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CCN activation of fumed silica aerosols mixed with soluble pollutants

Particle–water interactions of completely soluble or insoluble particles are fairly well understood but less is known of aerosols consisting of mixtures of soluble and insoluble components. In this study, laboratory measurements were performed to investigate cloud condensation nuclei (CCN) activity of silica particles mixed with ammonium sulfate (a salt), sucrose (a sugar) and bovine serum albumin known as BSA (a protein). The agglomerated structure of the silica particles was investigated using measurements with a differential mobility analyser (DMA) and an aerosol particle mass analyser (APM). Based on these data, the particles were assumed to be compact agglomerates when studying their CCN activation capabilities. Furthermore, the critical supersaturations of particles consisting of pure and mixed soluble and insoluble compounds were explored using existing theoretical frameworks. These results showed that the CCN activation of single-component particles was in good agreement with Köhler- and adsorption theory based models when the agglomerated structure was accounted for. For mixed particles the CCN activation was governed by the soluble components, and the soluble fraction varied considerably with particle size for our wet-generated aerosols. Our results confirm the hypothesis that knowing the soluble fraction is the key parameter needed for describing the CCN activation of mixed aerosols, and highlight the importance of controlled coating techniques for acquiring a detailed understanding of the CCN activation of atmospheric insoluble particles mixed with soluble pollutants.
Transport of anthropogenic and biomass burning aerosols from Europe to the Arctic during spring 2008

During the POLARCAT-France airborne campaign in April 2008, pollution originating from anthropogenic and biomass burning emissions was measured in the European Arctic. We compare these aircraft measurements with simulations using the WRF-Chem model to investigate model representation of aerosols transported from Europe to the Arctic. Modeled PM2.5 is evaluated using European Monitoring and Evaluation Programme (EMEP) measurements in source regions and POLARCAT aircraft measurements in the Scandinavian Arctic. Total PM2.5 agrees well with the measurements, although the model overestimates nitrate and underestimates organic carbon in source regions. Using WRF-Chem in combination with the Lagrangian model FLEXPART-WRF, we find that during the campaign the research aircraft sampled two different types of European plumes: mixed anthropogenic and fire plumes from eastern Europe and Russia transported below 2 km, and anthropogenic plumes from central Europe uplifted by warm conveyor belt circulations to 5–6 km. Both modeled plume types had undergone significant wet scavenging (> 50% PM10) during transport. Modeled aerosol vertical distributions and optical properties below the aircraft are evaluated in the Arctic using airborne lidar measurements. Model results show that the pollution event transported aerosols into the Arctic (> 66.6° N) for a 4-day period. During this 4-day period, biomass burning emissions have the strongest influence on concentrations between 2.5 and 3 km altitudes, while European anthropogenic emissions influence aerosols at both lower (~ 1.5 km) and higher altitudes (~ 4.5 km). As a proportion of PM2.5, modeled black carbon and SO4= concentrations are more enhanced near the surface in anthropogenic plumes. The European plumes sampled during the POLARCAT-France campaign were transported over the region of springtime snow cover in northern Scandinavia, where they had a significant local atmospheric warming effect. We find that, during this transport event, the average modeled top-of-atmosphere (TOA) shortwave direct and semi-direct radiative effect (DSRE) north of 60° N over snow and ice-covered surfaces reaches +0.58 W m−2, peaking at +3.3 W m−2 at noon over Scandinavia and Finland.
Determination of interfacial parameters of a soluble particle in a nonideal solution from measured deliquescence and efflorescence humidities

In order to study the growth/shrinking of a hygroscopic nanoparticle during hydration/dehydration in an atmosphere of water vapour, we have employed a thermodynamic approach proposed by Shchekin et al. (2008). This approach uses the mechanic and thermodynamic concept of disjoining pressure of thin films and allows, among others, the prediction of the humidity growth factor of both (i) a homogeneous solution droplet with completely dissolved residual core and (ii) a heterogeneous solution droplet with partially dissolved residual core as a function of the ambient relative humidity. For application to a nanometric sodium chloride particle we have extended the original approach by (i) considering the nonideality of the solution through the dependence of molecular volumes of the solvent and solute molecules and the solute and solvent activities on the solution concentration, (ii) deriving an equation for the estimation of the efflorescence properties of a homogeneous solution droplet, and (iii) combining the empirical power law fittings for the size dependence of the deliquescence and efflorescence relative humidity values by Biskos et al. (2006a). It was demonstrated how the solution/solute interface energy and the correlation length of a thin solution film can be determined from a combination of experimentally determinable efflorescence and deliquescence humidities with the present calculus. The solution/solute interface energy was found to be in close agreement with some previous values reported in the literature, while it strongly differs from data of some other sources. The calculated deliquescence humidity shows a low sensitivity to the choice of the numerical value for the film correlation length. The estimated film correlation length of 1 nm for a nanometric sodium chloride particle with dry particle radius of 5 nm was found to be reconcilable with available a priori estimates of the correlation length from the literature when the measurement uncertainty of the deliquescence humidity is considered. Considering the combination of an extensive calculus, a comprehensive set of thermophysical constraints, and independent measurements of the deliquescence and efflorescence humidities as functions of dry particle radius, the obtained values of the solution/solute interface energy and the correlation length are in close agreement with previous estimations. The humidification of sodium chloride particles in the initial hydration stages was found to be very sensitive to the specification of the disjoining pressure. The enhancement of the wettability of the particle surface leads to an earlier onset of hygroscopic growth.
Comparisons of polar processing diagnostics from 34 years of the ERA-Interim and MERRA reanalyses

We present a comprehensive comparison of polar processing diagnostics derived from the National Aeronautics and Space Administration (NASA) Modern Era Retrospective-analysis for Research and Applications (MERRA) and the European Centre for Medium-Range Weather Forecasts (ECMWF) Interim Reanalysis (ERA-Interim). We use diagnostics that focus on meteorological conditions related to stratospheric chemical ozone loss based on temperatures, polar vortex dynamics, and air parcel trajectories to evaluate the effects these reanalyses might have on polar processing studies. Our results show that the agreement between MERRA and ERA-Interim changes significantly over the 34 years from 1979 to 2013 in both hemispheres and in many cases improves. By comparing our diagnostics during five time periods when an increasing number of higher-quality observations were brought into these reanalyses, we show how changes in the data assimilation systems (DAS) of MERRA and ERA-Interim affected their meteorological data. Many of our stratospheric temperature diagnostics show a convergence toward significantly better agreement, in both hemispheres, after 2001 when Aqua and GOES (Geostationary Operational Environmental Satellite) radiances were introduced into the DAS. Other diagnostics, such as the winter mean volume of air with temperatures below polar stratospheric cloud formation thresholds (VPSC) and some diagnostics of polar vortex size and strength, do not show improved agreement between the two reanalyses in recent years when data inputs into the DAS were more comprehensive. The polar processing diagnostics calculated from MERRA and ERA-Interim agree much better than those calculated from earlier reanalysis data sets. We still, however, see fairly large differences in many of the diagnostics in years prior to 2002, raising the possibility that the choice of one reanalysis over another could significantly influence the results of polar processing studies. After 2002, we see overall good agreement among the diagnostics, which demonstrates that the ERA-Interim and MERRA reanalyses are equally appropriate choices for polar processing studies of recent Arctic and Antarctic winters.
Simulations of atmospheric OH, O3 and NO3 reactivities within and above the boreal forest

Using the 1-D atmospheric chemistry transport model SOSAA, we have investigated the atmospheric reactivity of a boreal forest ecosystem during the HUMPPA-COPEC-10 campaign (summer 2010, at SMEAR~II in southern Finland). For the very first time, we present vertically resolved model simulations of the NO3 and O3 reactivity (R) together with the modelled and measured reactivity of OH. We find that OH is the most reactive oxidant (R &sim; 3 s-1) followed by NO3 (R &sim; 0.07 s-1) and O3 (R &sim; 2 × 10-5s-1). The missing OH reactivity was found to be large in accordance with measurements (&sim; 65%) as would be expected from the chemical subset described in the model. The accounted OH radical sinks were inorganic compounds (&sim; 41%, mainly due to reaction with CO), emitted monoterpenes (&sim; 14%) and oxidised biogenic volatile organic compounds (&sim; 44%). The missing reactivity is expected to be due to unknown biogenic volatile organic compounds and their photoproducts, indicating that the true main sink of OH is not expected to be inorganic compounds. The NO3 radical was found to react mainly with primary emitted monoterpenes (&sim; 60%) and inorganic compounds (&sim; 37%, including NO2). NO2 is, however, only a temporary sink of NO3 under the conditions of the campaign (with typical temperatures of 20–25 °C) and does not affect the NO3 concentration. We discuss the difference between instantaneous and steady-state reactivity and present the first boreal forest steady-state lifetime of NO3 (113 s). O3 almost exclusively reacts with inorganic compounds (&sim; 91%, mainly NO, but also NO2 during night) and less with primary emitted sesquiterpenes (&sim; 6%) and monoterpenes (&sim; 3%). When considering the concentration of the oxidants investigated, we find that OH is the oxidant that is capable of removing organic compounds at a faster rate during daytime, whereas NO3 can remove organic molecules at a faster rate during night-time. O3 competes with OH and NO3 during a short period of time in the early morning (around 5 a.m. local time) and in the evening (around 7–8 p.m.). As part of this study, we developed a simple empirical parameterisation for conversion of measured spectral irradiance into actinic flux. Further, the meteorological conditions were evaluated using radiosonde observations and ground-based measurements. The overall vertical structure of the boundary layer is discussed, together with validation of the surface energy balance and turbulent fluxes. The sensible heat and momentum fluxes above the canopy were on average overestimated, while the latent heat flux was underestimated.
Heavy air pollution episodes in Beijing during January 2013: inorganic ion chemistry and source analysis using Highly Time-Resolved Measurements in an urban site

Heavy air pollution episodes occurred in Beijing in January 2013 attracted intensively attention around the whole world. During this period, the authors conducted highly time-resolved measurements of water soluble ions associated with PM2.5 at an urban site, and attempted to distinguish the ion chemistry and potential sources. In this study, hourly mean concentrations of Cl−, NO3−, SO42−, Na+, NH4+, K+, Mg2+ and Ca2+ were measured during the air pollution episode in January 2013, and the ions were found to exist mainly in the form of (NH4)2SO4, NH4NO3, NaCl and KCl in aerosol particles by correlation and linear analysis. SO42− and NO3− were observed peak concentrations in 10–15, 18–20, 21–24, and 26–30 January during this monitoring campaign. The percentage of SO42− and NH4+ in total ions concentrations exhibited an increasing trend with the enhancement of PM2.5 concentration, indicating high concentrations of SO42− and NH4+ had played important roles in the formation of air pollution episodes. Ratio of [NO3−]/[SO42−] was calculated, finding the sources of SO42− would contribute more to the formation of PM2.5 than mobile sources. Diurnal variations of SO42−, NO3−, NH4+ were examined, and all of them exhibited similar pattern with high concentration in night and relative low level at daytime. Emission from coal combustion, remote transportation at night or impact of meteorological was likely to be responsible for the high level of SO42−, NH4+ andNO3−. Potential sources were identified by applying PMF. Secondary nitrate, secondary sulfate, coal combustion and biomass burning, as well as fugitive dust were considered as the major contributors to total ions.
Evaluation of the GEM-AQ model in the context of the AQMEII Phase 1 project

In the scope of the AQMEII Phase 1 project the GEM-AQ model was run over Europe for the year 2006. The modelling domain was defined using a global variable resolution grid with a rotated equator and uniform resolution of 0.2° × 0.2° over the European continent. Spatial distribution and temporal variability of the GEM-AQ model results were analysed for surface ozone and PM10 concentrations. Model results were compared with measurements available in the ENSEMBLE database. Statistical measures were used to evaluate performance of the GEM-AQ model. The mean bias error, the mean absolute gross error and the Pearson correlation coefficient were calculated for the maximum 8 h running average ozone concentrations and daily mean PM10 concentrations. The GEM-AQ model performance was characterized for station types, European climatic regions and seasons. The best performance for ozone was obtained at suburban stations, and the worst performance was obtained for rural stations where the model tends to underestimate. The best results for PM10 were calculated for urban stations, while over most of Europe concentrations at rural sites were too high. Discrepancies between modelled and observed concentrations were discussed in the context of emission data uncertainty as well as the impact of large-scale dynamics and circulation of air masses. Presented analyses suggest that interpretation of modelling results is enhanced when regional climate characteristics are taken into consideration.
Trends and drivers of ozone human health and vegetation impact metrics from UK EMEP supersite measurements (1990–2013)

Analyses have been undertaken of the spatial and temporal trends and drivers of the distributions of ground-level O3 concentrations associated with potential impacts on human health and vegetation using measurements at the two UK European Monitoring and Evaluation Program (EMEP) supersites of Harwell and Auchencorth. These two sites provide representation of rural O3 over the wider geographic areas of south-east England and northern UK respectively. The O3 exposures associated with health and vegetation impacts were quantified respectively by the SOMO10 and SOMO35 metrics and by the flux-based PODY metrics for wheat, potato, beech and Scots pine. Statistical analyses of measured O3 and NOx concentrations were supplemented by analyses of meteorological data and NOx emissions along air-mass back trajectories. The findings highlight the differing responses of impact metrics to the decreasing contribution of regional O3 episodes in determining O3 concentrations at Harwell between 1990 and 2013, associated with European NOx emission reductions. An improvement in human health-relevant O3 exposure observed when calculated by SOMO35, which decreased significantly, was not observed when quantified by SOMO10. The decrease in SOMO35 is driven by decreases in regionally produced O3 which makes a larger contribution to SOMO35 than to SOMO10. For the O3 vegetation impacts at Harwell, no significant trend was observed for the PODY metrics of the four species, in contrast to the decreasing trend in vegetation-relevant O3 exposure perceived when calculated using the crop AOT40 metric. The decreases in regional O3 production have not decreased PODY as climatic and plant conditions reduced stomatal conductance and uptake of O3 during regional O3 production. Ozone concentrations at Auchencorth (2007–2013) were more influenced by hemispheric background concentrations than at Harwell. For health-related O3 exposures this resulted in lower SOMO35 but similar SOMO10 compared with Harwell; for vegetation PODY values, this resulted in greater impacts at Auchencorth for vegetation types with lower exceedance ("Y") thresholds and longer growing seasons (i.e. beech and Scots pine). Additionally, during periods influenced by regional O3 production, a greater prevalence of plant conditions which enhance O3 uptake (such as higher soil water potential) at Auchencorth compared to Harwell resulted in exacerbation of vegetation impacts at Auchencorth, despite being further from O3 precursor emission sources. These analyses indicate that quantifications of future improvement in health-relevant O3 exposure achievable from pan-European O3 mitigation strategies are highly dependent on the choice of O3 concentration cut-off threshold, and reduction in potential health impact associated with more modest O3 concentrations requires reductions in O3 precursors on a larger (hemispheric) spatial scale. Additionally, while further reduction in regional O3 is more likely to decrease O3 vegetation impacts within the spatial domain of Auchencorth compared to Harwell, larger reductions in vegetation impact could be achieved across the UK from reduction of hemispheric background O3 concentrations.
Aerosol optical hygroscopicity measurements during the 2010 CARES campaign

Measurements of the effect of water uptake on particulate light extinction or scattering made at two locations during the 2010 Carbonaceous Aerosols and Radiative Effects Study (CARES) study around Sacramento, CA are reported. The observed influence of water uptake, characterized through the dimensionless optical hygroscopicity parameter γ, is compared with calculations constrained by observed particle size distributions and size-dependent particle composition. A closure assessment has been carried out that allowed for determination of the average hygroscopic growth factors (GFs) at 85% relative humidity and the dimensionless hygroscopicity parameter κ for oxygenated organic aerosol (OA) and for supermicron particles (defined here as particles with aerodynamic diameters between 1 and 2.5 microns), yielding κ = 0.1–0.15 and 0.9–1.0, respectively. The derived range of oxygenated OA κ values are in line with previous observations. The relatively large values for supermicron particles is consistent with substantial contributions of sea-salt-containing particles in this size range. Analysis of time-dependent variations in the supermicron particle hygroscopicity suggest that atmospheric processing, specifically chloride displacement by nitrate and the accumulation of secondary organics on supermicron particles, can lead to substantial depression of the observed GF.
Corrigendum to "Photosensitised heterogeneous oxidation kinetics of biomass burning aerosol surrogates by ozone using an irradiated rectangular channel flow reactor" published in Atmos. Chem. Phys., 13, 6507–6522, 2013