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Lidar observation and model simulation of a volcanic-ash-induced cirrus cloud during the Eyjafjallajökull eruption

Heterogeneous ice formation induced by volcanic ash from the Eyjafjallajökull volcano eruption in April 2010 is investigated based on the combination of a cirrus cloud observed with a backscatter lidar over Jülich (western Germany) and model simulations along backward trajectories. The microphysical properties of the cirrus cloud could only be represented by the microphysical model under the assumption of an enhanced number of efficient ice nuclei originating from the volcanic eruption. The ice nuclei (IN) concentration determined by lidar measurements directly before and after cirrus cloud occurrence implies a value of around 0.1 cm−3 (in comparison normal IN conditions: 0.01 cm−3). This leads to a cirrus cloud with rather small ice crystals having a mean radius of 12 μm and a modification of the ice particle number (0.08 cm−3 instead of 3 × 10−4 cm−3 under normal IN conditions). The effectiveness of ice nuclei was estimated by the use of the microphysical model and the backward trajectories based on ECMWF data, establishing a freezing threshold of around 105% relative humidity with respect to ice in a temperature range from −45 to −55 °C . Only with these highly efficient ice nuclei was it possible for the cirrus cloud to be formed in a slightly supersaturated environment.
Chamber simulation of photooxidation of dimethyl sulfide and isoprene in the presence of NOx

To improve the model prediction for the formation of H2SO4 and methanesulfonic acid (MSA), aerosol-phase reactions of gaseous dimethyl sulfide (DMS) oxidation products [e.g., dimethyl sulfoxide (DMSO)] in aerosol have been included in the DMS kinetic model with the recently reported gas-phase reactions and their rate constants. To determine the rate constants of aerosol-phase reactions of both DMSO and its major gaseous products [e.g., dimethyl sulfone (DMSO2) and methanesulfinic acid (MSIA)], DMSO was photooxidized in the presence of NOx using a 2 m3 Teflon film chamber. The rate constants tested in the DMSO kinetic mechanisms were then incorporated into the DMS photooxidation mechanism. The model simulation using the newly constructed DMS oxidation mechanims was compared to chamber data obtained from the phototoxiation of DMS in the presence of NOx. Within 120-min simulation, the predicted concentrations of MSA increase by 200–400% and those of H2SO4, by 50–200% due to aerosol-phase chemistry. This was well substantiated with experimental data. To study the effect of coexisting volatile organic compounds, the photooxidation of DMS in the presence of isoprene and NOx has been simulated using the newly constructed DMS kinetic model integrated with the Master Chemical Mechanism (MCM) for isoprene oxidation, and compared to chamber data. With the high concentrations of DMS (250 ppb) and isoprene (560–2248 ppb), both the model simulation and experimental data showed an increase in the yields of MSA and H2SO4 as the isoprene concentration increased.
Aerosol radiative forcing during African desert dust events (2005–2010) over Southeastern Spain

The daily (24 h) averages of the aerosol radiative forcing (ARF) at the surface and the top of the atmosphere (TOA) were calculated during desert dust events over Granada (southeastern Spain) from 2005 to 2010. A radiative transfer model (SBDART) was utilized to simulate the solar irradiance values (0.31–2.8 μm) at the surface and TOA, using as input aerosol properties retrieved from CIMEL sun photometer measurements via an inversion methodology that uses the sky radiance measurements in principal plane configuration and a spheroid particle shape approximation. This inversion methodology was checked by means of simulated data from aerosol models, and the derived aerosol properties were satisfactorily compared against well-known AERONET products. Good agreement was found over a common spectral interval (0.2–4.0 μm) between the simulated SBDART global irradiances at surface and those provided by AERONET. In addition, simulated SBDART solar global irradiances at the surface have been successfully validated against CM-11 pyranometer measurements. The comparison indicates that the radiative transfer model slightly overestimates (mean bias of 3%) the experimental solar global irradiance. These results show that the aerosol optical properties used to estimate ARF represent appropriately the aerosol properties observed during desert dust outbreak over the study area. The ARF mean monthly values computed during desert dust events ranged from −13 ± 8 W m−2 to −34 ± 15 W m−2 at surface, from −4 ± 3 W m−2 to −13 ± 7 W m−2 at TOA and from +6 ± 4 to +21 ± 12 W m−2 in the atmosphere. We have checked if the differences found in aerosol optical properties among desert dust sectors translate to differences in ARF. The mean ARF at surface (TOA) were −20 ± 12 (−5 ± 5) W m−2, −21 ± 9 (−7 ± 5) W m−2 and −18 ± 9 (−6 ± 5) W m−2 for sector A (northern Morocco; northwestern Algeria), sector B (western Sahara, northwestern Mauritania and southwestern Algeria), and sector C (eastern Algeria, Tunisia), respectively. The Kolmogorov-Smirnov statistical test revealed that daily {ARF} values at TOA for sector A were significantly different from the other two sectors, likely as a result of the lower values of single scattering albedo obtained for sector A. The mean values of aerosol radiative forcing efficiency at surface (TOA) were −74 ± 12 W m−2 (−17 ± 7 W m−2) for sector A, −70 ± 14 W m−2 (−20 ± 9 W m−2) for sector B, and −65 ± 16 W m−2 (−22 ± 10 W m−2) for sector C, and thus comparable between the three sectors in all seasons.
Relationships between Brewer-Dobson circulation, double tropopauses, ozone and stratospheric water vapour

Statistical relationships between the variability of the area covered by double tropopause events (DTs), the strength of the tropical upwelling, the total column ozone and of the lower stratospheric water vapour are analyzed. The QBO and ENSO signals in the double tropopause and tropical upwelling as well as their influence on the statistical relationships are also presented. The analysis is based on both reanalysed data (ERA-Interim) and satellite data. Significant anticorrelations were found between the area covered by DTs and the total column ozone in the midlatitudes of the Northern Hemisphere. This relationship is confirmed by a large positive correlation between the areas covered by ozone laminae and double tropopause events as found in the HIRDLS satellite dataset. Significant anticorrelations were also found between the global area of double tropopause events and the near global (50° S–50° N) water vapour in the lower stratosphere. The correlations of DT variables with total column ozone and ozone laminae are both consistent with the poleward displacement of tropical air with lower ozone mixing ratio and with tropospheric intrusions of tropical tropospheric air into the lower extratropical stratosphere. The association of DTs with the poleward displacements of the tropical air is also consistent with a strong positive correlation between the area covered by DTs and the wave activity in the lower most stratosphere, between the first and second lapse rate tropopauses, as found in the ERA-Interim reanalysis. Finally, a significant anticorrelation was found between the tropical upwelling and the near global lower stratospheric water vapour. Moreover, the step like decrease in the lower stratospheric water vapour after 2001 is mirrored by a step like increase in the tropical upwelling.
Atmospheric ammonia and particulate inorganic nitrogen over the United States

We use in situ observations from the Interagency Monitoring of PROtected Visual Environments (IMPROVE) network, the Midwest Ammonia Monitoring Project, 11 surface site campaigns as well as Infrared Atmospheric Sounding Interferometer (IASI) satellite measurements with the GEOS-Chem model to investigate inorganic aerosol loading and atmospheric ammonia concentrations over the United States. IASI observations suggest that current ammonia emissions are underestimated in California and in the springtime in the Midwest. In California this underestimate likely drives the underestimate in nitrate formation in the GEOS-Chem model. However in the remaining continental United States we find that the nitrate simulation is biased high (normalized mean bias > = 1.0) year-round, except in Spring (due to the underestimate in ammonia in this season). None of the uncertainties in precursor emissions, the uptake efficiency of N2O5 on aerosols, OH concentrations, the reaction rate for the formation of nitric acid, or the dry deposition velocity of nitric acid are able to explain this bias. We find that reducing nitric acid concentrations to 75% of their simulated values corrects the bias in nitrate (as well as ammonium) in the US. However the mechanism for this potential reduction is unclear and may be a combination of errors in chemistry, deposition and sub-grid near-surface gradients. This "updated" simulation reproduces PM and ammonia loading and captures the strong seasonal and spatial gradients in gas-particle partitioning across the United States. We estimate that nitrogen makes up 15−35% of inorganic fine PM mass over the US, and that this fraction is likely to increase in the coming decade, both with decreases in sulfur emissions and increases in ammonia emissions.
Thermodynamics of reactions of ClHg and BrHg radicals with atmospherically abundant free radicals

Quantum calculations are used to determine the stability of reactive gaseous mercury (Hg(II)) compounds likely to be formed in the Br-initiated oxidation of gaseous elemental mercury (Hg(0)). Due to the absence of any evidence, current models neglect the possible reaction of BrHg with abundant radicals such as NO, NO2, HO2, ClO, or BrO. The present work demonstrates that BrHg forms stable compounds, BrHgY, with all of these radicals except NO. Additional calculations on the analogous ClHgY compounds reveal that the strength of the XHg-Y bond (for X = Cl, Br) varies little with the identity of the halogen. Calculations further suggest that HO2 and NO3 do not form strong bonds with Hg(0), and cannot initiate Hg(0) oxidation in the gas phase. The theoretical approach is validated by comparison to published data on HgX2 compounds, both from experiment and highly refined quantum chemical calculations. Quantum calculations on the stability of the anions of XHgY are carried out in order to aid future laboratory studies aimed at molecular-level characterization of gaseous Hg(II) compounds. Spectroscopic data on BrHg is analyzed to determine the equilibrium constant for its formation, and BrHg is determined to be much less stable than previously estimated. An expression is presented for the rate constant for BrHg dissociation.
Mixing state and compositional effects on CCN activity and droplet growth kinetics of size-resolved CCN in an urban environment

Aerosol composition and mixing state near anthropogenic sources can be highly variable and can challenge predictions of cloud condensation nuclei (CCN). The impacts of chemical composition on CCN activation kinetics is also an important, but largely unknown, aspect of cloud droplet formation. Towards this, we present in-situ size-resolved CCN measurements carried out during the 2008 summertime August Mini Intensive Gas and Aerosol Study (AMIGAS) campaign in Atlanta, GA. Aerosol chemical composition was measured by two particle-into-liquid samplers measuring water-soluble inorganic ions and total water-soluble organic carbon. Size-resolved CCN data were collected using the Scanning Mobility CCN Analysis (SMCA) method and were used to obtain characteristic aerosol hygroscopicity distributions, whose breadth reflects the aerosol compositional variability and mixing state. Knowledge of aerosol mixing state is important for accurate predictions of CCN concentrations and that the influence of an externally-mixed, CCN-active aerosol fraction varies with size from 31% for particle diameters less than 40 nm to 93% for accumulation mode aerosol during the day. Assuming size-dependent aerosol mixing state and size-invariant chemical composition decreases the average CCN concentration overprediction (for all but one mixing state and chemical composition scenario considered) from over 190–240% to less than 20%. CCN activity is parameterized using a single hygroscopicity parameter, κ, which averages to 0.16 ± 0.07 for 80 nm particles and exhibits considerable variability (from 0.03 to 0.48) throughout the study period. Particles in the 60–100 nm range exhibited similar hygroscopicity, with a κ range for 60 nm between 0.06–0.076 (mean of 0.18 ± 0.09). Smaller particles (40 nm) had on average greater κ, with a range of 0.20–0.92 (mean of 0.3 ± 0.12). Analysis of the droplet activation kinetics of the aerosol sampled suggests that most of the CCN activate as rapidly as calibration aerosol, suggesting that aerosol composition exhibits a minor (if any) impact on CCN activation kinetics.
FTIR time-series of biomass burning products (HCN, C2H6, C2H2, CH3OH, and HCOOH) at Reunion Island (21° S, 55° E) and comparisons with model data

Reunion Island (21° S, 55° E), situated in the Indian Ocean at about 800 km east of Madagascar, is appropriately located to monitor the outflow of biomass burning pollution from Southern Africa and Madagascar, in the case of short-lived compounds, and from other Southern Hemispheric landmasses such as South America, in the case of longer-lived species. Ground-based Fourier transform infrared (FTIR) solar absorption observations are sensitive to a large number of biomass burning products. We present in this work the FTIR retrieval strategies, suitable for very humid sites such as Reunion Island, for hydrogen cyanide (HCN), ethane (C2H6), acetylene (C2H2), methanol (CH3OH), and formic acid (HCOOH). We provide their total columns time-series obtained from the measurements during August–October 2004, May–October 2007, and May 2009–December 2010. We show that biomass burning explains a large part of the observed seasonal and interannual variability of the chemical species. The correlations between the daily mean total columns of each of the species and those of CO, also measured with our FTIR spectrometer at Reunion Island, are very good from August to November (R &geq; 0.86). This allows us to derive, for that period, the following enhancement ratios with respect to CO: 0.0047, 0.0078, 0.0020, 0.012, and 0.0046 for HCN, C2H6, C2H2, CH3OH, and HCOOH, respectively. The HCN ground-based data are compared to the chemical transport model GEOS-Chem, while the data for the other species are compared to the IMAGESv2 model. We show that using the HCN/CO ratio derived from our measurements (0.0047) in GEOS-Chem reduces the underestimation of the modeled HCN columns compared with the FTIR measurements. The comparisons between IMAGESv2 and the long-lived species C2H6 and C2H2 indicate that the biomass burning emissions used in the model (from the GFED3 inventory) are probably underestimated in the late September–October period for all years of measurements, and especially in 2004. The comparisons with the short-lived species, CH3OH and HCOOH, with lifetimes of around 5 days, suggest that the emission underestimation in late September–October 2004, occurs more specifically in the Southeastern Africa-Madagascar region. The very good correlation of CH3OH and HCOOH with CO suggests that, despite the dominance of the biogenic source of these compounds on the global scale, biomass burning is their major source at Reunion Island between August and November.
Impact of urban parameterization on high resolution air quality forecast with the GEM – AQ model

The aim of this study is to assess the impact of urban cover on high-resolution air quality forecast simulations with the GEM-AQ (Global Environmental Multiscale and Air Quality) model. The impact of urban area on the ambient atmosphere is non-stationary, and short-term variability of meteorological conditions may result in significant changes of the observed intensity of urban heat island and pollutant concentrations. In this study we used the Town Energy Balance (TEB) parameterization to represent urban effects on modelled meteorological and air quality parameters at the final nesting level with horizontal resolution of ~5 km over Southern Poland. Three one-day cases representing different meteorological conditions were selected and the model was run with and without the TEB parameterization. Three urban cover categories were used in the TEB parameterization: mid-high buildings, very low buildings and low density suburbs. Urban cover layers were constructed based on an area fraction of towns in a grid cell. To analyze the impact of urban parameterization on modelled meteorological and air quality parameters, anomalies in the lowest model layer for the air temperature, wind speed and pollutant concentrations were calculated. Anomalies of the specific humidity fields indicate that the use of the TEB parameterization leads to a systematic reduction of moisture content in the air. Comparison with temperature and wind speed measurements taken at urban background monitoring stations shows that application of urban parameterization improves model results. For primary pollutants the impact of urban areas is most significant in regions characterized with high emissions. In most cases the anomalies of NO2 and CO concentrations were negative. This reduction is most likely caused by an enhanced vertical mixing due to elevated surface temperature and modified vertical stability.
Wintertime Arctic Ocean sea water properties and primary marine aerosol concentrations

Sea spray aerosols are an important part of the climate system through their direct and indirect effects. Due to the diminishing sea ice, the Arctic Ocean is one of the most rapidly changing sea spray aerosol source areas. However, the influence of these changes on primary particle production is not known. In laboratory experiments we examined the influence of Arctic Ocean water temperature, salinity, and oxygen saturation on primary particle concentration characteristics. Sea water temperature was identified as the most important of these parameters. A strong decrease in sea spray aerosol production with increasing water temperature was observed for water temperatures between −1°C and 9°C. Aerosol number concentrations decreased from at least 1400 cm−3 to 350 cm−3. In general, the aerosol number size distribution exhibited a robust shape with one mode close to dry diameter Dp 0.2 μm with approximately 45% of particles at smaller sizes. Changes in sea water temperature did not result in pronounced change of the shape of the aerosol size distribution, only in the magnitude of the concentrations. Our experiments indicate that changes in aerosol emissions are most likely linked to changes of the physical properties of sea water at low temperatures. The observed strong dependence of sea spray aerosol concentrations on sea water temperature, with a large fraction of the emitted particles in the typical cloud condensation nuclei size range, provide strong arguments for a more careful consideration of this effect in climate models.