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As part of Campaigns of Air Quality Research in Beijing and Surrounding Region-2008 (CAREBeijing-2008), an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed in urban Beijing to characterize submicron aerosol particles during the time of 2008 Beijing Olympic Games and Paralympic Games (24 July to 20 September 2008). The campaign mean PM<sub>1</sub> mass concentration was 63.1 ± 39.8 μg m<sup>−3</sup>; the mean composition consisted of organics (37.9%), sulfate (26.7%), ammonium (15.9%), nitrate (15.8%), black carbon (3.1%), and chloride (0.87%). The average size distributions of the species (except BC) were all dominated by an accumulation mode peaking at about 600 nm in vacuum aerodynamic diameter, and organics was characterized by an additional smaller mode extending below 100 nm. Positive Matrix Factorization (PMF) analysis of the high resolution organic mass spectral dataset differentiated the organic aerosol into four components, i.e., hydrocarbon-like (HOA), cooking-related (COA), and two oxygenated organic aerosols (OOA-1 and OOA-2), which on average accounted for 18.1, 24.4, 33.7 and 23.7% of the total organic mass, respectively. The HOA was identified to be closely associated with primary combustion sources, while the COA mass spectrum and diurnal pattern showed similar characteristics to that measured for cooking emissions. The OOA components correspond to aged secondary organic aerosol. Although the two OOA components have similar elemental (O/C, H/C) compositions, they display differences in mass spectra and time series which appear to correlate with the different source regions sampled during the campaign. Back trajectory clustering analysis indicated that the southerly air flows were associated with the highest PM<sub>1</sub> pollution during the campaign. Aerosol particles in southern airmasses were especially rich in inorganic and oxidized organic species. Aerosol particles in northern airmasses contained a large fraction of primary HOA and COA species, probably due to stronger influences from local emissions. The lowest concentration levels for all major species were obtained during the Olympic game days (8 to 24 August 2008), possibly due to the effects of both strict emission controls and favorable meteorological conditions.
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A time-dependent map of radon-222 flux density at the Australian land surface has been constructed with a spatial resolution of 0.05° and temporal resolution of one month. Radon flux density was calculated from a simple model utilising data from national gamma-ray aerial surveys; modelled soil moisture, available from 1900 in near real-time; and maps of soil properties. The model was calibrated against a data set of accumulation chamber measurements, thereby constraining it with experimental data. A notable application of the map is in atmospheric mixing and transport studies which use radon as a tracer, where it is a clear improvement on the common assumption of uniform radon flux density.
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The resolution of regional chemical/dynamical models has important effects on the calculation of the distributions of air pollutants in urban areas. In this study, the sensitivity of air pollutants and photochemical ozone production to different model resolutions is assessed by applying a regional chemical/dynamical model (version 3 of Weather Research and Forecasting Chemical model – WRF-Chemv3) to the case of Mexico City. The model results with 3, 6, 12, and 24 km resolutions are compared to local surface measurements of CO, NO<sub>x</sub>, and O<sub>3</sub>. The study shows that the model resolutions of 3 and 6 km provide reasonable simulations of surface CO, NO<sub>x</sub>, and O<sub>3</sub> concentrations and of diurnal variations. The model tends to underestimate the measurements when the resolution is reduced to 12 km or less. The calculated surface CO, NO<sub>x</sub>, and O<sub>3</sub> concentrations at 24 km resolution are significantly lower than measured values. This study suggests that the ratio of the city size to the threshold resolution is 6 to 1, and that this ratio can be considered as a test value in other urban areas for model resolution setting. There are three major factors related to the effects of model resolution on the calculations of O<sub>3</sub> and O<sub>3</sub> precursors, including; (1) the calculated meteorological conditions, (2) the spatial distribution for the emissions of ozone precursors, and (3) the non-linearity in the photochemical ozone production. Model studies suggest that, for the calculations of O<sub>3</sub> and O<sub>3</sub> precursors, spatial resolutions (resulting from different meteorological condition and transport processes) have larger impacts than the effect of the resolution associated with emission inventories. The model shows that, with coarse resolution of emission inventory (24 km) and high resolution for meteorological conditions (6 km), the calculated CO and O<sub>3</sub> are considerably improved compared to the results obtained with coarse resolution for both emission inventory and meteorological conditions (24 km). The resolution of the surface emissions has important effects on the calculated concentration fields, but the effects are smaller than those resulting from the model resolution. This study also suggests that the effect of model resolution on O<sub>3</sub> precursors leads to important impacts on the photochemical formation of ozone. This results directly from the non-linear relationship between O<sub>3</sub> formation and O<sub>3</sub> precursor concentrations. Finally, this study suggests that, considering the balance between model performance and required computation time on current computers, the 6 km resolution is an optimal resolution for the calculation of ozone and its precursors in urban areas like Mexico City.
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Ten different approaches for applying lateral and top climatological boundary conditions for ozone have been evaluated using the off-line regional air-quality model AURAMS, driven with meteorology provided by the GEM weather-forecast model. All ten approaches employ the same climatological ozone profiles, but differ in the manner in which they are applied, via the inclusion or exclusion of (i) a dynamic adjustment of the climatological ozone profile in response to the model-predicted tropopause height, (ii) a sponge zone for ozone on the model top, (iii) upward extrapolation of the climatological ozone profile, and (iv) different mass consistency corrections. The model performance for each approach was evaluated against North American surface ozone and ozonesonde observations from the BAQS-Met field study period in the summer of 2007. The original daily one-hour maximum surface ozone biases of about +15 ppbv were greatly reduced (halved) in some simulations using alternative methodologies. However, comparisons to ozonesonde observations showed that the reduction in surface ozone bias sometimes came at the cost of significant positive biases in ozone concentrations in the free troposphere and upper troposphere. The best overall performance throughout the troposphere was achieved using a methodology that included dynamic tropopause height adjustment, no sponge zone at the model top, extrapolation of ozone when required above the limit of the climatology, and no mass consistency corrections (global mass conservation was still enforced). The simulation using this model version had a one-hour daily maximum surface ozone bias of +8.6 ppbv, with small reductions in model correlation, and the best comparison to ozonesonde profiles. This recommended and original methodologies were compared for two further case studies: a high-resolution simulation of the BAQS-Met measurement intensive, and a study of the downwind region of the Canadian Rockies. Significant improvements were noted for the high resolution simulations during the BAQS-Met measurement intensive period, both in formal statistical comparisons and time series comparisons of events at surface stations. The tests for the downwind-Rockies region showed that the coupling between vertical transport associated with troposphere/stratosphere exchange, and that associated with boundary layer turbulent mixing, may contribute to ozone positive biases. The results may be unique to the modelling setup employed, but the results also highlight the importance of evaluating boundary condition and mass consistency/correction algorithms against three-dimensional datasets.
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An improved method for the measurement of hydroperoxy radicals (HO<sub>2</sub>) and organic peroxy radicals (RO<sub>2</sub>, where R is any organic group) has been developed that combines two previous chemical conversion/chemical ionization mass spectrometry (CIMS) peroxy radical measurement techniques. Applicable to both ground-based and aircraft platforms, the method provides good separation between HO<sub>2</sub> and RO<sub>2</sub> and frequent measurement capability with observations of both HO<sub>2</sub> and HO<sub>2</sub> + RO<sub>2</sub> amounts each minute. This allows for analyses of measured [HO<sub>2</sub>]/[HO<sub>2</sub> + RO<sub>2</sub>] ratios on timescales relevant to tropospheric photochemistry. By varying both [NO] and [O<sub>2</sub>] simultaneously in the chemical conversion region of the PeRCIMS (Peroxy Radical CIMS) inlet, the method exploits the changing conversion efficiency of RO<sub>2</sub> to HO<sub>2</sub> under different inlet [NO]/[O<sub>2</sub>] to selectively observe either primarily HO<sub>2</sub> or the sum of HO<sub>2</sub> and RO<sub>2</sub>. Two modes of operation have been established for ambient measurements: in the first half of the minute, RO<sub>2</sub> radicals are measured at close to 100% efficiency along with HO<sub>2</sub> radicals (low [NO]/[O<sub>2</sub>] = 2.53 × 10<sup>−5</sup>) and in the second half of the minute, HO<sub>2</sub> is detected while the majority of ambient RO<sub>2</sub> radicals are measured with approximately 15% efficiency (high [NO]/[O<sub>2</sub>] = 6.80 × 10<sup>−4</sup>). The method has been tested extensively in the laboratory under various conditions and for a variety of organic peroxy radicals relevant to the atmosphere and the results of these tests are presented. The modified PeRCIMS instrument has been deployed successfully using the current measurement technique on a number of aircraft campaigns, including on the NSF/NCAR C-130 during the MIRAGE-Mex and NASA INTEX-B field campaigns in the spring of 2006. A brief comparison of the peroxy radical measurements during these campaigns to a photochemical box model confirms that the PeRCIMS is able to successfully separate and measure HO<sub>2</sub> and RO<sub>2</sub> under the majority of tropospheric conditions.
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Ambient samples of volatile organic compounds (VOCs) were measured between 2000 and 2007 in Southeastern Mexico City, quantifying 13 species (ethane, propane, propylene, butane, acetylene, pentane, hexane, heptane, benzene, octane, toluene, nonane, o-xylene). These time series were analyzed for long-term trends, using linear regression models. A main finding was that the concentrations for several VOC species were decreasing during this period. A receptor model was applied to identify possible VOC sources, as well as temporal patterns in their respective contributions. Domestic use of liquefied petroleum gas (LPG) and vehicle exhaust are suggested to be the principal emission sources, contributing together between 70% and 80% to the total of quantified species. Both diurnal and seasonal patterns, as well as a weekend effect were recognized in the modelled source contributions. Furthermore, decreasing trends over time were found for LPG and hot soak (−7.8% and −12.7% per year, respectively, <i>p</i> < 0.01), whereas for vehicle exhaust no significant trend was found.
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A series of laboratory experiments at the Fire Laboratory at Missoula (FLAME) investigated chemical, physical, and optical properties of fresh smoke samples from combustion of wildland fuels that are burned annually in the western and southeastern US The burns were conducted in the combustion chamber of the US Forest Service Fire Sciences Laboratory in Missoula, Montana. Here we discuss retrieval of optical properties for a variety of fuels burned in FLAME 2, using nephelometer-measured scattering coefficients, photoacoustically-measured aerosol absorption coefficients, and size distribution measurements. Uncertainties are estimated from various instrument characteristics and instrument calibration studies. Our estimates of single scattering albedo for different dry smoke samples varied from 0.428 to 0.990, indicative of observed wide variations in smoke aerosol chemical composition. In selected case studies, we retrieved the complex refractive index from measurements but show that these are highly sensitive to uncertainties in measured size distributions.
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Methylation reactions of gaseous elementary mercury by halogen containing molecules such as halogenomethane species CH<sub>3</sub>X (with X=Cl, Br and I) and the dimethylchlorinium ion CH<sub>3</sub>ClCH<sub>3</sub><sup>+</sup> were investigated at the DFT level. With CH<sub>3</sub>X, the reaction is predicted to be almost athermic and kinetically demanding for a thermal reaction. The reaction can proceed photochemically in the visible range; therefore sunlight may increase the reaction rate. These results compare well with the experimental data. Consecutive methylation of the CH<sub>3</sub>HgX products (with X=Cl, Br and I) and subsequent formation of CH<sub>3</sub>HgCH<sub>3</sub> were also studied. These reactions are predicted to be kinetically inaccessible and thermodynamically unfavorable. With CH<sub>3</sub>ClCH<sub>3</sub><sup>+</sup>, the reaction is predicted to be athermic but kinetically easy. This is due to the suitability of the methyl transfer reagent. Geometrical and electronic data were systematically analyzed in order to rationalize the results.
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This article, the fifth in the ACP journal series, presents data evaluated by the IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry. It covers the heterogeneous processes on surfaces of solid particles present in the atmosphere, for which uptake coefficients and adsorption parameters have been presented on the IUPAC website in 2010. The article consists of an introduction and guide to the evaluation, giving a unifying framework for parameterisation of atmospheric heterogeneous processes. We provide summary sheets containing the recommended uptake parameters for the evaluated processes. Four substantial appendices contain detailed data sheets for each process considered for ice, mineral dust, sulfuric acid hydrate and nitric acid hydrate surfaces, which provide information upon which the recommendations are made.
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