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Global model simulations of air pollution during the 2003 European heat wave

Three global Chemistry Transport Models – MOZART, MOCAGE, and TM5 – as well as MOZART coupled to the IFS meteorological model including assimilation of ozone (O3) and carbon monoxide (CO) satellite column retrievals, have been compared to surface measurements and MOZAIC vertical profiles in the troposphere over Western/Central Europe for summer 2003. The models reproduce the meteorological features and enhancement of pollution during the period 2–14 August, but not fully the ozone and CO mixing ratios measured during that episode. Modified normalised mean biases are around −25% (except ~5% for MOCAGE) in the case of ozone and from −80% to −30% for CO in the boundary layer above Frankfurt. The coupling and assimilation of CO columns from MOPITT overcomes some of the deficiencies in the treatment of transport, chemistry and emissions in MOZART, reducing the negative biases to around 20%. The high reactivity and small dry deposition velocities in MOCAGE seem to be responsible for the overestimation of O3 in this model. Results from sensitivity simulations indicate that an increase of the horizontal resolution to around 1°×1° and potential uncertainties in European anthropogenic emissions or in long-range transport of pollution cannot completely account for the underestimation of CO and O3 found for most models. A process-oriented TM5 sensitivity simulation where soil wetness was reduced results in a decrease in dry deposition fluxes and a subsequent ozone increase larger than the ozone changes due to the previous sensitivity runs. However this latest simulation still underestimates ozone during the heat wave and overestimates it outside that period. Most probably, a combination of the mentioned factors together with underrepresented biogenic emissions in the models, uncertainties in the modelling of vertical/horizontal transport processes in the proximity of the boundary layer as well as limitations of the chemistry schemes are responsible for the underestimation of ozone (overestimation in the case of MOCAGE) and CO found in the models during this extreme pollution event.
The effect of Arctic sea-ice extent on the absorbed (net) solar flux at the surface, based on ISCCP-D2 cloud data for 1983–2007

We estimate the effect of the Arctic sea ice on the absorbed (net) solar flux using a radiative transfer model. Ice and cloud input data to the model come from satellite observations, processed by the International Satellite Cloud Climatology Project (ISCCP) and span the period July 1983–June 2007. The sea-ice effect on the solar radiation fluctuates seasonally with the solar flux and decreases interannually in synchronisation with the decreasing sea-ice extent. A disappearance of the Arctic ice cap during the sunlit period of the year would radically reduce the local albedo and cause an annually averaged 19.7 W m−2 increase in absorbed solar flux at the Arctic Ocean surface, or equivalently an annually averaged 0.55 W m−2 increase on the planetary scale. In the clear-sky scenario these numbers increase to 34.9 and 0.97 W m−2, respectively. A meltdown only in September, with all other months unaffected, increases the Arctic annually averaged solar absorption by 0.32 W m−2. We examined the net solar flux trends for the Arctic Ocean and found that the areas absorbing the solar flux more rapidly are the North Chukchi and Kara Seas, Baffin and Hudson Bays, and Davis Strait. The sensitivity of the Arctic absorbed solar flux on sea-ice extent and cloud amount was assessed. Although sea ice and cloud affect jointly the solar flux, we found little evidence of strong non-linearities.
Source attribution and interannual variability of Arctic pollution in spring constrained by aircraft (ARCTAS, ARCPAC) and satellite (AIRS) observations of carbon monoxide

We use aircraft observations of carbon monoxide (CO) from the NASA ARCTAS and NOAA ARCPAC campaigns in April 2008 together with multiyear (2003–2008) CO satellite data from the AIRS instrument and a global chemical transport model (GEOS-Chem) to better understand the sources, transport, and interannual variability of pollution in the Arctic in spring. Model simulation of the aircraft data gives best estimates of CO emissions in April 2008 of 26 Tg month−1 for Asian anthropogenic, 9.4 for European anthropogenic, 4.1 for North American anthropogenic, 15 for Russian biomass burning (anomalously large that year), and 23 for Southeast Asian biomass burning. We find that Asian anthropogenic emissions are the dominant source of Arctic CO pollution everywhere except in surface air where European anthropogenic emissions are of similar importance. Russian biomass burning makes little contribution to mean CO (reflecting the long CO lifetime) but makes a large contribution to CO variability in the form of combustion plumes. Analysis of two pollution events sampled by the aircraft demonstrates that AIRS can successfully observe pollution transport to the Arctic in the mid-troposphere. The 2003–2008 record of CO from AIRS shows that interannual variability averaged over the Arctic cap is very small. AIRS CO columns over Alaska are highly correlated with the Ocean Niño Index, suggesting a link between El Niño and Asian pollution transport to the Arctic. AIRS shows lower-than-average CO columns over Alaska during April 2008, despite the Russian fires, due to a weakened Aleutian Low hindering transport from Asia and associated with the moderate 2007–2008 La Niña. This suggests that Asian pollution influence over the Arctic may be particularly large under strong El Niño conditions.
Size-resolved aerosol water-soluble ionic compositions in the summer of Beijing: implication of regional secondary formation

To characterize aerosol pollution in Beijing, size-resolved aerosols were collected by MOUDIs during CAREBEIJING-2006 field campaign at Peking University (urban site) and Yufa (upwind rural site). Fine particle concentrations (PM1.8 by MOUDI) were 99.8±77.4 μg/m3 and 78.2±58.4 μg/m3, with PM1.8/PM10 ratios of 0.64±0.08 and 0.76±0.08 at PKU and Yufa, respectively, and secondary compounds accounted for more than 50% in fine particles. PMF model analysis was used to resolve the particle modes. Three modes were resolved at Yufa, representing condensation, droplet and coarse mode. However, one more droplet mode with bigger size was resolved, which was considered probably from regional transport. Condensation mode accounted for 10%–60% of the total mass at both sites, indicating that the gas-to-particle condensation process was important in summer. The formation of sulfate was mainly attributed to in-cloud or aerosol droplet process (PKU 80%, Yufa 70%) and gas condensation process (PKU 14%, Yufa 22%). According to the thermodynamic instability of NH4NO3, size distributions of nitrate were classified as three categories by RH. The existence of Ca(NO3)2 in droplet mode indicated the reaction of HNO3 with crustal particles was also important in fine particles. A rough estimation was given that 69% of the PM10 and 87% of the PM1.8 in Beijing urban were regional contributions. Sulfate, ammonium and oxalate were formed regionally, with the regional contributions of 90%, 87% and 95% to PM1.8. Nitrate formation was local dominant. In summary regional secondary formation led to aerosol pollution in the summer of Beijing.
Microscopic characterization of carbonaceous aerosol particle aging in the outflow from Mexico City

This study was part of the Megacities Initiative: Local and Global Research Observations (MILAGRO) field campaign conducted in Mexico City metropolitan area during spring 2006. The physical and chemical transformations of particles aged in the outflow from Mexico City were investigated for the transport event of 22 March 2006. A detailed chemical analysis of individual particles was performed using a combination of complementary microscopy and micro-spectroscopy techniques. The applied techniques included scanning transmission X-ray microscopy (STXM) coupled with near edge X-ray absorption fine structure spectroscopy (NEXAFS) and computer controlled scanning electron microscopy with an energy dispersive X-ray analyzer (CCSEM/EDX). As the aerosol plume evolves from the city center, the organic mass per particle increases and the fraction of carbon-carbon double bonds (associated with elemental carbon) decreases. Organic functional groups enhanced with particle age include: carboxylic acids, alkyl groups, and oxygen bonded alkyl groups. At the city center (T0) the most prevalent aerosol type contained inorganic species (composed of sulfur, nitrogen, oxygen, and potassium) coated with organic material. At the T1 and T2 sites, located northeast of T0 (~29 km and ~65 km, respectively), the fraction of homogenously mixed organic particles increased in both size and number. These observations illustrate the evolution of the physical mixing state and organic bonding in individual particles in a photochemically active environment.
Global estimates of CO sources with high resolution by adjoint inversion of multiple satellite datasets (MOPITT, AIRS, SCIAMACHY, TES)

We combine CO column measurements from the MOPITT, AIRS, SCIAMACHY, and TES satellite instruments in a full-year (May 2004–April 2005) global inversion of CO sources at 4°×5° spatial resolution and monthly temporal resolution. The inversion uses the GEOS-Chem chemical transport model (CTM) and its adjoint applied to MOPITT, AIRS, and SCIAMACHY. Observations from TES, surface sites (NOAA/GMD), and aircraft (MOZAIC) are used for evaluation of the a posteriori solution. Using GEOS-Chem as a common intercomparison platform shows global consistency between the different satellite datasets and with the in situ data. Differences can be largely explained by different averaging kernels and a priori information. The global CO emission from combustion as constrained in the inversion is 1350 Tg a−1. This is much higher than current bottom-up emission inventories. A large fraction of the correction results from a seasonal underestimate of CO sources at northern mid-latitudes in winter and suggests a larger-than-expected CO source from vehicle cold starts and residential heating. Implementing this seasonal variation of emissions solves the long-standing problem of models underestimating CO in the northern extratropics in winter-spring. A posteriori emissions also indicate a general underestimation of biomass burning in the GFED2 inventory. However, the tropical biomass burning constraints are not quantitatively consistent across the different datasets.
Secondary organic material formed by methylglyoxal in aqueous aerosol mimics

We show that methylglyoxal forms light-absorbing secondary organic material in aqueous ammonium sulfate and ammonium nitrate solutions mimicking tropospheric aerosol particles. The kinetics were characterized using UV-Vis spectrophotometry. The results suggest that the bimolecular reaction of methylglyoxal with an ammonium or hydronium ion is the rate-limiting step for the formation of light-absorbing species, with kNH4+II=5×10−6 M−1 min−1 and kH3O+II≤10−3 M−1 min−1. Evidence of aldol condensation products and oligomeric species up to 759 amu was found using chemical ionization mass spectrometry with a volatilization flow tube inlet (Aerosol-CIMS). Tentative identifications of carbon-nitrogen species and a sulfur-containing compound were also made using Aerosol-CIMS. Aqueous solutions of methylglyoxal, with and without inorganic salts, exhibit significant surface tension depression. These observations add to the growing body of evidence that dicarbonyl compounds may form secondary organic material in the aerosol aqueous phase, and that secondary organic aerosol formation via heterogeneous processes may affect seed aerosol properties.
Vertical distribution of aerosols in the vicinity of Mexico City during MILAGRO-2006 Campaign

On 7 March 2006, a mobile, ground-based, vertical pointing, elastic lidar system made a North-South transect through the Mexico City basin. Column averaged, aerosol size distribution (ASD) measurements were made on the ground concurrently with the lidar measurements. The ASD ground measurements allowed calculation of the column averaged mass extinction efficiency (MEE) for the lidar system (1064 nm). The value of column averaged MEE was combined with spatially resolved lidar extinction coefficients to produce total aerosol mass concentration estimates with the resolution of the lidar (1.5 m vertical spatial and 1 s temporal). Airborne ASD measurements from DOE G-1 aircraft made later in the day on 7 March 2006, allowed the evaluation of the assumptions of constant ASD with height and time used for estimating the column averaged MEE. The results showed that the aerosol loading within the basin is about twice what is observed outside of the basin. The total aerosol base concentrations observed in the basin are of the order of 200 μg/m3 and the base levels outside are of the order of 100 μg/m3. The local heavy traffic events can introduce aerosol levels near the ground as high as 900 μg/m3. The article presents the methodology for estimating aerosol mass concentration from mobile, ground-based lidar measurements in combination with aerosol size distribution measurements. An uncertainty analysis of the methodology is also presented.
First remote sensing measurements of ClOOCl along with ClO and ClONO2 in activated and deactivated Arctic vortex conditions using new ClOOCl IR absorption cross sections

Active chlorine species play a dominant role in the catalytic destruction of stratospheric ozone in the polar vortices during the late winter and early spring seasons. Recently, the correct understanding of the ClO dimer cycle was challenged by the release of new laboratory absorption cross sections (Pope et al., 2007) yielding significant model underestimates of observed ClO and ozone loss (von Hobe et al., 2007). Under this aspect, nocturnal Arctic stratospheric limb emission measurements carried out by the balloon version of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS-B) from Kiruna (Sweden) on 11 January 2001 and 20/21 March 2003 have been reanalyzed with regard to the chlorine reservoir species ClONO2 and the active species, ClO and ClOOCl (Cl2O2). New laboratory measurements of IR absorption cross sections of ClOOCl for various temperatures and pressures allowed for the first time the retrieval of ClOOCl mixing ratios from remote sensing measurements. High values of active chlorine (ClOx) of roughly 2.3 ppbv at 20 km were observed by MIPAS-B in the cold mid-winter Arctic vortex on 11 January 2001. While nighttime ClOOCl shows enhanced values of nearly 1.1 ppbv at 20 km, ClONO2 mixing ratios are less than 0.1 ppbv at this altitude. In contrast, high ClONO2 mixing ratios of nearly 2.4 ppbv at 20 km have been observed in the late winter Arctic vortex on 20 March 2003. No significant ClOx amounts are detectable on this date since most of the active chlorine has already recovered to its main reservoir species ClONO2. The observed values of ClOx and ClONO2 are in line with the established polar chlorine chemistry. The thermal equilibrium constants between the dimer formation and its dissociation, as derived from the balloon measurements, are on the lower side of reported data and in good agreement with values recommended by von Hobe et al. (2007). Calculations with the ECHAM/MESSy Atmospheric Chemistry model (EMAC) using established kinetics show similar chlorine activation and deactivation, compared to the measurements in January 2001 and March 2003, respectively.
Acetaldehyde in the Alaskan subarctic snowpack

Acetaldehyde is a reactive intermediate in hydrocarbon oxidation. It is both emitted and taken up by snowpacks and photochemical and physical processes are probably involved. Understanding the reactivity of acetaldehyde in snow and its processes of physical and chemical exchanges requires the knowledge of its incorporation mechanism in snow crystals. We have performed a season-long study of the evolution of acetaldehyde concentrations in the subarctic snowpack near Fairbanks (65° N), central Alaska, which is subjected to a vigorous metamorphism due to persistent elevated temperature gradients in the snowpack, between 20 and 200° C m−1. The snowpack therefore almost entirely transforms into depth hoar. We have also analyzed acetaldehyde in a manipulated snowpack where temperature gradients were suppressed. Snow crystals there transformed much more slowly and their original shapes remained recognizable for months. The specific surface area of snow layers in both types of snowpacks was also measured. We deduce that acetaldehyde is not adsorbed onto the surface of snow crystals and that most of the acetaldehyde is probably not dissolved in the ice lattice of the snow crystals. We propose that most of the acetaldehyde measured is either trapped or dissolved within organic aerosol particles trapped in snow, or that acetaldehyde is formed by the hydrolysis of organic precursors contained in organic aerosols trapped in the snow, when the snow is melted for analysis. These precursors are probably aldehyde polymers formed within the aerosol particles by acid catalysis, but might also be biological molecules. In a laboratory experiment, acetaldehyde-di-n-hexyl acetal, representing a potential acetaldehyde precursor, was subjected to our analytical procedure and reacted to form acetaldehyde. This confirms our suggestion that acetaldehyde detected in snow could be produced during the melting of snow for analysis.