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An extended version of the German operational weather forecast model was used to simulate the ash dispersion during the eruption of the Eyjafjallajökull. As an operational forecast was launched every 6 hours, a time-lagged ensemble was obtained. Sensitivity runs show the ability of the model to simulate thin ash layers when an increased vertical resolution is used. Calibration of the model results with measured data allows for a quantitative forecast of the ash concentration. After this calibration an independent comparison of the simulated number concentration of 3 μm particles and observations at Hohenpeißenberg gives a correlation coefficient of 0.79. However, this agreement could only be reached after additional modifications of the emissions. Based on the time lagged ensemble the conditional probability of violation of a certain threshold is calculated. Improving the ensemble technique used in our study such probabilities could become valuable information for the forecasters advising the organizations responsible for the closing of the airspace.
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Black carbon fractal aggregates have complicated shapes that make the calculation of their optical properties particularly computationally expensive. Here, a method is presented to estimate fractal aggregate light scattering properties by optimising simplified models to full light scattering calculations. It is found that there are no possible spherical models (at any size or refractive index) that well represent the light scattering in the visible or near-thermal infrared. As such, parameterisations of the light scattering as a function of the number of aggregate particles is presented as the most pragmatic choice for modelling distributions of black carbon when the large computational overheads of rigorous scattering calculations cannot be justified. This parameterisation can be analytically integrated to provide light scattering properties for lognormal distributions of black carbon fractal aggregates and return extinction cross sections with 0.1% accuracy for typical black carbon size distributions. Scattering cross sections and the asymmetry parameter can be obtained to within 3%.
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Sources, composition and occurrence of secondary organic aerosols in the Arctic were investigated at Zeppelin Mountain, Svalbard, and Station Nord, northeastern Greenland, during the full annual cycle of 2008 and 2010, respectively. Speciation of organic acids, organosulfates and nitrooxy organosulfates – from both anthropogenic and biogenic precursors were in focus. A total of 11 organic acids (terpenylic acid, benzoic acid, phthalic acid, pinic acid, suberic acid, azelaic acid, adipic acid, pimelic acid, pinonic acid, diaterpenylic acid acetate and 3-methyl-1,2,3-butanetricarboxylic acid), 12 organosulfates and 1 nitrooxy organosulfate were identified in aerosol samples from the two sites using a high-performance liquid chromatograph (HPLC) coupled to a quadrupole Time-of-Flight mass spectrometer. At Station Nord, compound concentrations followed a distinct annual pattern, where high mean concentrations of organosulfates (47 ± 14 ng m<sup>−3</sup>) and organic acids (11.5 ± 4 ng m<sup>−3</sup>) were observed in January, February and March, contrary to considerably lower mean concentrations of organosulfates (2 ± 3 ng m<sup>−3</sup>) and organic acids (2.2 ± 1 ng m<sup>−3</sup>) observed during the rest of the year. At Zeppelin Mountain, organosulfate and organic acid concentrations remained relatively constant during most of the year at a mean concentration of 15 ± 4 ng m<sup>−3</sup> and 3.9 ± 1 ng m<sup>−3</sup>, respectively. However during four weeks of spring, remarkably higher concentrations of total organosulfates (23–36 ng m<sup>−3</sup>) and total organic acids (7–10 ng m<sup>−3</sup>) were observed. Elevated organosulfate and organic acid concentrations coincided with the Arctic haze period at both stations, where northern Eurasia was identified as the main source region. Air mass transport from northern Eurasia to Zeppelin Mountain was associated with a 100% increase in the number of detected organosulfate species compared with periods of air mass transport from the Arctic Ocean, Scandinavia and Greenland. The results from this study suggested that the presence of organic acids and organosulfates at Station Nord was mainly due to long-range transport, whereas indications of local sources were found for some compounds at Zeppelin Mountain. Furthermore, organosulfates contributed significantly to organic matter throughout the year at Zeppelin Mountain (annual mean of 13 ± 8%) and during Arctic haze at Station Nord (7 ± 2%), suggesting organosulfates to be important compounds in Arctic aerosols.
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To improve dust storm identification over the western United States, historical dust events measured by air quality and satellite observations are analyzed based on their characteristics in data sets of regular meteorology, satellite-based aerosol optical depth (AOD), and air quality measurements. Based on the prevailing weather conditions associated with dust emission, dust storm events are classified into the following four typical types: <br><br> (1) The key feature of cold front-induced dust storms is their rapid process with strong dust emissions.<br><br> (2) Events caused by meso- to small-scale weather systems have the highest levels of emissions.<br><br> (3) Dust storms caused by tropical disturbances show a stronger air concentration of dust and last longer than those in (1) and (2).<br><br> (4) Dust storms triggered by cyclogenesis last the longest.<br><br> In this paper, sample events of each type are selected and examined to explore characteristics observed from in situ and remote-sensing measurements. These characteristics include the lasting period, surface wind speeds, areas affected, average loading on ground-based optical and/or air quality measurements, peak loading on ground-based optical and/or air quality measurements, and loading on satellite-based aerosol optical depth. Based on these analyses, we compare the characteristics of the same dust events captured in different data sets in order to define the dust identification criteria. The analyses show that the variability in mass concentrations captured by in situ measurements is consistent with the variability in AOD from stationary and satellite observations. Our analyses also find that different data sets are capable of identifying certain common characteristics, while each data set also provides specific information about a dust storm event. For example, the meteorological data are good at identifying the lasting period and area impacted by a dust event; the ground-based air quality and optical measurements can capture the peak strength well; aerosol optical depth (AOD) from satellite data sets allows us to better identify dust-storm-affected areas and the spatial extent of dust. The current study also indicates that the combination of in situ and satellite observations is a better method to fill gaps in dust storm recordings.
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Hydroxyl radicals (OH) are the most important reagent for the oxidation of trace gases in the atmosphere. OH concentrations measured during recent field campaigns in isoprene-rich environments were unexpectedly large. A number of studies showed that unimolecular reactions of organic peroxy radicals (RO<sub>2</sub>) formed in the initial reaction step of isoprene with OH play an important role for the OH budget in the atmosphere at low mixing ratios of nitrogen monoxide (NO) of less than 100 pptv. It has also been suggested that similar reactions potentially play an important role for RO<sub>2</sub> from other compounds. Here, we investigate the oxidation of methacrolein (MACR), one major oxidation product of isoprene, by OH in experiments in the simulation chamber SAPHIR under controlled atmospheric conditions. The experiments show that measured OH concentrations are approximately 50% larger than calculated by the Master Chemical Mechanism (MCM) for conditions of the experiments (NO mixing ratio of 90 pptv). The analysis of the OH budget reveals an OH source that is not accounted for in MCM, which is correlated with the production rate of RO<sub>2</sub> radicals from MACR. In order to balance the measured OH destruction rate, 0.77 OH radicals (1σ error: ± 0.31) need to be additionally reformed from each reaction of OH with MACR. The strong correlation of the missing OH source with the production of RO<sub>2</sub> radicals is consistent with the concept of OH formation from unimolecular isomerization and decomposition reactions of RO<sub>2</sub>. The comparison of observations with model calculations gives a lower limit of 0.03 s<sup>−1</sup> for the reaction rate constant if the OH source is attributed to an isomerization reaction of MACR-1-OH-2-OO and MACR-2-OH-2-OO formed in the MACR + OH reaction as suggested in the literature (Crounse et al., 2012). This fast isomerization reaction would be a competitor to the reaction of this RO<sub>2</sub> species with a minimum of 150 pptv NO. The isomerization reaction would be the dominant reaction pathway for this specific RO<sub>2</sub> radical in forested regions, where NO mixing ratios are typically much smaller.
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Within the framework of the "Hill Cap Cloud Thuringia 2010" (HCCT-2010) international cloud experiment, the influence of cloud processing on the activation properties of ambient aerosol particles was investigated. Particles were probed upwind and downwind of an orographic cap cloud on Mt Schmücke, which is part of a large mountain ridge in Thuringia, Germany. The activation properties of the particles were investigated by means of size-segregated cloud condensation nuclei (CCN) measurements at 3 to 4 different supersaturations. The observed CCN spectra together with the total particle spectra were used to calculate the hygroscopicity parameter κ for the upwind and downwind stations. The upwind and downwind critical diameters and κ values were then compared for defined cloud events (FCE) and non-cloud events (NCE). Cloud processing was found to increase the hygroscopicity of the aerosol particles significantly, with an average increase in κ of 50%. Mass spectrometry analysis and isotopic analysis of the particles suggest that the observed increase in the hygroscopicity of the cloud-processed particles is due to an enrichment of sulfate and possibly also nitrate in the particle phase.
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Biogenic acids were measured in aerosols at the SMEAR II (Station for Measuring Forest Ecosystem-Atmosphere Relations II) station in Finland from June 2010 until October 2011. The analysed organic acids were pinic, pinonic, caric, limonic and caryophyllinic acids from oxidation of α-pinene, β-pinene, limonene, Δ<sup>3</sup>-carene and β-caryophyllene, respectively. Due to a lack of authentic standards, the caric, limonic and caryophyllinic acids were synthesised for this study. The mean, median, maximum and minimum concentrations (ng m<sup>−3</sup>) were as follows: limonic acid (1.26, 0.80, 16.5, below detection limit (< LOD)), pinic acid (5.53, 3.25, 31.4, 0.15), pinonic acid (9.87, 5.07, 80.1, < LOD), caric acid (5.52, 3.58, 49.8, < LOD), and caryophyllinic acid (7.87, 6.07, 86.1, < LOD). <br><br> The highest terpenoic acid concentrations were measured during the summer. Of the acids, β-caryophyllinic acid showed the highest concentrations in summer, but during other times of the year pinonic acid was the most abundant. The β-caryophyllinic acid contribution was higher than expected, based on the emission calculations of the precursor compounds and yields from oxidation experiments in smog chambers, implying that the β-caryophyllene emissions or β-caryophyllinic acid yields were underestimated. The concentration ratios between terpenoic acids and their precursors were clearly lower in summer than in winter, indicating stronger partitioning to the aerosol phase during the cold winter season. The β-caryophyllinic and caric acids were weakly correlated with the accumulation-mode particle number concentrations.
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In this study we investigate to what degree it is possible to reconcile continuously recorded particle light extinction coefficients derived from dry in situ measurements at Zeppelin station (78.92° N, 11.85° E; 475 m above sea level), Ny-Ålesund, Svalbard, that are recalculated to ambient relative humidity, as well as simultaneous ambient observations with the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) aboard the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) satellite. To our knowledge, this represents the first study that compares spaceborne lidar measurements to optical aerosol properties from short-term in situ observations (averaged over 5 h) on a case-by-case basis. Finding suitable comparison cases requires an elaborate screening and matching of the CALIOP data with respect to the location of Zeppelin station as well as the selection of temporal and spatial averaging intervals for both the ground-based and spaceborne observations. Reliable reconciliation of these data cannot be achieved with the closest-approach method, which is often used in matching CALIOP observations to those taken at ground sites. This is due to the transport pathways of the air parcels that were sampled. The use of trajectories allowed us to establish a connection between spaceborne and ground-based observations for 57 individual overpasses out of a total of 2018 that occurred in our region of interest around Svalbard (0 to 25° E, 75 to 82° N) in the considered year of 2008. Matches could only be established during winter and spring, since the low aerosol load during summer in connection with the strong solar background and the high occurrence rate of clouds strongly influences the performance and reliability of CALIOP observations. Extinction coefficients in the range of 2 to 130 Mm<sup>−1</sup> at 532 nm were found for successful matches with a difference of a factor of 1.47 (median value for a range from 0.26 to 11.2) between the findings of in situ and spaceborne observations (the latter being generally larger than the former). The remaining difference is likely to be due to the natural variability in aerosol concentration and ambient relative humidity, an insufficient representation of aerosol particle growth, or a misclassification of aerosol type (i.e., choice of lidar ratio) in the CALIPSO retrieval.
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We conducted long-term network observations using standardized Multi-Axis Differential optical absorption spectroscopy (MAX-DOAS) instruments in Russia and ASia (MADRAS) from 2007 onwards and made the first synthetic data analysis. At seven locations (Cape Hedo, Fukue and Yokosuka in Japan, Hefei in China, Gwangju in Korea, and Tomsk and Zvenigorod in Russia) with different levels of pollution, we obtained 80 927 retrievals of tropospheric NO<sub>2</sub> vertical column density (TropoNO2VCD) and aerosol optical depth (AOD). In the technique, the optimal estimation of the TropoNO2VCD and its profile was performed using aerosol information derived from O<sub>4</sub> absorbances simultaneously observed at 460–490 nm. This large data set was used to analyze NO<sub>2</sub> climatology systematically, including temporal variations from the seasonal to the diurnal scale. The results were compared with Ozone Monitoring Instrument (OMI) satellite observations and global model simulations. Two NO<sub>2</sub> retrievals of OMI satellite data (NASA ver. 2.1 and Dutch OMI NO<sub>2</sub> (DOMINO) ver. 2.0) generally showed close correlations with those derived from MAX-DOAS observations, but had low biases of up to ~50%. The bias was distinct when NO<sub>2</sub> was abundantly present near the surface and when the AOD was high, suggesting a possibility of incomplete accounting of NO<sub>2</sub> near the surface under relatively high aerosol conditions for the satellite observations. Except for constant biases, the satellite observations showed nearly perfect seasonal agreement with MAX-DOAS observations, suggesting that the analysis of seasonal features of the satellite data were robust. Weekend reduction in the TropoNO2VCD found at Yokosuka and Gwangju was absent at Hefei, implying that the major sources had different weekly variation patterns. While the TropoNO2VCD generally decreased during the midday hours, it increased exceptionally at urban/suburban locations (Yokosuka, Gwangju, and Hefei) during winter. A global chemical transport model, MIROC-ESM-CHEM (Model for Interdisciplinary Research on Climate–Earth System Model–Chemistry), was validated for the first time with respect to background NO<sub>2</sub> column densities during summer at Cape Hedo and Fukue in the clean marine atmosphere.
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In this paper, we investigated production and growth of new particles in the marine atmosphere during two cruise campaigns in China Seas using a Fast Mobility Particle Sizer. Only eight new particle formation (NPF) events (> 30 min) occurred on 5 days out of 31 sampling days, and the subsequent growth of new particles was observed only in five events. Apparent formation rates of new particles (in the range of 5.6–30 nm) varied from 0.3 to 15.2 particles cm<sup>−3</sup> s<sup>−1</sup> in eight events, and growth rates ranged from 2.5 to 10 nm h<sup>−1</sup> in five NPF events. Modeling results simulated by US EPA Community Multi-scale Air Quality Model (CMAQ) showed that ammonium nitrate (NH<sub>4</sub>NO<sub>3</sub>) was newly formed in the atmosphere over the corresponding sea zone during 2 out of 5 events, in which new particles partially or mostly grew over 50 nm. However, in the remaining three events, new particles cannot grow over 30 nm, and the modeling results showed that no NH<sub>4</sub>NO<sub>3</sub> was newly formed in the corresponding marine atmosphere. Modeling results also showed that formation of secondary organics occurred through all new particle growth periods. Difference between the two types of new particle growth patterns suggested that a combination of ammonium nitrate and organics newly formed likely contributed to the growth of new particles from 30 nm to larger size. However, the findings were obtained from the limited data, and the simulations of CMAQ also suffered from several weaknesses such as only having three size bins for different particles, lack of marine aerosol precursors, etc. More future studies are thereby needed for confirmation.
