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The continuing increase in demand for commercial aviation transport raises questions about the effects of resulting emissions on the environment. The purpose of this study is to investigate, using a global chemistry transport model, to what extent aviation emissions outside the boundary layer influence air quality in the boundary layer. The large-scale effects of current levels of aircraft emissions were studied through comparison of multiple simulations allowing for the separated effects of aviation emissions occurring in the low, middle and upper troposphere. We show that emissions near cruise altitudes (9–11 km in altitude) rather than emissions during landing and take-off are responsible for most of the total odd-nitrogen (NO<sub>y</sub>), ozone (O<sub>3</sub>) and aerosol perturbations near the ground with a noticeable seasonal difference. Overall, the perturbations of these species are smaller than 1 ppb even in winter when the perturbations are greater than in summer. Based on the widely used air quality standards and uncertainty of state-of-the-art models, we conclude that aviation-induced perturbations have a negligible effect on air quality even in areas with heavy air traffic. Aviation emissions lead to a less than 1% aerosol enhancement in the boundary layer due to a slight increase in ammonium nitrate (NH<sub>4</sub>NO<sub>3</sub>) during cold seasons and a statistically insignificant aerosol perturbation in summer. In addition, statistical analysis using probability density functions, Hellinger distance, and <i>p</i> value indicate that aviation emissions outside the boundary layer do not affect the occurrence of extremely high aerosol concentrations in the boundary layer. An additional sensitivity simulation assuming the doubling of surface ammonia emissions demonstrates that the aviation induced aerosol increase near the ground is highly dependent on background ammonia concentrations whose current range of uncertainty is large.
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The MIRAGE-Shanghai experiment was designed to characterize the factors controlling regional air pollution near a Chinese megacity (Shanghai) and was conducted during September 2009. This paper provides information on the measurements conducted for this study. In order to have some deep analysis of the measurements, a regional chemical/dynamical model (version 3 of Weather Research and Forecasting Chemical model – WRF-Chemv3) is applied for this study. The model results are intensively compared with the measurements to evaluate the model capability for calculating air pollutants in the Shanghai region, especially the chemical species related to ozone formation. The results show that the model is able to calculate the general distributions (the level and the variability) of air pollutants in the Shanghai region, and the differences between the model calculation and the measurement are mostly smaller than 30%, except the calculations of HONO (nitrous acid) at PD (Pudong) and CO (carbon monoxide) at DT (Dongtan). <br><br> The main scientific focus is the study of ozone chemical formation not only in the urban area, but also on a regional scale of the surrounding area of Shanghai. The results show that during the experiment period, the ozone photochemical formation was strongly under the VOC (volatile organic compound)-limited condition in the urban area of Shanghai. Moreover, the VOC-limited condition occurred not only in the city, but also in the larger regional area. There was a continuous enhancement of ozone concentrations in the downwind of the megacity of Shanghai, resulting in a significant enhancement of ozone concentrations in a very large regional area in the surrounding region of Shanghai. The sensitivity study of the model suggests that there is a threshold value for switching from VOC-limited condition to NO<sub>x</sub> (nitric oxide and nitrogen dioxide)-limited condition. The threshold value is strongly dependent on the emission ratio of NO<sub>x</sub> / VOCs. When the ratio is about 0.4, the Shanghai region is under a strong VOC-limited condition over the regional scale. In contrast, when the ratio is reduced to about 0.1, the Shanghai region is under a strong NO<sub>x</sub>-limited condition. The estimated threshold value (on the regional scale) for switching from VOC-limited to NO<sub>x</sub>-limited condition ranges from 0.1 to 0.2. This result has important implications for ozone production in this region and will facilitate the development of effective O<sub>3</sub> control strategies in the Shanghai region.
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Measurements carried out on the island of Lampedusa, in the central Mediterranean, on 7 September 2005, show the occurrence of a quasi-periodic oscillation of aerosol optical depth, column water vapour, and surface irradiance in different spectral bands. The oscillation has a period of about 13 min and is attributed to the propagation of a gravity wave able to modify the vertical structure of the planetary boundary layer, as also confirmed by satellite images. The wave occurred during a Saharan dust event. The oscillation amplitude is about 0.1 for the aerosol optical depth, and about 0.4 cm for the column water vapour. The modulation of the downward surface irradiances is in opposition of phase with respect to aerosol optical depth and water vapour column variations. The perturbation of the downward irradiance produced by the aerosols is determined by comparing the measured irradiances with estimated irradiances at a fixed value of the aerosol optical depth, and by correcting for the effect of the water vapour in the shortwave spectral range. The direct radiative forcing efficiency, i.e., the radiative perturbation of the net surface irradiance produced by a unit of optical depth aerosol layer, is determined at different solar zenith angles as the slope of the irradiance perturbation versus the aerosol optical depth. The estimated direct surface forcing efficiency at about 60° solar zenith angle is −(181 ± 17) W m<sup>−2</sup> in the shortwave, and −(83 ± 7) W m<sup>−2</sup> in the photosynthetic spectral range. The estimated daily average forcing efficiencies are of about −79 and −46 W m<sup>−2</sup> for the shortwave and photosynthetic spectral range, respectively.
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Trade wind cumulus clouds often organize in along-wind cloud streets and across-wind mesoscale arcs. We present a benchmark large-eddy simulation which resolves the individual clouds as well as the mesoscale organization on scales of O(10 km). Different methods to quantify organization of cloud fields are applied and discussed. Using perturbed physics large-eddy simulation experiments, the processes leading to the formation of cloud clusters and the mesoscale arcs are revealed. We find that both cold pools as well as the sub-cloud layer moisture field are crucial to understand the organization of precipitating shallow convection. Further sensitivity studies show that microphysical assumptions can have a pronounced impact on the onset of cloud organization.
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The ozonolysis of alkenes is considered to be an important source of atmospheric peroxides, which serve as oxidants, reservoirs of HO<sub>x</sub> radicals, and components of secondary organic aerosols (SOAs). Recent laboratory investigations of this reaction identified hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) and hydroxymethyl hydroperoxide (HMHP) in ozonolysis of isoprene. Although larger hydroxyalkyl hydroperoxides (HAHPs) were also expected, their presence is not currently supported by experimental evidence. In the present study, we investigated the formation of peroxides in the gas phase ozonolysis of isoprene at various relative humidities on a time scale of tens of seconds, using a quartz flow tube reactor coupled with the online detection of peroxides. We detected a variety of conventional peroxides, including H<sub>2</sub>O<sub>2</sub>, HMHP, methyl hydroperoxide, bis-hydroxymethyl hydroperoxide, and ethyl hydroperoxide, and interestingly found three unknown peroxides. The molar yields of the conventional peroxides fell within the range of values provided in the literature. The three unknown peroxides had a combined molar yield of ~ 30% at 5% relative humidity (RH), which was comparable with that of the conventional peroxides. Unlike H<sub>2</sub>O<sub>2</sub> and HMHP, the molar yields of these three unknown peroxides were inversely related to the RH. On the basis of experimental kinetic and box model analysis, we tentatively assigned these unknown peroxides to C2−C4 HAHPs, which are produced by the reactions of different Criegee intermediates with water. Our study provides experimental evidence for the formation of large HAHPs in the ozonolysis of isoprene (one of the alkenes). These large HAHPs have a sufficiently long lifetime, estimated as tens of minutes, which allows them to become involved in atmospheric chemical processes, e.g., SOA formation and radical recycling.
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A regional haze episode occurred in the Beijing, Tianjin and Hebei province (BTH) area in the North China Plain (NCP) from 16 to 19 January 2010. Data were collected and analyzed during the time frame of 14 through 23 January 2010 to include the haze event. The increase of secondary inorganic pollutants (SO<sub>4</sub><sup>2−</sup>, NO<sub>3</sub><sup>−</sup>, NH<sub>4</sub><sup>+</sup>) in PM<sub>2.5</sub> was observed simultaneously at four sites, especially in the plain area of the BTH, which could be identified as a common characteristic of pollution haze in east China. The sulfate and nitrate in PM<sub>2.5</sub> were mainly formed through the heterogeneous reaction process in the urban area. The organic matter (OM) increased more significantly at the Chengde (CD) site than the other three sites in the plain area. The secondary organic aerosols only existed during haze days at CD but in both haze and non-haze days at the other three sites, which suggested the greater regional impact of secondary formation process during the haze episode. The secondary formation of aerosol was one important formation mechanism of haze. The strong temperature inversion and descending air motions in the planetary boundary layer (PBL) allowed pollutants to accumulate in a shallow layer. The weak surface wind speed produced high pollutants concentration within source regions. The accumulation of pollutants was one main factor in the haze formation. The enhanced southwest wind in the last period of this episode transported pollutants to the downwind area and expanded the regional scope of the haze.
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Simulations with the chemistry transport model CHIMERE are compared to measurements performed during the MEGAPOLI (Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation) summer campaign in the Greater Paris region in July 2009. The volatility-basis-set approach (VBS) is implemented into this model, taking into account the volatility of primary organic aerosol (POA) and the chemical aging of semi-volatile organic species. Organic aerosol is the main focus and is simulated with three different configurations with a modified treatment of POA volatility and modified secondary organic aerosol (SOA) formation schemes. In addition, two types of emission inventories are used as model input in order to test the uncertainty related to the emissions. Predictions of basic meteorological parameters and primary and secondary pollutant concentrations are evaluated, and four pollution regimes are defined according to the air mass origin. Primary pollutants are generally overestimated, while ozone is consistent with observations. Sulfate is generally overestimated, while ammonium and nitrate levels are well simulated with the refined emission data set. As expected, the simulation with non-volatile POA and a single-step SOA formation mechanism largely overestimates POA and underestimates SOA. Simulation of organic aerosol with the VBS approach taking into account the aging of semi-volatile organic compounds (SVOC) shows the best correlation with measurements. High-concentration events observed mostly after long-range transport are well reproduced by the model. Depending on the emission inventory used, simulated POA levels are either reasonable or underestimated, while SOA levels tend to be overestimated. Several uncertainties related to the VBS scheme (POA volatility, SOA yields, the aging parameterization), to emission input data, and to simulated OH levels can be responsible for this behavior. Despite these uncertainties, the implementation of the VBS scheme into the CHIMERE model allowed for much more realistic organic aerosol simulations for Paris during summertime. The advection of SOA from outside Paris is mostly responsible for the highest OA concentration levels. During advection of polluted air masses from northeast (Benelux and Central Europe), simulations indicate high levels of both anthropogenic and biogenic SOA fractions, while biogenic SOA dominates during periods with advection from Southern France and Spain.
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Peroxy radicals were measured by a PeRCA (Peroxy Radical Chemical Amplifier) instrument in the boundary layer during the DOMINO (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) campaign at a coastal, forested site influenced by urban-industrial emissions in southern Spain in late autumn. Total peroxy radicals (RO<sub>2</sub>* = HO<sub>2</sub> + ΣRO<sub>2</sub>) generally showed a daylight maximum between 10 and 50 pptv at 13:00 UTC, with an average of 18 pptv over the 15 days of measurements. Emissions from the industrial area of Huelva often impacted the measurement site at night during the campaign. The processing of significant levels of anthropogenic organics leads to an intense nocturnal radical chemistry accompanied by formation of organic peroxy radicals at comparable levels to those of summer photochemical conditions with peak events up to 60–80 pptv. The RO<sub>2</sub> production initiated by reactions of NO<sub>3</sub> with organic trace gases was estimated to be significant, but not sufficient to account for the concentrations of RO<sub>2</sub>* observed in air masses carrying high pollutant loading. The nocturnal production of peroxy radicals in those periods seems therefore to be dominated by ozonolysis of volatile organic compounds, in particular alkenes of industrial petrochemical origin. <br><br> RO<sub>2</sub>* diurnal variations were consistent with HO<sub>2</sub> measurements available at the site. HO<sub>2</sub>/RO<sub>2</sub>* ratios generally varied between 0.3 and 0.6, though on some occasions this ratio was likely to have been affected by instrumental artifacts (overestimated HO<sub>2</sub>) associated with high RO<sub>2</sub> loads.
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The photo-oxidation chemistry of isoprene (ISOP; C<sub>5</sub>H<sub>8</sub>) was studied in a continuous-flow chamber under conditions such that the reactions of the isoprene-derived peroxyl radicals (RO<sub>2</sub>) were dominated by the hydroperoxyl (HO<sub>2</sub>) pathway. A proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS) with switchable H<sub>3</sub>O<sup>+</sup> and NO<sup>+</sup> reagent ions was used for product analysis. The products methyl vinyl ketone (MVK; C<sub>4</sub>H<sub>6</sub>O) and methacrolein (MACR; C<sub>4</sub>H<sub>6</sub>O) were differentiated using NO<sup>+</sup> reagent ions. The MVK and MACR yields via the HO<sub>2</sub> pathway were (3.8 ± 1.3)% and (2.5 ± 0.9)%, respectively, at +25 °C and < 2% relative humidity. The respective yields were (41.4 ± 5.5)% and (29.6 ± 4.2)% via the NO pathway. Production of MVK and MACR via the HO<sub>2</sub> pathway implies concomitant production of hydroxyl ((6.3 ± 2.1)%) and hydroperoxyl ((6.3 ± 2.1)%) radicals, meaning a HO<sub>x</sub> recycling of (12.6 ± 4.2)% given that HO<sub>2</sub> was both a reactant and product. Other isoprene oxidation products, believed to be mostly organic hydroperoxides, also contributed to the ion intensity at the same mass-to-charge (<i>m/z</i>) ratios as the MVK and MACR product ions for HO<sub>2</sub>-dominant conditions. These products were selectively removed from the gas phase by placement of a cold trap (−40 °C) inline prior to the PTR-TOF-MS. When incorporated into regional and global chemical transport models, the yields of MVK and MACR and the concomitant HO<sub>x</sub> recycling reported in this study can improve the accuracy of the simulation of the HO<sub>2</sub> reaction pathway of isoprene, which is believed to be the fate of approximately half of atmospherically produced isoprene-derived peroxy radicals on a global scale.
