ion sink rate. The widely known sinks of small ions are the recombination with small ions of opposite polarity and attachment to aerosol particles. The dependence of small ion concentration on the concentration of aerosol particles was investigated applying a model of the bipolar diffusion charging of particles by small ions. When the periods of relative humidity above 95% and wind speed less than 0.6 m s<sup>−1</sup> were excluded, then the small ion concentration and the theoretically calculated small ion sink rate were closely negatively correlated (correlation coefficient −87%). However, an extra ion loss term of the same magnitude as the ion loss onto aerosol particles is needed for a quantitative explanation of the observations. This term is presumably due to the small ion deposition on coniferous forest. The hygroscopic growth correction of the measured aerosol particle size distributions was also found to be necessary for the proper estimation of the ion sink rate. In the case of nucleation burst events, the concentration of small positive ions followed the general balance equation, no extra ion loss in addition to the deposition on coniferous forest was detected, and the hypothesis of the conversion of ions into particles in the process of ion-induced nucleation was not proved. The estimated average ionization rate of the air at the Hyytiälä station in early spring, when the ground was partly covered with snow, was about 6 ion pairs cm<sup>−3</sup> s<sup>−1</sup>. The study of the charging state of nanometer aerosol particles (diameter 2.5–8 nm) in the atmosphere revealed a strong correlation (correlation coefficient 88%) between the concentrations of particles neutralized in the aerosol spectrometer and naturally positively charged particles (air ions) during nucleation bursts. The charged fraction of particles varied from 3% to 6% in accordance with the hypothesis that the particles are quasi-steady state charged.
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Vertical (cross-isentropic) mixing is produced by small-scale turbulent processes which are still poorly understood and paramaterized in numerical models. In this work we provide estimates of local equivalent diffusion in the lower stratosphere by comparing balloon borne high-resolution measurements of chemical tracers with reconstructed mixing ratio from large ensembles of random Lagrangian backward trajectories using European Centre for Medium-range Weather Forecasts analysed winds and a chemistry-transport model (REPROBUS). We focus on a case study in subtropical latitudes using data from HIBISCUS campaign. An upper bound on the vertical diffusivity is found in this case study to be of the order of 0.5 m<sup>2</sup> s<sup>−1</sup> in the subtropical region, which is larger than the estimates at higher latitudes. The relation between diffusion and dispersion is studied by estimating Lyapunov exponents and studying their variation according to the presence of active dynamical structures.
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Global distributions of profiles of sulphur hexafluoride (SF<sub>6</sub>) have been retrieved from limb emission spectra recorded by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on Envisat covering the period September 2002 to March 2004. Individual SF<sub>6</sub> profiles have a precision of 0.5 pptv below 25 km altitude and a vertical resolution of 4–6 km up to 35 km altitude. These data have been validated versus in situ observations obtained during balloon flights of a cryogenic whole-air sampler. For the tropical troposphere a trend of 0.230±0.008 pptv/yr has been derived from the MIPAS data, which is in excellent agreement with the trend from ground-based flask and in situ measurements from the National Oceanic and Atmospheric Administration Earth System Research Laboratory, Global Monitoring Division. For the data set currently available, based on at least three days of data per month, monthly 5° latitude mean values have a 1σ standard error of 1%. From the global SF<sub>6</sub> distributions, global daily and monthly distributions of the apparent mean age of air are inferred by application of the tropical tropospheric trend derived from MIPAS data. The inferred mean ages are provided for the full globe up to 90° N/S, and have a 1σ standard error of 0.25 yr. They range between 0 (near the tropical tropopause) and 7 years (except for situations of mesospheric intrusions) and agree well with earlier observations. The seasonal variation of the mean age of stratospheric air indicates episodes of severe intrusion of mesospheric air during each Northern and Southern polar winter observed, long-lasting remnants of old, subsided polar winter air over the spring and summer poles, and a rather short period of mixing with midlatitude air and/or upward transport during fall in October/November (NH) and April/May (SH), respectively, with small latitudinal gradients, immediately before the new polar vortex starts to form. The mean age distributions further confirm that SF<sub>6</sub> is destroyed in the mesosphere to a considerable degree. Model calculations with the Karlsruhe simulation model of the middle atmosphere (KASIMA) chemical transport model agree well with observed global distributions of the mean age only if the SF<sub>6</sub> sink reactions in the mesosphere are included in the model.
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Only recently, ground- and satellite-based measurements have reported high concentrations of IO in coastal Antarctica. The sources of such a large iodine burden in the Antarctic atmosphere remain unknown. We propose a novel mechanism for iodine release from sea-ice surfaces. The release is triggered by the biological production of iodide (I<sup>-</sup>) and hypoiodous acid (HOI) from marine algae, contained within and underneath sea-ice, and their diffusion through sea-ice brine channels to accumulate in the quasi-liquid layer on the surface of sea-ice. A multiphase chemical model of polar atmospheric chemistry has been developed to investigate the biology-ice-atmosphere coupling in the polar environment. Model simulations were conducted to interpret recent observations of elevated IO in the coastal Antarctic springtime. The results show that the levels of inorganic iodine (i.e. I<sub>2</sub>, IBr, ICl) released from sea-ice through this mechanism account for the observed IO concentrations in the Antarctic springtime environment. The model results also indicate that iodine may trigger the catalytic release of bromine from sea-ice through phase equilibration of IBr. Considering the extent of sea-ice around the Antarctic continent, we suggest that the resulting high levels of iodine may have widespread impact on catalytic ozone destruction and aerosol formation in the Antarctic lower troposphere.
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The European heat wave of July 2006 was caused by advection of very hot and dry air from North Africa. Air masses were transported on the western edge of the high pressure system, centred over Eastern Europe, resulting in exceptionally high air temperatures over large areas of the continent. In the first two weeks of July 2006 a severe heat wave affected Central and North-Eastern Europe. We present a synoptic analysis of the July 2006 European heat wave, resulting formation and transport of photooxidants over Europe as simulated by the on-line tropospheric chemistry model GEM-AQ. The model was executed on a global variable grid with ~15 km resolution over the entire European continent. Modelling results have been compared with surface observations and vertical soundings of meteorological and air quality parameters. We find that the calculated error measures, as well as analysis of time series and trends for selected quantities, indicate good model performance over the simulation period. The spatial pattern of two exposure indicators – SOMO35 and AOT40 – showed similarities with the high temperatures distribution. The zone of highest exposure was located over Central Europe along the advection path of the hot African air mass. The exposure to high ozone concentrations in higher latitudes was reduced by the dilution and aging of polluted air masses advected from over Central Europe.
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Recent observations of the polar mesosphere have revealed that waves with periods near two days reach significant amplitudes in both summer and winter. This is in striking contrast to mid-latitude observations where two-day waves maximise in summer only. Here, we use data from a meteor radar at Esrange (68° N, 21° E) in the Arctic and data from the MLS instrument aboard the EOS Aura satellite to investigate the wintertime polar two-day wave in the stratosphere, mesosphere and lower thermosphere. The radar data reveal that mesospheric two-day wave activity measured by horizontal-wind variance has a semi-annual cycle with maxima in winter and summer and equinoctial minima. The MLS data reveal that the summertime wave in the mesosphere is dominated by a westward-travelling zonal wavenumber three wave with significant westward wavenumber four present. It reaches largest amplitudes at mid-latitudes in the southern hemisphere. In the winter polar mesosphere, however, the wave appears to be an eastward-travelling zonal wavenumber two, which is not seen during the summer. At the latitude of Esrange, the eastward-two wave reaches maximum amplitudes near the stratopause and appears related to similar waves previously observed in the polar stratosphere. We conclude that the wintertime polar two-day wave is the mesospheric manifestation of an eastward-propagating, zonal-wavenumber-two wave originating in the stratosphere, maximising at the stratopause and likely to be generated by instabilities in the polar night jet.
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Measurements of the vertical distribution of aerosol properties provide essential information for generating more accurate model estimates of radiative forcing and atmospheric heating rates compared with employing remotely sensed column averaged properties. A month long campaign over the Indian Ocean during March 2006 investigated the interaction of aerosol, clouds, and radiative effects. Routine vertical profiles of aerosol and water vapor were determined using autonomous unmanned aerial vehicles equipped with miniaturized instruments. Comparisons of these airborne instruments with established ground-based instruments and in aircraft-to-aircraft comparisons demonstrated an agreement within 10%. <br><br> Aerosol absorption optical depths measured directly using the unmanned aircraft differed from columnar AERONET sun-photometer results by only 20%. Measurements of total particle concentration, particle size distributions, aerosol absorption and black carbon concentrations are presented along with the trade wind thermodynamic structure from the surface to 3000 m above sea level. Early March revealed a well-mixed layer up to the cloud base at 500 m above mean sea level (m a.s.l.), followed by a decrease of aerosol concentrations with altitude. The second half of March saw the arrival of a high altitude plume existing above the mixed layer that originated from a continental source and increased aerosol concentrations by more than tenfold, yet the surface air mass showed little change in aerosol concentrations and was still predominantly influenced by marine sources. Black carbon concentrations at 1500 m above sea level increased from 70 ng/m<sup>3</sup> to more than 800 ng/m<sup>3</sup> with the arrival of this polluted plume. The absorption aerosol optical depth increased from as low as 0.005 to as much as 0.035 over the same period. The spectral dependence of the aerosol absorption revealed an absorption Angstrom exponent of 1.0, which is typical of an aerosol with most of its absorption attributed to black carbon and generally indicates the absorbing component originated from fossil fuel sources and other high-temperature combustion sources. The results indicate that surface measurements do not represent the aerosol properties within the elevated layers, especially if these layers are influenced by long range transport.
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With the global aerosol-climate model ECHAM5-HAM we investigate the potential influence of organic aerosol originating from the ocean on aerosol mass and chemical composition and the droplet concentration and size of marine clouds. We present sensitivity simulations in which the uptake of organic matter in the marine aerosol is prescribed for each aerosol mode with varying organic mass and mixing state, and with a geographical distribution and seasonality similar to the oceanic emission of dimethyl sulfide. Measurements of aerosol mass, aerosol chemical composition and cloud drop effective radius are used to assess the representativity of the model initializations. Good agreement with the measurements is obtained when organic matter is added to the Aitken, accumulation and coarse modes simultaneously. Representing marine organics in the model leads to higher cloud drop number concentrations and thus smaller cloud drop effective radii, and this improves the agreement with measurements. The mixing state of the organics and the other aerosol matter, i.e. internal or external depending on the formation process of aerosol organics, is an important factor for this. We estimate that globally about 75 Tg C yr<sup>−1</sup> of organic matter from marine origin enters the aerosol phase, with comparable contributions from primary emissions and secondary organic aerosol formation.
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Evidence of chemical isolation in the Asian monsoon anticyclone is presented using chemical constituents obtained from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer instrument during summer (June–August) of 2004–2006. Carbon monoxide (CO) shows a broad maximum over the monsoon anticyclone region in the upper troposphere and lower stratosphere (UTLS); these enhanced CO values are associated with air pollution transported upward by convection, and confined by the strong anticyclonic circulation. Profiles inside the anticyclone show enhancement of tropospheric tracers CO, HCN, C<sub>2</sub>H<sub>6</sub>, and C<sub>2</sub>H<sub>2</sub> between ~12 to 20 km, with maxima near 13–15 km. Strong correlations are observed among constituents, consistent with sources from near-surface pollution and biomass burning. Stratospheric tracers (O<sub>3</sub>, HNO<sub>3</sub> and HCl) exhibit decreased values inside the anticyclone between ~12–20 km. These observations are further evidence of transport of lower tropospheric air into the UTLS region, and isolation of air within the anticyclone. The relative enhancements of tropospheric species inside the anticyclone are closely related to the photochemical lifetime of the species, with strongest enhancement for shorter lived species. Vertical profiles of the ratio of C<sub>2</sub>H<sub>2</sub>/CO (used to measure the relative age of air) suggest relatively rapid transport of fresh emissions up to the tropopause level inside the anticyclone.
