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High resolution assimilation of IASI ozone data with a global CTM

The pixel size of the Infrared Atmospheric Sounding Interferometer (IASI) remote sensor is much smaller than the horizontal grid size of current Chemical Transport Models (CTMs). In order to assimilate the maximum of information from the IASI retrievals, we have increased the horizontal resolution of our model MOCAGE to be consistent with the IASI pixel size. Experiments are carried out with the Valentina data assimilation system using the standard and the high resolution versions of the model. Two resolutions of the horizontal Gaussian grid have been used for the model: with a T42 and a T170 triangular truncations. Our study is based on the combination of data from the IASI instrument and from the Microwave Limb Sounder (MLS), since this latter dataset allows the information to be spread through the whole atmospheric columns at a low computational cost. Two datasets of ozone super-observations have been constructed by averaging the IASI data on the two model grids. Direct model simulations without data assimilation first show that the increase of the horizontal resolution modifies the ozone smallest scale structures as well as the ozone meridional distribution. This modification results from a better representation of the vertical velocity with the T170 configuration. When the ozone assimilation is performed there is less influence of the horizontal resolution of the model. Nevertheless, in a general way, comparisons with independent data show large reductions of the ozone standard deviations when the resolution is increased. When the ozone assimilation is performed with the high resolution dataset, the high resolution model does not improve the ozone analysis compared to the one obtained with the same model resolution but with the low resolution IASI dataset. This result is due to the difficulty to combine IASI data and MLS data. For assimilating IASI data at high resolution the horizontal correlation length-scale has to be decreased to catch the small scale structures present in the dataset. By doing so the influence of the coarser resolution MLS data is decreased and part of the information brought on the vertical shape of the ozone profile is lost. It is concluded that it is essential to add information on the vertical distribution of ozone column when the IASI data is assimilated at a resolution close to the pixel size. Using IASI averaging kernels would likely improve the simulations, but the computational cost would be much higher. Alternatively, better results might be obtained by a careful tuning of the horizontal correlation length-scale.
Observation of neutral sulfuric acid-amine containing clusters in laboratory and ambient measurements

Recent ab initio calculations showed that amines can enhance atmospheric sulfuric acid-water nucleation more effectively than ammonia, and this prediction has been substantiated in laboratory measurements. Laboratory studies have also shown that amines can effectively displace ammonia in several types of ammonium clusters. However, the roles of amines in cluster formation and growth at a microscopic molecular scale (from molecular sizes up to 2 nm) have not yet been well understood. Processes that must be understood include the incorporation of amines into sulfuric acid clusters and the formation of organic salts in freshly nucleated particles, which contributes significantly to particle growth rates. We report the first laboratory and ambient measurements of neutral sulfuric acid-amine clusters using the Cluster CIMS, a recently-developed mass spectrometer designed for measuring neutral clusters formed in the atmosphere during nucleation. An experimental technique, which we refer to as Semi-Ambient Signal Amplification (SASA), was employed. Sulfuric acid was added to ambient air, and the concentrations and composition of clusters in this mixture were analyzed by the Cluster CIMS. This experimental approach led to significantly higher cluster concentrations than are normally found in ambient air, thereby increasing signal-to-noise levels and allowing us to study reactions between gas phase species in ambient air and sulfuric acid containing clusters. Mass peaks corresponding to clusters containing four H2SO4 molecules and one amine molecule were clearly observed, with the most abundant sulfuric acid-amine clusters being those containing a C2- or C4-amine (i.e. amines with masses of 45 and 73 amu). Evidence for C3- and C5-amines (i.e. amines with masses of 59 and 87 amu) was also found, but their correlation with sulfuric acid tetramer was not as strong as was observed for the C2- and C4-amines. The formation mechanisms for those sulfuric acid-amine clusters were investigated by varying the residence time in the inlet. It was concluded that the amines react directly with neutral clusters and that ion-induced clustering of sulfuric acid cluster ions with amines was not a dominant process. Results from ambient measurements using the Cluster CIMS without addition of sulfuric acid have shown that the sulfuric acid-amine clusters were reasonably well correlated with sulfuric acid tetramer and consistent with the SASA experiments at the same Boulder sampling site. Also, clusters that contain C2- or C4-amines were more abundant and better correlated with sulfuric acid tetramer than other types of amine containing clusters. However, ambient measurements of sulfuric acid-amine clusters remain difficult and highly uncertain because their concentrations are only slightly above background levels, even during nucleation events.
Chemical characteristics of inorganic ammonium salts in PM2.5 in the atmosphere of Beijing (China)

The atmospheric concentrations of gaseous HNO3, HCl and NH3 and their relative salts have been measured during two field campaigns in the winter and in the summer of 2007 at Beijing (China), as part of CAREBEIJING (Campaigns of Air Quality Research in Beijing and Surrounding Region). In this study, annular denuder technique used with integration times of 2 and 24h to collect inorganic and soluble PM2.5 without interferences from gas–particle and particle–particle interactions. The results were discussed from the standpoint of temporal and diurnal variations and meteorological effects. Fine particulate Cl−, NH4+ and SO42− exhibited distinct temporal variations, while fine particulate NO3− did not show much variation with respect to season. Daily mean concentrations of fine particulate NH4+ and SO42− were higher during summer (12.30 μg m−3 and 18.24 μg m−3, respectively) than during winter (6.51 μg m−3 and 7.50 μg m−3, respectively). Daily mean concentrations of fine particulate Cl− were higher during winter (2.94 μg m−3) than during summer (0.79 μg m−3), while fine particulate NO3− showed similar both in winter (8.38 μg m−3) and in summer (9.62 μg m−3) periods. The presence of large amounts of fine particulate NO3− even in summer are due to higher local and regional concentrations of NH3 in the atmosphere available to neutralize H2SO4 and HNO3, which is consistent with the observation that the measured particulate species were neutralized. The composition of fine particulate matter indicated the domination of (NH4)2SO4 during winter and summer periods. In addition, the high relative humidity conditions in summer period seemed to dissolve a significant fraction of HNO3 and NH3 enhancing fine particulate NO3− and NH4+ in the atmosphere. All measured particulate species showed diurnal similar patterns during the winter and summer periods with higher peaks in the early morning, especially in summer, when humid and stable atmospheric conditions occurred. These diurnal variations were affected by wind direction suggesting regional and local source influences. The fine particulate species were correlated with NOx and PM2.5, supporting the hypothesis that traffic may be also an important source of secondary particles.
Yields of oxidized volatile organic compounds during the OH radical initiated oxidation of isoprene, methyl vinyl ketone, and methacrolein under high-NOx conditions

We present first-generation and total production yields of glyoxal, methylglyoxal, glycolaldehyde, and hydroxyacetone from the oxidation of isoprene, methyl vinyl ketone (MVK), and methacrolein (MACR) with OH under high NOx conditions. Several of these first-generation yields are not included in commonly used chemical mechanisms, such as the Leeds Master Chemical Mechanism (MCM) v. 3.2. The first-generation yield of glyoxal from isoprene was determined to be 2.1 (±0.6)%. Inclusion of first-generation production of glyoxal, glycolaldehyde and hydroxyacetone from isoprene greatly improves performance of an MCM based model during the initial part of the experiments. In order to further improve performance of the MCM based model, higher generation glyoxal production was reduced by lowering the first-generation yield of glyoxal from C5 hydroxycarbonyls. The results suggest that glyoxal production from reaction of OH with isoprene under high NOx conditions can be approximated by inclusion of a first-generation production term together with secondary production only via glycolaldehyde. Analogously, methylglyoxal production can be approximated by a first-generation production term from isoprene, and secondary production via MVK, MACR and hydroxyacetone. The first-generation yields reported here correspond to less than 5% of the total oxidized yield from isoprene and thus only have a small effect on the fate of isoprene. However, due to the abundance of isoprene, the combination of first-generation yields and reduced higher generation production of glyoxal from C5 hydroxycarbonyls is important for models that include the production of the small organic molecules from isoprene.
Rate coefficients for the reaction of methylglyoxal (CH3COCHO) with OH and NO3 and glyoxal (HCO)2 with NO3

Rate coefficients, k, for the gas-phase reaction of CH3COCHO (methylglyoxal) with the OH and NO3 radicals and (CHO)2 (glyoxal) with the NO3 radical are reported. Rate coefficients for the OH + CH3COCHO (k1) reaction were measured under pseudo-first-order conditions in OH as a function of temperature (211–373 K) and pressure (100–220 Torr, He and N2 bath gases) using pulsed laser photolysis to produce OH radicals and laser induced fluorescence to measure its temporal profile. k1 was found to be independent of the bath gas pressure with k1(295 K) = (1.29 ± 0.13) × 10−11 cm3 molecule−1 s−1 and a temperature dependence that is well represented by the Arrhenius expression k1(T) = (1.74 ± 0.20) × 10−12 exp[(590 ± 40)/T] cm3 molecule−1 s−1 where the uncertainties are 2σ and include estimated systematic errors. Rate coefficients for the NO3 + (CHO)2 (k3) and NO3 + CH3COCHO (k4) reactions were measured using a relative rate technique to be k3(296 K) = (4.0 ± 1.0) × 10−16 cm3 molecule−1 s−1 and k4(296 K) = (5.1 ± 2.1) × 10−16 cm3 molecule−1 s−1. k3(T) was also measured using an absolute rate coefficient method under pseudo-first-order conditions at 296 and 353 K to be (4.2 ± 0.8) × 10−16 and (7.9 ± 3.6) × 10−16 cm3 molecule−1 s−1, respectively, in agreement with the relative rate result obtained at room temperature. The atmospheric implications of the OH and NO3 reaction rate coefficients measured in this work are discussed.
Calibration of TCCON column-averaged CO2: the first aircraft campaign over European TCCON sites

The Total Carbon Column Observing Network (TCCON) is a ground-based network of Fourier Transform Spectrometer (FTS) sites around the globe, where the column abundances of CO2, CH4, N2O, CO and O2 are measured. CO2 is constrained with a precision better than 0.25% (1-σ). To achieve a similarly high accuracy, calibration to World Meteorological Organization (WMO) standards is required. This paper introduces the first aircraft calibration campaign of five European TCCON sites and a mobile FTS instrument. A series of WMO standards in-situ profiles were obtained over European TCCON sites via aircraft and compared with retrievals of CO2 column amounts from the TCCON instruments. The results of the campaign show that the FTS measurements are consistently biased 1.1% ± 0.2% low with respect to WMO standards, in agreement with previous TCCON calibration campaigns. The standard a priori profile for the TCCON FTS retrievals is shown to not add a bias. The same calibration factor is generated using aircraft profiles as a priori and with the TCCON standard a priori. With a calibration to WMO standards, the highly precise TCCON CO2 measurements of total column concentrations provide a suitable database for the calibration and validation of nadir-viewing satellites.
Springtime carbon emission episodes at the Gosan background site revealed by total carbon, stable carbon isotopic composition, and thermal characteristics of carbonaceous particles

In order to investigate the emission of carbonaceous aerosols at the Gosan background super-site (33.17° N, 126.10° E) in East Asia, total suspended particles (TSP) were collected during spring of 2007 and 2008 and analyzed for particulate organic carbon, elemental carbon, total carbon (TC), total nitrogen (TN), and stable carbon isotopic composition (δ13C) of TC. The stable carbon isotopic composition of TC (δ13CTC) was found to be lowest during pollen emission episodes (range: −26.2&permil; to −23.5&permil;, avg. −25.2 ± 0.9&permil;), approaching those of the airborne pollen (−28.0&permil;) collected at the Gosan site. Based on a carbon isotope mass balance equation, we found that ~42% of TC in the TSP samples during the pollen episodes was attributed to airborne pollen from Japanese cedar trees planted around tangerine farms in Jeju Island. A negative correlation between the citric acid-carbon/TC ratios and δ13CTC was obtained during the pollen episodes. These results suggest that citric acid emitted from tangerine fruit may be adsorbed on the airborne pollen and then transported to the Gosan site. Thermal evolution patterns of organic carbon during the pollen episodes were characterized by high OC evolution in the OC2 temperature step (450 °C). Since thermal evolution patterns of organic aerosols are highly influenced by their molecular weight, they can be used as additional information on the formation of secondary organic aerosols and the effect of aging of organic aerosols during the long-range atmospheric transport and sources of organic aerosols.
Estimation of NOx emissions from Delhi using Car MAX-DOAS observations and comparison with OMI satellite data

We present the first Multi-Axis-(MAX-) DOAS observations in India performed during April 2010 and January 2011 in Delhi and nearby regions. The MAX-DOAS instrument was mounted on a car roof, which allowed us to perform measurements along individual driving routes. From car MAX-DOAS observations along closed circles around Delhi, together with information on wind speed and direction, the NOx emissions from the greater Delhi area were determined: our estimate of 4.4 × 1025 molecules s−1 is found to be slightly lower than the corresponding emission estimates using the EDGAR emission inventory and substantially smaller compared to a recent study by Gurjar et al. (2004). We also determined NOx emissions from Delhi using OMI satellite observations on the same days. These emissions are slightly smaller than those from the car MAX-DOAS measurements. Finally the car MAX-DOAS observations were also used for the validation of simultaneous OMI satellite measurements of the tropospheric NO2 VCD and found a good agreement of the spatial patterns. Concerning the absolute values, OMI data are, on average, higher than the car MAX-DOAS observations close to strong emission sources, and vice versa over less polluted regions. Our results indicate that OMI NO2 VCDs are biased low over strongly polluted regions, probably caused by inadequate a-priori profiles used in the OMI satellite retrieval.
Variable lifetimes and loss mechanisms for NO3 and N2O5 during the DOMINO campaign: contrasts between marine, urban and continental air

Nighttime mixing ratios of boundary layer N2O5 were determined using cavity-ring-down spectroscopy during the DOMINO campaign in Southern Spain (Diel Oxidant Mechanisms In relation to Nitrogen Oxides, 21 November 2008–8 December 2008). N2O5 mixing ratios ranged from below the detection limit (~5 ppt) to ~500 ppt. A steady-state analysis constrained by measured mixing ratios of N2O5, NO2 and O3 was used to derive NO3 lifetimes and compare them to calculated rates of loss via gas-phase and heterogeneous reactions of both NO3 and N2O5. Three distinct types of air masses were encountered, which were largely marine (Atlantic), continental or urban-industrial in origin. NO3 lifetimes were longest in the Atlantic sector (up to ~30 min) but were very short (a few seconds) in polluted, air masses from the local city and petroleum-related industrial complex of Huelva. Air from the continental sector was an intermediate case. The high reactivity to NO3 of the urban air mass was not accounted for by gas-phase and heterogeneous reactions, rates of which were constrained by measurements of NO, volatile organic species and aerosol surface area. In general, high NO2 mixing ratios were associated with low NO3 lifetimes, though heterogeneous processes (e.g. reaction of N2O5 on aerosol) were generally less important than direct gas-phase losses of NO3. The presence of SO2 at levels above ~2 ppb in the urban air sector was always associated with very low N2O5 mixing ratios indicating either very short NO3 lifetimes in the presence of combustion-related emissions or an important role for reduced sulphur species in urban, nighttime chemistry. High production rates coupled with low lifetimes of NO3 imply an important contribution of nighttime chemistry to removal of both NOx and VOC.
Physical and chemical properties of pollution aerosol particles transported from North America to Greenland as measured during the POLARCAT summer campaign

Within the framework of the POLARCAT-France campaign, aerosol physical, chemical and optical properties over Greenland were measured onboard the French ATR-42 research aircraft. The origins of CO excess peaks detected in the aircraft measurements then have been identified through FLEXPART simulations. The study presented here focuses particularly on the characterization of air masses transported from the North American continent to Greenland. Air masses that picked up emissions from Canadian boreal forest fires as well as from the cities on the American east coast were identified and selected for a detailed study. Measurements of CO concentrations, aerosol chemical composition, aerosol number size distributions, aerosol volume volatile fractions and aerosol light absorption (mainly from black carbon) are used in order to study the relationship between CO enhancement (ΔCO), aerosol particle concentrations and number size distributions. Aerosol number size distributions (normalised with their respective ΔCO) are in good agreement with previous studies. Nonetheless, wet scavenging may have occurred along the pathway between the emission sources and Greenland leading to a less pronounced accumulation mode in the POLARCAT data. Chemical analyses from mass spectrometry show that submicrometer aerosol particles are mainly composed of sulphate and organics. The observed bimodal (Aitken and accumulation) aerosol number size distributions show a significant enhancement in Aitken mode particles. Furthermore, results from the thermodenuder analysis demonstrate the external mixture of boreal fire (BF) air masses from North America (NA). This is particularly observed in the accumulation mode, containing a volume fraction of up to 25–30% of refractory material at the applied temperature of 280 °C. NA anthropogenic air masses with only 6% refractory material in the accumulation mode can be clearly distinguished from BF air masses. Overall, during the campaign rather small amounts of black carbon from the North American continent were transported towards Greenland during the summer POLARCAT observation period, which also is a valuable finding with respect to potential climate impacts of black carbon in the Arctic.