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Peroxy radicals (HO<sub>2</sub>+Σ RO<sub>2</sub>) were measured at the Weybourne Atmospheric Observatory (52° N, 1° E), Norfolk using a PEroxy Radical Chemical Amplifier (PERCA) during the winter and summer of 2002. The peroxy radical diurnal cycles showed a marked difference between the winter and summer campaigns with maximum concentrations of 12 pptv at midday in the summer and maximum concentrations as high as 30 pptv (10 min averages) in winter at night. The corresponding nighttime peroxy radical concentrations were not as high in summer (3 pptv). The peroxy radical concentration shows a distinct anti-correlation with increasing NO<sub>x</sub> during the daylight hours. At night, peroxy radicals increase with increasing NO<sub>x</sub> indicative of the role of NO<sub>3</sub> chemistry. The average diurnal cycles for net ozone production, N(O<sub>3</sub>) show a large variability in ozone production, P(O<sub>3</sub>), and a large ozone loss, L(O<sub>3</sub>) in summer relative to winter. For a daylight average, net ozone production in summer was higher than winter (1.51±0.5 ppbv h<sup>−1</sup> and 1.11±0.47 ppbv h<sup>−1</sup>, respectively). The variability in NO concentration has a much larger effect on N(O<sub>3</sub>) than the peroxy radical concentrations. Photostationary state (PSS) calculations show an NO<sub>2</sub> lifetime of 5 min in summer and 21 minutes in the winter, implying that steady-state NO-NO<sub>2</sub> ratios are not always attained during the winter months. The results show an active peroxy radical chemistry at night and that significant oxidant levels are sustained in winter. The net effect of this with respect to production of ozone in winter is unclear owing to the breakdown in the photostationary state.
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In global models of the atmosphere convection is parameterised, since the typical scale of this process is smaller than the model resolution. Here we address some of the uncertainties arising from the selection of different algorithms to simulate this process. Four different parameterisations for atmospheric convection, all used in state-of-the-art models, are implemented in the model system ECHAM5/MESSy for a consistent inter-comparison and evaluation against observations. Relatively large differences are found in the simulated precipitation patterns, whereas simulated water vapour columns distributions are quite similar and close to observations. The effects on the hydrological cycle and on the simulated meteorological conditions are discussed.
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First results of a multiannual integration with the new global aerosol model system ECHAM4/MADE are presented. This model system enables simulations of the particle number concentration and size-distribution, which is a fundamental innovation compared to previous global model studies considering aerosol mass cycles only. The data calculated by the model provide detailed insights into the properties of the global submicrometer aerosol regarding global burden, chemical composition, atmospheric residence time, particle number concentration and size-distribution. The aerosol components considered by the model are sulfate (SO<sub>4</sub>), nitrate (NO<sub>3</sub>), ammonium (NH<sub>4</sub>), black carbon (BC), organic matter (OM), mineral dust, sea salt and aerosol water. The simulated climatological annual mean global atmospheric burdens (residence times) of the dominant submicrometer aerosol components are 2.25 Tg (4.5 d) for SO<sub>4</sub>, 0.46 Tg (4.5 d) for NH<sub>4</sub>, 0.26 Tg (6.6 d) for BC, and 1.77 Tg (6.5 d) for OM. The contributions of individual processes such as emission, nucleation, condensation or dry and wet deposition to the global sources and sinks of specific aerosol components and particle number concentration are quantified. Based on this analysis, the significance of aerosol microphysical processes (nucleation, condensation, coagulation) is evaluated by comparison to the importance of other processes relevant for the submicrometer aerosol on the global scale. The results reveal that aerosol microphysics are essential for the simulation of the particle number concentration and important but not vital for the simulation of particle mass concentration. Hence aerosol microphysics should be taken into account in simulations of atmospheric processes showing a significant dependence on aerosol particle number concentration. The analysis of the vertical variation of the microphysical net production and net depletion rates performed for particle number concentration, sulfate mass and black carbon mass concentration unveils the dominant source and sink regions. Prominent features can be attributed to dominant microphysical processes such as nucleation in the upper troposphere or wet deposition in the lower troposphere. Regions of efficient coagulation can be identified.
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On 18 January 2005, two small, instrumented rockets were launched from Andøya Rocket Range (69.3° N, 16° E) during conditions with Polar Mesosphere Winter Echoes (PMWE). Each of the rockets was equipped with a Positive Ion Probe (PIP) and a Faraday rotation/differential absorption experiment, and was launched as part of a salvo of meteorological rockets measuring temperature and wind using falling spheres and chaff. Layers of PMWE were detected between 55 and 77 km by the 53.5 MHz ALWIN radar. The rockets were launched during a solar proton event, and measured extremely high ion densities, of order 10<sup>10</sup> m<sup>−3</sup>, in the region where PMWE were observed. The density measurements were analyzed with the wavelet transform technique. At large length scales, ~10<sup>3</sup> m, the power spectral density can be fitted with a <i>k</i><sup>−3</sup> wave number dependence, consistent with saturated gravity waves. Outside the PMWE layers the <i>k</i><sup>−3</sup> spectrum extends down to approximately 10<sup>2</sup> m where the fluctuations are quickly damped and disappear into the instrumental noise. Inside the PMWE layers the spectrum at smaller length scales is well fitted with a <i>k</i><sup>−5/3</sup> dependence over two decades of scales. The PMWE are therefore clearly indicative of turbulence, and the data are consistent with the turbulent dissipation of breaking gravity waves. We estimate a lower limit for the turbulent energy dissipation rate of about 10<sup>−2</sup> W/kg in the upper (72 km) layer.
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An automated, ground-based instrument was used to measure gas-phase hydroperoxides at the Jungfraujoch High Altitude Research Station as part of the Free Tropospheric EXperiment (FREETEX) during February/March 2003. A nebulising reflux concentrator sampled ambient air twice hourly, prior to on-site analysis by HPLC speciation, coupled with post-column peroxidase derivatisation and fluorescence detection. Hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) concentrations reached up to 1330 pptv over the 13-day period with a mean of 183±233 pptv (± one standard deviation). Methyl hydroperoxide (CH<sub>3</sub>OOH) reached up to 379 pptv with a mean of 51±55 pptv. No other organic hydroperoxides were detected. The lack of an explicit diurnal cycle suggests that hydroperoxide concentrations are chiefly influenced by transport processes rather than local photochemistry at this mountainous site. There was some evidence that elevated concentrations of H<sub>2</sub>O<sub>2</sub> existed in air-masses originating from the south-west, suggesting higher concentrations of HO<sub>x</sub> due to more active photochemistry. Air which had been recently polluted exhibited low H<sub>2</sub>O<sub>2</sub> concentration due to a combination of suppression of HO<sub>2</sub> by NO<sub>x</sub> and deposition. The concentrations of H<sub>2</sub>O<sub>2</sub> sampled here are consistent with previous box modelling studies of hydroperoxides, except in periods influenced by the boundary layer, where agreement required a depositional sink.
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TSP and PM<sub>2.5</sub> aerosol samples were synchronously collected at six sites along the transport pathway of dust storm from desert regions to coastal areas in the spring of 2004. The aerosol concentration and composition were measured to investigate the regional characteristics of spring Asian dust and its impact on aerosol chemistry over northern China. Based on the daily PM<sub>10</sub> concentrations in 13 cities, the northern China could be divided into five regions, i.e., Northern Dust Region, Northeastern Dust Region, Western Dust Region, Inland Passing Region, and Coastal Region. Northern Dust Region was characterized by high content of Ca and Northeastern Dust Region was characterized by low one instead. Northeastern Dust Region was a relatively clean area with the lowest concentrations of pollutants and secondary ions among all sites. Inland Passing Region and Coastal Region showed high concentrations of pollutants, of which As and Pb in Inland Passing Region, and Na<sup>+</sup>, SO<sub>4</sub><sup>2−</sup> and NO<sub>3</sub><sup>−</sup> in Coastal Region were the highest, respectively. The impact of dust on air quality was the greatest in the cities near source regions, and this impact decreased in the order of Yulin/Duolun > Beijing > Qingdao/Shanghai as the increase of transport distance. The spring Asian dust was inclined to affect the chemical components in coarse particles near source regions and those in fine particles in the cities far from source regions. Dust storm could mix significant quantities of pollutants on the pathway and carry them to the downwind cities or dilute the pollutants in the cities over northern China. Each dust episode corresponded to a low ratio of NO<sub>3</sub><sup>−</sup>/SO<sub>4</sub><sup>2−</sup> with the lowest value appearing after the peak of dust storm. Asian dust played an important role in buffering and neutralizing the acidity of atmosphere in the cities over northern China, which could lead to the pH in the aerosols increase ~1 in spring.
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A lightning NO<sub>x</sub> (LiNOx) source has been implemented in the deep convection scheme of the Meso-NH mesoscale model following a mass-flux formalism coherent with the transport and scavenging of gases inside the convective scheme. In this approach the vertical transport of NO inside clouds is calculated by the parameterization of deep convective transport, thus eliminating the need for a-priori LiNOx profiles. Once produced inside the convective column, NO molecules are redistributed by updrafts and downdrafts and detrained in the environment when the conditions are favorable. The model was applied to three particular flights during the Tropical Convection, Cirrus and Nitrogen Oxides (TROCCINOX) campaign over the tropical area around Bauru on 3–4 March 2004. The convective activity during the three flights was investigated using brightness temperature at 10.7 μm observed from GOES-12 satellite. The use of a model-to-satellite approach reveals that the simulation appears rather realistic compared to the observations. The diurnal cycle of the simulated brightness temperature, CAPE, number of IC flashes, NO entrainment flux are in phase, with a succession of three marked peaks at 18:00 UTC (15:00 LT). These simulated peaks precede the observed afternoon one by about three hours. Comparison of the simulated NO<sub>x</sub> with observations along the flight tracks show that the model reproduces well the observed NO<sub>x</sub> levels when the LiNOx source is applied. The budget of entrainment, detrainment and LiNOx convective fluxes shows that the majority of the NO detrained back to the environment comes from lightning source inside the convective columns. Entrainment of NO from the environment and vertical transport from the boundary layer were not significant during the episode. The troposphere is impacted by detrainment fluxes of LiNOx from 4 km altitude to 16 km with maximum values around 14 km altitude. Detrainment fluxes vary between 75 kg(N)/s during nighttime to 400 kg(N)/s at the times of maximun convective activity. Extrapolation of the regional LiNOx source would yield a global LiNOx production around 5.7 Tg(N)/year which is within the current estimates but should not hide the overestimation of the number of flash rates by the model.
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More than three years of measurements of aerosol size-distribution and different gas and meteorological parameters made in Po Valley, Italy were analysed for this study to examine which of the meteorological and trace gas variables effect on the emergence of nucleation events. As the analysis method, we used discriminant analysis with non-parametric Epanechnikov kernel, included in non-parametric density estimation method. The best classification result in our data was reached with the combination of relative humidity, ozone concentration and a third degree polynomial of radiation. RH appeared to have a preventing effect on the new particle formation whereas the effects of O<sub>3</sub> and radiation were more conductive. The concentration of SO<sub>2</sub> and NO<sub>2</sub> also appeared to have significant effect on the emergence of nucleation events but because of the great amount of missing observations, we had to exclude them from the final analysis.
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Measurements are presented from a sampling location 50 km downwind of Greater London, UK, to investigate the timescales required for the atmospheric transformations of aerosol in urban emissions plumes in the context of photochemical age based on the benzene to toluene ratio. It is shown that particles at or around 100 nm in diameter exhibit the greatest systematic variability in chemical properties, and thus hygroscopic properties, on a timescale of 1–2 days. The smaller Aitken mode and larger accumulation mode particles exhibit less variability on these timescales, which we propose is as a result of their different residence times in the atmosphere. The larger accumulation particles have been in the atmosphere longer than the 100 nm particles and their chemistry and hygroscopic properties have been integrated over several days and potentially over several source regions. In contrast, the smaller Aitken mode particles show little systematic variability with photochemical age because their atmospheric lifetimes are short, thus chemical changes and hence changes in water affinity have not had time to occur. Increases in the particle diameter of up to 40% are observed at 90% relative humidity in the accumulation mode from the uptake of water as the particles become increasingly soluble in nature.
