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Combustion of elemental carbon (EC) and organic carbon (OC) contained in ambient aerosol matter was explored using scanning electron microscopy (SEM) in combination with energy dispersive X-ray analysis (EDX). To ease identification of the particles of interest and to avoid or at least reduce interaction with simultaneously sampled inorganic oxides and salts, the approach used in this work differed in two ways from commonly applied procedures. First, rather than using a mixture of particles of vastly different sizes, as in PM10 or PM2.5, aerosol matter was collected in a 5-stage impactor. Second, the water soluble fraction of the collected matter was removed prior to analysis. Diesel soot particles, which appeared in the well-known form of chain-type aggregates, constituted the major fraction of EC. In contrast, OC containing particles were observed in a variety of shapes, including a sizable amount of bioaerosol matter appearing mostly in the size range above about 1 µm. During heating in ambient air for 1h, diesel soot particles were found to be stable up to 470°C, but complete combustion occurred in a narrow temperature interval between about 480 and 510°C. After diesel soot combustion, minute quantities of "ash" were observed in the form of aggregated tiny particles with sizes less than 10 nm. These particles could be due to elemental or oxidic contaminants of diesel soot. Combustion of OC was observed over a wide range of temperatures, from well below 200°C to at least 500°C. Incompletely burnt bioaerosol matter was still found after heating to 600°C. The results imply that the EC fraction in aerosol matter can be overestimated significantly if the contribution of OC to a thermogram is not well separated.
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Black carbon (BC) particles in the atmosphere have important impacts on climate. The amount of BC in the atmosphere must be carefully quantified to allow evaluation of the climate effects of this type of aerosol. In this study, we present the treatment of BC aerosol in the developmental version of the 4th generation Canadian Centre for Climate modelling and analysis (CCCma) atmospheric general circulation model (AGCM). The focus of this work is on the conversion of insoluble BC to soluble/mixed BC by physical and chemical ageing. Physical processes include the condensation of sulphuric and nitric acid onto the BC aerosol, and coagulation with more soluble aerosols such as sulphates and nitrates. Chemical processes that may age the BC aerosol include the oxidation of organic coatings by ozone. <P style="line-height: 20px;"> Four separate parameterizations of the ageing process are compared to a control simulation that assumes no ageing occurs. These simulations use 1) an exponential decay with a fixed 24h half-life, 2) a condensation and coagulation scheme, 3) an oxidative scheme, and 4) a linear combination of the latter two ageing treatments. Global BC burdens are 2.15, 0.15, 0.11, 0.21, and 0.11TgC for the control run, and four ageing schemes, respectively. The BC lifetimes are 98.1, 6.6, 5.0, 9.5, and 4.9 days, respectively. The sensitivity of modelled BC burdens, and concentrations to the factor of two uncertainty in the emissions inventory is shown to be greater than the sensitivity to the parameterization used to represent the BC ageing, except for the oxidation based parameterization. A computationally efficient parameterization that represents the processes of condensation, coagulation, and oxidation is shown to simulate BC ageing well in the CCCma AGCM. As opposed to the globally fixed ageing time scale, this treatment of BC ageing is responsive to varying atmospheric composition.
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Research during the past decades has outlined the importance of biogenic isoprene emission in tropospheric chemistry and regional ozone photo-oxidant pollution. The first part of this article focuses on the development and validation of a simple biogenic emission scheme designed for regional studies. Experimental data sets relative to Boreal, Tropical, Temperate and Mediterranean ecosystems are used to estimate the robustness of the scheme at the canopy scale, and over contrasted climatic and ecological conditions. A good agreement is generally found when comparing field measurements and simulated emission fluxes, encouraging us to consider the model suitable for regional application. Limitations of the scheme are nevertheless outlined as well as further on-going improvements. In the second part of the article, the emission scheme is used on line in the broader context of a meso-scale atmospheric chemistry model. Dynamically idealized simulations are carried out to study the chemical interactions of pollutant plumes with realistic isoprene emissions coming from a Mediterranean oak forest. Two types of anthropogenic sources, respectively representative of the Marseille (urban) and Martigues (industrial) French Mediterranean sites, and both characterized by different VOC/NOx are considered. For the Marseille scenario, the impact of biogenic emission on ozone production is larger when the forest is situated in a sub-urban configuration (i.e. downwind distance TOWN-FOREST <30km, considering an advection velocity of 4.2 m.s<sup>-1</sup>). In this case the enhancement of ozone production due to isoprene can reach +37% in term of maximum surface concentrations and +11% in term of total ozone production. The impact of biogenic emission decreases quite rapidly when the TOWN-FOREST distance increases. For the Martigues scenario, the biogenic impact on the plume is significant up to TOWN-FOREST distance of 90km where the ozone maximum surface concentration enhancement can still reach +30%. For both cases, the importance of the VOC/NO<sub>x</sub> ratio in the anthropogenic plume and its evolution when interacting with the forest emission are outlined. In complement to real case studies, this idealized approach can be particularly useful for process and sensitivity studies and constitutes a valuable tool to build regional ozone control strategies.
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Measurements of acetone, methanol, acetaldehyde and a range of non-methane hydrocarbons have been made in North Atlantic marine air at the Mace Head observatory. Under maritime conditions the combination of OVOCs (acetone, methanol and acetaldehyde) contributed up to 85% of the total mass of measured non methane organics in air and up to 80% of the OH radical organic sink, when compared with the sum of all other organic compounds including non-methane hydrocarbons, DMS and OH-reactive halocarbons (trichloromethane and tetrachloroethylene). The observations showed anomalies in the variance and abundance of acetaldehyde and acetone over that expected for species with a remote terrestrial emission source and OH controlled chemical lifetime. A detailed model incorporating an explicit chemical degradation mechanism indicated in situ formation during air mass transport was on timescales longer than the atmospheric lifetime of precursor hydrocarbons or primary emission. The period over which this process was significant was similar to that of airmass motion on intercontinental scales, and formation via this route may reproduce that of a widespread diffuse source. The model indicates that continued short chain OVOC formation occurs many days from the point of emission, via longer lived intermediates of oxidation such as organic peroxides and long chain alcohols.
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The potentiality of dust particles to mix with sulphate over Tropical Africa and the Atlantic Ocean is investigated by combining a meso-scale meteorological model with a dust production model and an SO<sub>2</sub> emission database. This mixing process study is based on a qualitative approach where the reactivity of dust is estimated from its calcite content, which is the main mineral known to be reactive with sulphur species. We are presenting a 1-month simulation (January 1993). Our results show that the regions Northern Egypt and Libya (NEL), Western Sahara (WS) and Sahel (S) are the major sources of dust plumes. The simulated dust loading is in agreement with the measured data close to the African coasts. The Mediterranean and Maghreb regions are highly influenced by European sources of sulphate, for which the simulated concentrations are consistent with the observed trends. This simplified study identifies two zones that favour the mixing process between dust and sulphate: 1. the Eastern Mediterranean basin due to the concomitance of high concentrations of dust and sulphate and 2. the North-Eastern Atlantic Ocean due to the high amount of calcite in the ejected dust which is very reactive. Thus, we assume that the coating process takes place mainly in these regions and the sulphate-coated dust found on the other side of the Atlantic Ocean (Caribbean and American coasts) is principally due to this phenomenon.
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While water insoluble organics are prevalent in the atmosphere, it is not clear how the presence of such species alters the chemical and physical properties of atmospheric aerosols. Here we use a combination of FTIR spectroscopy, Transmission Electron Microscopy (TEM) and Aerosol Mass Spectrometry (AMS) to characterize ammonium sulfate particles coated with palmitic acid. Coated aerosols were generated by atomizing pure ammonium sulfate, mixing the particles with a heated flow of nitrogen with palmitic acid vapor, and then flowing the mixture through an in-line oven to create internally mixed particles. The mixing state of the particles was probed using the AMS data and images from the TEM. Both of these probes suggest that the particles were internally mixed. Water uptake by the mixed particles was then probed at 273 K. It was found that for ammonium sulfate containing ~20 wt% palmitic acid the deliquescence relative humidity (DRH) was the same as for pure ammonium sulfate (80±3% RH). For particles with ~50 wt% palmitic acid however, the mixed particles began to take up water at relative humidities as low at 69% and continued to slowly take up water to 85% RH without fully deliquescing. In addition to studies of water uptake, water loss was also investigated. Here coatings of up to 50 wt% had no impact on the efflorescence relative humidity. These studies suggest that even if insoluble substances coat salt particles in the atmosphere, there may be relatively little effect on the resulting water uptake and loss.
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In September 2002, the first INSPECTRO campaign to study the influence of clouds on the spectral actinic flux in the lower troposphere was carried out in East Anglia, England. Measurements of the actinic flux, the irradiance and aerosol and cloud properties were made from four ground stations and by aircraft. The radiation measurements were modelled using the uvspec model and ancillary data. For cloudless conditions, the measurements of the actinic flux were reproduced by 1-D radiative transfer modelling within the measurement and model uncertainties of about ±10%. For overcast days, the ground-based and aircraft radiation measurements and the cloud microphysical property measurements are consistent within the framework of 1-D radiative transfer and within experimental uncertainties. Furthermore, the actinic flux is increased by between 60-100% above the cloud when compared to a cloudless sky, with the largest increase for the optically thickest cloud. Correspondingly, the below cloud actinic flux is decreased by about 55-65%. Just below the cloud top, the downwelling actinic flux has a maximum that is seen in both the measurements and the model results. For broken clouds the traditional cloud fraction approximation is not able to simultaneously reproduce the measured above-cloud enhancement and below-cloud reduction in the actinic flux.
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A multi-column radiative transfer code is used to assess the direct radiative effect of biomass burning aerosols over the southern African region during September. The horizontal distribution of biomass smoke is estimated from two sources; i) General Circulation Model (GCM) simulations combined with measurements from the Aerosol Robotic Network (AERONET) of Sun photometers; ii) data from the Moderate resolution Imaging Spectrometer (MODIS) satellite. Aircraft and satellite measurements are used to constrain the cloud fields, aerosol optical properties, vertical structure, and land surface albedo included in the model. The net regional direct effect of the biomass smoke is -3.1 to -3.6 Wm<sup>-2</sup> at the top of atmosphere, and -14.4 to -17.0 Wm<sup>-2</sup> at the surface for the MODIS and GCM distributions of aerosol. The direct radiative effect is shown to be highly sensitive to the prescribed vertical profiles and aerosol optical properties. The diurnal cycle of clouds and the spectral dependency of surface albedo are also shown to play an important role.
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A regression method was developed to retrieve upper tropospheric water vapor (UTWV in kg/m<sup>2</sup>) and upper tropospheric humidity (UTH in % <i>RH</i>) from radiances measured by the Advanced Microwave Sounding Unit (AMSU). In contrast to other UTH retrieval methods, UTH is defined as the average relative humidity between 500 and 200hPa, not as a Jacobian weighted average, which has the advantage that the UTH altitude does not depend on the atmospheric conditions. The method uses AMSU channels 6-10, 18, and 19, and should achieve an accuracy of 0.48 kg/m<sup>2</sup> for UTWV and 6.3% <i>RH</i> for UTH, according to a test against an independent synthetic data set. This performance was confirmed for northern mid-latitudes by a comparison against radiosonde data from station Lindenberg in Germany, which yielded errors of 0.23 kg/m<sup>2</sup> for UTWV and 6.1% <i>RH</i> for UTH.
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CO, CH<sub>4</sub>, N<sub>2</sub>O and CO<sub>2</sub> were retrieved from high resolution solar absorption spectra obtained during a ship cruise from Capetown to Bremerhaven in January/February 2003 by Fourier Transform Infrared (FTIR) spectroscopy. Precisions of better than 0.5% for the column averaged volume mixing ratios (VMR) of CH<sub>4</sub> and CO<sub>2</sub> are achieved using of O<sub>2</sub> as a reference gas. Shipborne FTIR-measurements of CO and data from SCIAMACHY/ENVISAT retrieved by the Weighting Function Modified Differential Optical Absorption Spectroscopy (WFM-DOAS) retrieval algorithm show qualitatively the same latitudinal variations. WFM-DOAS data of CH<sub>4</sub>, N<sub>2</sub>O and CO<sub>2</sub> measured over sea exhibit a great spread. The spread is significantly reduced for satellite measurements over land and a reasonable agreement can be obtained if the shipborne data are compared with the closest SCIAMACHY measurements over land. The number of comparisons is too small to draw conclusions. However, by including only WFM-DOAS data with small errors the shipborne and WFM-DOAS data compare within 5% for CH<sub>4</sub> and CO<sub>2</sub> and within 30% for N<sub>2</sub>O.
