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The electron-excited chemistry of sulfur dioxide oxidation induced by UV irradiation of air with trace O<sub>3</sub> and SO<sub>2</sub> is considered. The importance of this mechanism is evaluated based on recent laboratory experiments on SO<sub>2</sub> oxidation in a laminar tube with air induced by UV irradiation. Results show that under respective conditions the route of SO<sub>2</sub> oxidation involving electron excited oxygen molecules may present an additional source of gaseous H<sub>2</sub>SO<sub>4</sub> production to known OH-radical mechanism.
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Much uncertainty in the value of the imaginary part of the refractive index of mineral dust contributes to uncertainty in the radiative effect of mineral dust in the atmosphere. A synthesis of optical, chemical and physical in-situ aircraft measurements from the DODO experiments during February and August 2006 are used to calculate the refractive index mineral dust encountered over West Africa. Radiative transfer modeling and measurements of broadband shortwave irradiance at a range of altitudes are used to test and validate these calculations for a specific dust event on 23 August 2006 over Mauritania. Two techniques are used to determine the refractive index: firstly a method combining measurements of scattering, absorption, size distributions and Mie code simulations, and secondly a method using composition measured on filter samples to apportion the content of internally mixed quartz, calcite and iron oxide-clay aggregates, where the iron oxide is represented by either hematite or goethite and clay by either illite or kaolinite. The imaginary part of the refractive index at 550 nm (<i>n</i><sub>i</sub><sup>550</sup>) is found to range between 0.0001 i to 0.0046 i, and where filter samples are available, agreement between methods is found depending on mineral combination assumed. The refractive indices are also found to agree well with AERONET data where comparisons are possible. <i>n</i><sub>i</sub><sup>550</sup> is found to vary with dust source, which is investigated with the NAME model for each case. The relationship between both size distribution and <i>n</i><sub>i</sub><sup>550</sup> on the accumulation mode single scattering albedo at 550 nm (ω<sub>0</sub><sup>550</sup>) are examined and size distribution is found to have no correlation to ω<sub>0</sub><sup>550</sup>, while <i>n</i><sub>i</sub><sup>550</sup> shows a strong linear relationship with ω<sub>0</sub><sup>550</sup>. Radiative transfer modeling was performed with different models (Mie-derived refractive indices, but also filter sampling composition assuming both internal and external mixing). Our calculations indicate that Mie-derived values of <i>n</i><sub>i</sub><sup>550</sup> and the externally mixed dust where the iron oxide-clay aggregate corresponds to the goethite-kaolinite combination result in the best agreement with irradiance measurements. The radiative effect of the dust is found to be very sensitive to the mineral combination (and hence refractive index) assumed, and to whether the dust is assumed to be internally or externally mixed.
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We identify solar cycle signals in 155 years of global sea level pressure (SLP) and sea surface temperature (SST) data using a multiple linear regression approach. In SLP we find in the North Pacific a statistically significant weakening of the Aleutian Low and a northward shift of the Hawaiian High in response to higher solar activity, confirming the results of previous authors using different techniques. We also find a weak but broad reduction in pressure across the equatorial Pacific. In SST we identify a weak El Niño-like pattern in the tropics for the 155 year period, unlike the strong La Niña-like signal found recently by some other authors. We show that the latter have been influenced by the technique of compositing data from peak years of the sunspot cycle because these years have often coincided with the negative phase of the ENSO cycle. Furthermore, the date of peak annual sunspot number (SSN) generally falls a year or more in advance of the broader maximum of the 11-year solar cycle so that analyses which incorporate data from all years represent more coherently the difference between periods of high and low solar activity on these timescales. We also find that studies of the solar signal in SST over the second half of the 20th century may alias as ENSO signal if this is not properly taken into account.
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Vertical number fluxes of aerosol particles and vertical fluxes of CO<sub>2</sub> were measured with the eddy covariance method at the top of a 53 m high tower in the Amazon rain forest as part of the LBA (The Large Scale Biosphere Atmosphere Experiment in Amazonia) experiment. The observed aerosol number fluxes included particles with sizes down to 10 nm in diameter. The measurements were carried out during the wet and dry season in 2008. In this study focus is on the dry season aerosol fluxes, with significant influence from biomass burning, and these are compared with aerosol fluxes measured during the wet season. <br><br> Net particle deposition fluxes dominated in daytime in both seasons and the deposition flux was considerably larger in the dry season due to the much higher dry season particle concentration. The particle transfer velocity increased linearly with increasing friction velocity in both seasons. The difference in transfer velocity between the two seasons was small, indicating that the seasonal change in aerosol number size distribution is not enough for causing any significant change in deposition velocity. In general, particle transfer velocities in this study are low compared to studies over boreal forests. The reasons are probably the high percentage of accumulation mode particles and the low percentage of nucleation mode particles in the Amazon boundary layer, both in the dry and wet season, and low wind speeds in the tropics compared to the midlatitudes. <br><br> In the dry season, nocturnal particle fluxes behaved very similar to the nocturnal CO<sub>2</sub> fluxes. Throughout the night, the measured particle flux at the top of the tower was close to zero, but early in the morning there was an upward particle flux peak that is not likely a result of entrainment or local pollution. It is possible that these morning upward particle fluxes are associated with emission of primary biogenic particles from the rain forest. Emitted particles may be stored within the canopy during stable conditions at nighttime, similarly to CO<sub>2</sub>, and being released from the canopy when conditions become more turbulent in the morning.
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To elaborate stratospheric ozone depletion processes, measurements of diffusion coefficients of selected gas phase molecules (i.e. HCl, CH<sub>3</sub>OH, HCOOH and CH<sub>3</sub>COOH; Katsambas et al., 1997; Kondratyev and Varotsos, 1996; Varotsos et al., 1994, 1995) in ice in the temperature range 170–195 K have been analyzed with respect to the mechanisms and rates of diffusion. It is argued that the diffusion in ice of these compounds is governed by a vacancy – mediated mechanism, i.e. H<sub>2</sub>O vacancies are required to diffuse to lattice sites adjacent to these compounds prior to the diffusion of the corresponding molecule into the vacancy sites. In addition, we show that the diffusion coefficients of these compounds exhibit a specific interconnection, i.e. a linear relationship holds between the logarithm of the pre-exponential factor, <i>D</i><sub>o</sub>, and the activation energy <i>E</i>. The physical meaning of this interconnection is discussed.
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An inverse model using atmospheric CO<sub>2</sub> observations from a European network of stations to reconstruct daily CO<sub>2</sub> fluxes and their uncertainties over Europe at 50 km resolution has been developed within a Bayesian framework. We use the pseudo-data approach in which we try to recover known fluxes using a range of perturbations to the input. In this study, the focus is put on the sensitivity of flux accuracy to the inverse setup, varying the prior flux errors, the pseudo-data errors and the network of stations. We show that, under a range of assumptions about prior error and data error we can recover fluxes reliably at the scale of 1000 km and 10 days. At smaller scales the performance is highly sensitive to details of the inverse set-up. The use of temporal correlations in the flux domain appears to be of the same importance as the spatial correlations. We also note that the use of simple, isotropic correlations on the prior flux errors is more reliable than the use of apparently physically-based errors. Finally, increasing the European atmospheric network density improves the area with significant error reduction in the flux retrieval.
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We introduce a global-to-regional nesting scheme for atmospheric transport models used in simulating concentrations of green house gases from globally distributed surface fluxes. The coupled system of the regional Stochastic Time-Inverted Lagrangian Transport (STILT) model and the global atmospheric transport model (TM3) is designed to resolve atmospheric trace gas concentrations at high temporal and spatial resolutions in a specified domain e.g. for regional inverse applications. The nesting technique used for the coupling is based on a decomposition of the atmospheric concentration signal into a far-field and a near-field contribution enabling the usage of different model types for global (Eulerian) and regional (Lagrangian) scales. For illustrating the performance of the coupled TM3-STILT system we compare simulated mixing ratios of carbon dioxide with available observations at 10 sites in Europe. For all chosen sites the TM3-STILT provided higher correlations between the modelled and the measured time series than the TM3 global model. Autocorrelation analysis demonstrated that the TM3-STILT model captured temporal variability of measured tracer concentrations better than TM3 at most sites.
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We study the impact of temporal and spatial resolution and changes in modelled meteorological winds in the context of diffusive ensemble Lagrangian reconstructions. In situ tracer measurements are modelled based on coarse resolution global 3-D tracer distributions from a chemistry-transport model and on different time series of meteorological wind fields including a special set of 1-hourly analysed winds which is compared with 3 and 6-hourly operational analysed winds and with 3-hourly ERA-interim reanalysis. Increasing the time resolution of the advecting winds from three to one hour using the operational winds provides an improvement on diffusive reconstructions in the period studied but smaller than that obtained from six to three hours. The positive impact of using 1-hourly winds is similar to that obtained using ERA-Interim 3-hourly winds instead of the 3-hourly ECMWF operational analysis for the same period. This study sets out a technique to quantify differences in time series of meteorological wind fields here applied to assess the optimal space and time resolutions for ensemble Lagrangian reconstructions in the lower stratosphere.
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Aerosol particles in the submicrometer size range (PM<sub>1</sub>) have serious impacts on human health and climate. This work aims at studying the processes relevant for physical particle properties in and downwind Copenhagen and evaluating the capability of a detailed aerosol dynamics and chemistry model (ADCHEM) to describe the submicrometer aerosol dynamics in a complex urbanized region, subjected to a variety of important anthropogenic sources. The study area is the Oresund Region with Copenhagen (about 1.8 million people) as the major city, including the strait separating Denmark and Sweden with intense ship traffic. Modeled aerosol particle number size distributions and NO<sub>x</sub> concentrations are evaluated against ground-based measurements from two stations in the Copenhagen area in Denmark and one station in southern Sweden. <br><br> The measured and modeled increments in NO<sub>x</sub> concentrations from rural background to the urban area showed satisfactory agreement, indicating that the estimated NO<sub>x</sub> emissions and modeled atmospheric dispersion are reasonable. For three out of five case studies, the modeled particle number concentrations and size distributions are in satisfactory agreement with the measurements at all stations along the trajectories. For the remaining cases the model significantly underestimates the particle number concentration over Copenhagen, but reaches acceptable agreement with the measurements at the downwind background station in Sweden. The major causes for this were identified as being the lack of spatial resolution in the meteorological data in describing boundary layer mixing heights and the uncertainty in the exact air mass trajectory path over Copenhagen. In addition, particle emission factors may also have been too low. It was shown that aerosol dynamics play a minor role from upwind to urban background, but are important 1–2 h downwind the city. Real-world size-resolved traffic number emission factors which take into account the initial ageing in the street canyon can be used to model traffic emissions in urban plume studies.
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Results from a measurement study performed in the Tropical Atlantic on board the RHaMBLe Discovery Cruise D319 are presented. Measurements of aerosol composition, hygroscopicity and CCN activity were used to test the ability of a single parameter model to describe water uptake in sub- and supersaturated conditions. <br><br> It was found that the magnitude and temporal variability of the sub-saturated water uptake could be well represented using the non-refractory composition to derive the model input for 2 periods when the large majority of the aerosol mass was non-refractory. As may be expected, when a significant fraction of the aerosol volume is refractory the sub-saturated water uptake is not well predicted by the non-refractory composition. When predicting the cloud activation potential from the composition and the hygroscopicity there is a consistent under-prediction of the CCN activity. The prediction of CCN activity from the sub-saturated water uptake gives a better prediction of the CCN activity than the composition when the non-refractory components are not fully representative of the aerosol composition. <br><br> Based on these observations it appears that a single parameter cannot always capture the behavior fully across the sub- and supersaturated regimes. Measurements made at relative humidities (RHs) up to 94% showed that the water activity appears satisfactorily represented by a single parameter derived at 90% RH. It therefore appears that the change in the observed hygroscopicity take place between 94% RH and the point of activation. This change may be due in part to a change solution non-ideality, surface tension effects or the presence of sparingly soluble compounds for example, but cannot be reconciled without measurements at higher RHs.
