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Equatorial transport as diagnosed from nitrous oxide variability

The mechanisms of transport on annual, semi-annual and quasi-biennial time scales in the equatorial (10° S–10° N) stratosphere are investigated using the nitrous oxide (N2O) measurements of the space-borne ODIN Sub-Millimetre Radiometer from November 2001 to June 2005, and the simulations of the three-dimensional chemical transport models MOCAGE and SLIMCAT. Both models are forced with analyses from the European Centre for Medium-range Weather Forecast, but the vertical transport is derived either from the forcing analyses by solving the continuity equation (MOCAGE), or from diabatic heating rates using a radiation scheme (SLIMCAT). The N2O variations in the mid-to-upper stratosphere at levels above 32 hPa are generally well captured by the models though significant differences appear with the observations as well as between the models, attributed to the difficulty of capturing correctly the slow upwelling associated with the Brewer-Dobson circulation. However, in the lower stratosphere, below 32 hPa, the observed variations are shown to be mainly seasonal with peak amplitude at 400–450 K (~17.5–19 km), totally missed by the models. The minimum N2O in June, out of phase by two months with the known minimum seasonal upwelling associated with the Brewer-Dobson circulation and moreover amplified over the Western Pacific compared to Africa is incompatible with the seasonal change of upwelling evoked to explain the O3 annual cycle in the same altitude range (Randel et al., 2007). Unless the 1.5 ppbv amplitude of N2O annual cycle in the upper troposphere is totally wrong, the explanation of the observed N2O annual cycle of 15 ppbv in the lower stratosphere requires another mechanism. A possible candidate for that might be the existence of a downward time-averaged mass flux above specific regions, as shown by Sherwood (2000) over Indonesia, required for compensating the energy sink resulting from the deep overshooting of cold and heavy air at high altitude over intense convective areas. But, since global models do currently not capture this subsidence, it must be recognised that a full explanation of the observations cannot be provided for the moment. However, the coincidence of the peak contrast between the Western Pacific and Africa with the maximum overshooting volume in May reported by the Tropical Rainfall Measuring Mission (TRMM) Precipitation Radar, suggests a strong influence of deep convection on the chemical composition of the tropical lower stratosphere up to 500 K (21 km).
Clouds, photolysis and regional tropospheric ozone budgets

We use a three-dimensional chemical transport model to examine the shortwave radiative effects of clouds on the tropospheric ozone budget. In addition to looking at changes in global concentrations as previous studies have done, we examine changes in ozone chemical production and loss caused by clouds and how these vary in different parts of the troposphere. On a global scale, we find that clouds have a modest effect on ozone chemistry, but on a regional scale their role is much more significant, with the size of the response dependent on the region. The largest averaged changes in chemical budgets (±10–14%) are found in the marine troposphere, where cloud optical depths are high. We demonstrate that cloud effects are small on average in the middle troposphere because this is a transition region between reduction and enhancement in photolysis rates. We show that increases in boundary layer ozone due to clouds are driven by large-scale changes in downward ozone transport from higher in the troposphere rather than by decreases in in-situ ozone chemical loss rates. Increases in upper tropospheric ozone are caused by higher production rates due to backscattering of radiation and consequent increases in photolysis rates, mainly J(NO2). The global radiative effect of clouds on isoprene, through decreases of OH in the lower troposphere, is stronger than on ozone. Tropospheric isoprene lifetime increases by 7% when taking clouds into account. We compare the importance of clouds in contributing to uncertainties in the global ozone budget with the role of other radiatively-important factors. The budget is most sensitive to the overhead ozone column, while surface albedo and clouds have smaller effects. However, uncertainty in representing the spatial distribution of clouds may lead to a large sensitivity of the ozone budget components on regional scales.
Aerosol characterization in Northern Africa, Northeastern Atlantic, Mediterranean Basin and Middle East from direct-sun AERONET observations

We provide an atmospheric aerosol characterization for North Africa, Northeastern Atlantic, Mediterranean and Middle East based on the analysis of quality-assured direct-sun observations of 39 stations of the AErosol RObotic NETwork (AERONET) which include at least an annual cycle within the 1994–2007 period. We extensively test and apply the recently introduced graphical method of Gobbi and co-authors to track and discriminate different aerosol types and quantify the contribution of mineral dust. The method relies on the combined analysis of the Ångström exponent (α) and its spectral curvature δα. Plotting data in these coordinates allows to infer aerosol fine mode radius (Rf) and fractional contribution (η) to total Aerosol Optical Depth (AOD) and separate AOD growth due to fine-mode aerosol humidification and/or coagulation from AOD growth due to the increase in coarse particles or cloud contamination. Our results confirm the robustness of this graphical method. Large mineral dust is found to be the most important constituent in Northern Africa and Middle East. Under specific meteorological conditions, its transport to Southern Europe is observed from spring to autumn and decreasing with latitude. We observe "pure Saharan dust" conditions to show AOD>0.7 (ranging up to 5), α<0.3 and δα<0 corresponding to η<40% and (Rf)~0.13 μm. Small pollution particles are abundant in sites close to urban and industrial areas of Continental and Eastern Europe and Middle East, as well as, important contributions of biomass burning are observed in the sub-Sahel region in winter. These small aerosols are associated to AOD<1, α>1.5 and δα~−0.2 corresponding to η>70% and Rf~0.13 μm. Here, dust mixed with fine pollution aerosols shifts the observations to the region α<0.75, in which the fine mode contribution is less than 40%.
Observations of heterogeneous reactions between Asian pollution and mineral dust over the Eastern North Pacific during INTEX-B

In-situ airborne measurements of trace gases, aerosol size distributions, chemistry and optical properties were conducted over Mexico and the Eastern North Pacific during MILAGRO and INTEX-B. Heterogeneous reactions between secondary aerosol precursor gases and mineral dust lead to sequestration of sulfur, nitrogen and chlorine in the supermicrometer particulate size range. Simultaneous measurements of aerosol size distributions and weak-acid soluble calcium result in an estimate of 11 wt% of CaCO3 for Asian dust. During transport across the North Pacific, ~5–30% of the CaCO3 is converted to CaSO4 or Ca(NO3)2 with an additional ~4% consumed through reactions with HCl. The 1996 to 2008 record from the Mauna Loa Observatory confirm these findings, indicating that, on average, 19% of the CaCO3 has reacted to form CaSO4 and 7% has reacted to form Ca(NO3)2 and ~2% has reacted with HCl. In the nitrogen-oxide rich boundary layer near Mexico City up to 30% of the CaCO3 has reacted to form Ca(NO3)2 while an additional 8% has reacted with HCl. These heterogeneous reactions can result in a ~3% increase in dust solubility which has an insignificant effect on their optical properties compared to their variability in-situ. However, competition between supermicrometer dust and submicrometer primary aerosol for condensing secondary aerosol species led to a 25% smaller number median diameter for the accumulation mode aerosol. A 10–25% reduction of accumulation mode number median diameter results in a 30–70% reduction in submicrometer light scattering at relative humidities in the 80–95% range. At 80% RH submicrometer light scattering is only reduced ~3% due to a higher mass fraction of hydrophobic refractory components in the dust-affected accumulation mode aerosol. Thus reducing the geometric mean diameter of the submicrometer aerosol has a much larger effect on aerosol optical properties than changes to the hygroscopic:hydrophobic mass fractions of the accumulation mode aerosol. In the presence of dust, nitric acid concentrations are reduced to <50% of total nitrate (nitric acid plus particulate nitrate). NOy as a fraction of total nitrogen (NOy plus particulate nitrate), is reduced from >85% to 60–80% in the presence of dust. These observations support previous model studies which predict irreversible sequestration of reactive nitrogen species through heterogeneous reactions with mineral dust during long-range transport.
Satellite measurements of formaldehyde linked to shipping emissions

International shipping is recognized as a pollution source of growing importance, in particular in the remote marine boundary layer. Nitrogen dioxide originating from ship emissions has previously been detected in satellite measurements. This study presents the first satellite measurements of formaldehyde (HCHO) linked to shipping emissions as derived from observations made by the Global Ozone Monitoring Experiment (GOME) instrument. We analyzed enhanced HCHO tropospheric columns from shipping emissions over the Indian Ocean between Sri Lanka and Sumatra. This region offers good conditions in term of plume detection with the GOME instrument as all ship tracks follow a single narrow track in the same east-west direction as used for the GOME pixel scanning. The HCHO signal alone is weak but could be clearly seen in the high-pass filtered data. The line of enhanced HCHO in the Indian Ocean as seen in the 7-year composite of cloud free GOME observations clearly coincides with the distinct ship track corridor from Sri Lanka to Indonesia. The observed mean HCHO column enhancement over this shipping route is about 2.0×1015 molec/cm2. Compared to the simultaneously observed NO2 values over the shipping route, those of HCHO are substantially higher; also the HCHO peaks are found at larger distance from the ship routes. These findings indicate that direct emissions of HCHO or degradation of emitted NMHC cannot explain the observed enhanced HCHO values. One possible reason might be increased CH4 degradation due to enhanced OH concentrations related to the ship emissions, but this source is probably too weak to fully explain the observed values. The observed HCHO pattern also agrees qualitatively well with results from the coupled earth system model ECHAM5/MESSy applied to atmospheric chemistry (EMAC). However, the modelled HCHO values over the ship corridor are two times lower than in the GOME high-pass filtered data. This might indicate uncertainties in the satellite data and used emission inventories and/or that the in-plume chemistry taking place in the narrow path of the shipping lanes are not well represented at the rather coarse model resolution.
Direct measurements of the effect of biomass burning over the Amazon on the atmospheric temperature profile

Aerosols suspended in the atmosphere interact with solar radiation and clouds, thus change the radiation energy fluxes in the atmospheric column. In this paper we measure changes in the atmospheric temperature profile as a function of the smoke loading and the cloudiness, over the Amazon basin, during the dry seasons (August and September) of 2005–2008. We show that as the aerosol optical depth (AOD) increases from 0.02 to a value of ~0.6, there is a decrease of ~4°C at 1000 hPa, and an increase of ~1.5°C at 850 hPa. The warming of the aerosol layer at 850 hPa is likely due to aerosol absorption when the particles are exposed to direct illumination by the sun. The large values of cooling in the lower layers could be explained by a combination of aerosol extinction of the solar flux in the layers aloft together with an aerosol-induced increase of cloud cover which shade the lower atmosphere. We estimate that the increase in cloud fraction due to aerosol contributes about half of the observed cooling in the lower layers.
Nitric acid and particulate matter measurements at Athens, Greece, in connection with corrosion studies

For a long time, scientists have been concerned about the effects of air pollution on materials and especially on the monuments of the cultural heritage. The EU funded a project, entitled MULTI-ASSESS, to determine these effects and to develop dose-response functions appropriate for the new multi-pollutant environment. The University of Athens participated in this effort as a targeted field exposure test site. In the present paper, the measurements of the passive samplers, which were exposed during the same period with the samples for corrosion studies, at the Athens station, are presented. The results have shown that only 16.5% of the deposited mass was water soluble. The vertical distribution of passive particle collectors has led to the conclusion that the height of maximum deposition of each ion is different. In addition, a variation of the water-soluble mass to total deposited mass between 8% and 31% was observed.
Eddy covariance methane measurements at a Ponderosa pine plantation in California

Long term methane flux measurements have been mostly performed with plant or soil enclosure techniques on specific components of an ecosystem. New fast response methane analyzers make it possible to use the eddy covariance (EC) technique instead. The EC technique is advantageous because it allows continuous flux measurements integrating over a larger and more representative area including the complete ecosystem, and allows fluxes to be observed as environmental conditions change naturally without disturbance. We deployed the closed-path Fast Methane analyzer (FMA) from Los Gatos Research Ltd and demonstrate its performance for EC measurements at a Ponderosa pine plantation at the Blodgett Forest site in central California. The fluctuations of the CH4 concentration measured at 10 Hz appear to be small and their standard deviation is comparable to the magnitude of the signal noise (±5 ppbv). Consequently, the power spectra typically have a white noise signature at the high frequency end (a slope of +1). Nevertheless, in the frequency range important for turbulent exchange, the cospectra of CH4 compare very well with all other scalar cospectra confirming the quality of the FMA measurements are good for the EC technique. We furthermore evaluate the complications of combined open and closed-path measurements when applying the Webb-Pearman-Leuning (WPL) corrections (Webb et al., 1980) and the consequences of a phase lag between the water vapor and methane signal inside the closed path system. The results of diurnal variations of CH4 concentrations and fluxes are summarized and compared to the monthly results of process-based model calculations.
Toward a general parameterization of N2O5 reactivity on aqueous particles: the competing effects of particle liquid water, nitrate and chloride

The heterogeneous reaction of N2O5 on mixed organic-inorganic aerosol particles was investigated using an entrained aerosol flow tube coupled to a custom-built chemical ionization mass spectrometer. Laboratory results on aqueous particles confirm a strong dependence of the reactive uptake coefficient (γ) on particle liquid water, for particle water concentrations below 15 M, and the molar ratio of particle water to nitrate. Measurements of γ (N2O5) on mixed chloride-nitrate particles indicate that the presence of trace chloride can negate the suppression of γ(N2O5) at high nitrate loadings with implications for polluted coastal regions. These results are used to construct a new parameterization for γ (N2O5), that when coupled to an aerosol thermodynamics model, can be used within regional and/or global chemical transport models.
VOC measurements within a boreal forest during spring 2005: on the occurrence of elevated monoterpene concentrations during night time intense particle concentration events

In this study we present measurements of selected trace gases and aerosols made in a boreal forest during the BACCI-QUEST IV intensive field campaign in Hyytiälä, Finland in April 2005. Springtime diel and vertical variations of VOCs are discussed in connection with the variations in other trace gases and with the prevailing meteorological conditions. A daytime and a nighttime event have been analysed in detail. The nighttime particle event occurred synchronously with huge increases in monoterpenes, while the second event type involved nucleation and was anti-correlated with sulphuric acid. Here we discuss the possible origins of these two distinct forms of aerosol production at the Hyytiälä site using the measurement data, air mass back trajectories and the optical stereoisomery of monoterpenes. Optical stereoisomery is used in source identification to distinguish between unnatural and natural monoterpene emissions.