Marine cloud brightening through sea spray injection has been proposed as a climate engineering method for avoiding the most severe consequences of global warming. A limitation of most of the previous modelling studies on marine cloud brightening is that they have either considered individual models or only investigated the effects of a specific increase in the number of cloud droplets. Here we present results from coordinated simulations with three Earth system models (ESMs) participating in the Geoengineering Model Intercomparison Project (GeoMIP) G4sea-salt experiment. Injection rates of accumulation-mode sea spray aerosol particles over ocean between 30 degrees N and 30 degrees S are set in each model to generate a global-mean effective radiative forcing (ERF) of -2.0 W m(-2) at the top of the atmosphere. We find that the injection increases the cloud droplet number concentration in lower layers, reduces the cloud-top effective droplet radius, and increases the cloud optical depth over the injection area. We also find, however, that the global-mean clear-sky ERF by the injected particles is as large as the corresponding total ERF in all three ESMs, indicating a large potential of the aerosol direct effect in regions of low cloudiness. The largest enhancement in ERF due to the presence of clouds occur as expected in the subtropical stratocumulus regions off the west coasts of the American and African continents. However, outside these regions, the ERF is in general equally large in cloudy and clear-sky conditions. These findings suggest a more important role of the aerosol direct effect in sea spray climate engineering than previously thought.

Sulfuric acid, amines and oxidized organics have been found to be important compounds in the nucleation and initial growth of atmospheric particles. Because of the challenges involved in determining the chemical composition of objects with very small mass, however, the properties of the freshly nucleated particles and the detailed pathways of their formation processes are still not clear. In this study,we focus on a challenging size range, i.e., particles that have grown to diameters of 10 and 15 nm following nucleation, and measure their water uptake. Water uptake is useful information for indirectly obtaining chemical composition of aerosol particles. We use a nanometer-hygroscopicity tandem differential mobility analyzer (nano-HTDMA) at sub-saturated conditions (ca. 90% relative humidity at 293 K) to measure the hygroscopicity of particles during the seventh Cosmics Leaving OUtdoor Droplets (CLOUD7) campaign performed at CERN in 2012. In CLOUD7, the hygroscopicity of nucleated nanoparticles was measured in the presence of sulfuric acid, sulfuric acid-dimethylamine, and sulfuric acid-organics derived from alpha-pinene oxidation. The hygroscopicity parameter kappa decreased with increasing particle size, indicating decreasing acidity of particles. No clear effect of the sulfuric acid concentration on the hygroscopicity of 10 nm particles produced from sulfuric acid and dimethylamine was observed, whereas the hygroscopicity of 15 nm particles sharply decreased with decreasing sulfuric acid concentrations. In particular, when the concentration of sulfuric acid was 5.1 x 10(6) molecules cm(-3) in the gas phase, and the dimethylamine mixing ratio was 11.8 ppt, the measured kappa of 15 nm particles was 0.31 +/- 0.01: close to the value reported for dimethylaminium sulfate (DMAS) (kappa(DMAS) similar to 0.28). Furthermore, the difference in kappa between sulfuric acid and sulfuric acid-dimethylamine experiments increased with increasing particle size. The kappa values of particles in the presence of sulfuric acid and organics were much smaller than those of particles in the presence of sulfuric acid and dimethylamine. This suggests that the organics produced from alpha-pinene ozonolysis play a significant role in particle growth even at 10 nm sizes.

The particle formation scheme within PMCAMx-UF, a three-dimensional chemical transport model, was updated with particle formation rates for the ternary H2SO4-NH3-H2O pathway simulated by the Atmospheric Cluster Dynamics Code (ACDC) using quantum chemical input data. The model was applied over Europe for May 2008, during which the EUCAARI-LONGREX (European Aerosol Cloud Climate and Air Quality Interactions-Long-Range Experiment) campaign was carried out, providing aircraft vertical profiles of aerosol number concentrations. The updated model reproduces the observed number concentrations of particles larger than 4 nm within 1 order of magnitude throughout the atmospheric column. This agreement is encouraging considering the fact that no semi-empirical fitting was needed to obtain realistic particle formation rates. The cloud adjustment scheme for modifying the photolysis rate profiles within PMCAMx-UF was also updated with the TUV (Tropospheric Ultraviolet and Visible) radiative-transfer model. Results show that, although the effect of the new cloud adjustment scheme on total number concentrations is small, enhanced new-particle formation is predicted near cloudy regions. This is due to the enhanced radiation above and in the vicinity of the clouds, which in turn leads to higher production of sulfuric acid. The sensitivity of the results to including emissions from natural sources is also discussed.

Dimethylamine (DMA) has a stabilizing effect on sulfuric acid (SA) clusters, and the SA and DMA molecules and clusters likely play important roles in both aerosol particle formation and growth in the atmosphere. We use the monodisperse particle growth model for acid-base chemistry in nanoparticle growth (MABNAG) together with direct and indirect observations from the CLOUD4 and CLOUD7 experiments in the cosmics leaving outdoor droplets (CLOUD) chamber at CERN to investigate the size and composition evolution of freshly formed particles consisting of SA, DMA, and water as they grow to 20nm in dry diameter. Hygroscopic growth factors are measured using a nano-hygroscopicity tandem differential mobility analyzer (nano-HTDMA), which combined with simulations of particle water uptake using the thermodynamic extended-aerosol inorganics model (E-AIM) constrain the chemical composition. MABNAG predicts a particle-phase ratio between DMA and SA molecules of 1.1-1.3 for a 2nm particle and DMA gas-phase mixing ratios between 3.5 and 80 pptv. These ratios agree well with observations by an atmospheric-pressure interface time-of-flight (APi-TOF) mass spectrometer. Simulations with MABNAG, direct observations of the composition of clusters <2nm, and indirect observations of the particle composition indicate that the acidity of the nucleated particles decreases as they grow from approximate to 1 to 20nm. However, MABNAG predicts less acidic particles than suggested by the indirect estimates at 10nm diameter using the nano-HTDMA measurements, and less acidic particles than observed by a thermal desorption chemical ionization mass spectrometer (TDCIMS) at 10-30nm. Possible explanations for these discrepancies are discussed.

The growth of freshly formed aerosol particles can be the bottleneck in their survival to cloud condensation nuclei. It is therefore crucial to understand how particles grow in the atmosphere. Insufficient experimental data has impeded a profound understanding of nano-particle growth under atmospheric conditions. Here we study nano-particle growth in the CLOUD (Cosmics Leaving OUtdoors Droplets) chamber, starting from the formation of molecular clusters. We present measured growth rates at sub-3 nm sizes with different atmospherically relevant concentrations of sulphuric acid, water, ammonia and dimethylamine. We find that atmospheric ions and small acid-base clusters, which are not generally accounted for in the measurement of sulphuric acid vapour, can participate in the growth process, leading to enhanced growth rates. The availability of compounds capable of stabilizing sulphuric acid clusters governs the magnitude of these effects and thus the exact growth mechanism. We bring these observations into a coherent framework and discuss their significance in the atmosphere.

About half of present-day cloud condensation nuclei originate from atmospheric nucleation, frequently appearing as a burst of new particles near midday(1). Atmospheric observations show that the growth rate of new particles often accelerates when the diameter of the particles is between one and ten nanometres(2,3). In this critical size range, new particles are most likely to be lost by coagulation with pre-existing particles(4), thereby failing to form new cloud condensation nuclei that are typically 50 to 100 nanometres across. Sulfuric acid vapour is often involved in nucleation but is too scarce to explain most subsequent growth(5,6), leaving organic vapours as the most plausible alternative, at least in the planetary boundary layer(7-10). Although recent studies(11-13) predict that low-volatility organic vapours contribute during initial growth, direct evidence has been lacking. The accelerating growth may result from increased photolytic production of condensable organic species in the afternoon(2), and the presence of a possible Kelvin (curvature) effect, which inhibits organic vapour condensation on the smallest particles (the nano-Kohler theory)(2,14), has so far remained ambiguous. Here we present experiments performed in a large chamber under atmospheric conditions that investigate the role of organic vapours in the initial growth of nucleated organic particles in the absence of inorganic acids and bases such as sulfuric acid or ammonia and amines, respectively. Using data from the same set of experiments, it has been shown(15) that organic vapours alone can drive nucleation. We focus on the growth of nucleated particles and find that the organic vapours that drive initial growth have extremely low volatilities (saturation concentration less than 10(-4.5) micrograms per cubic metre). As the particles increase in size and the Kelvin barrier falls, subsequent growth is primarily due to more abundant organic vapours of slightly higher volatility (saturation concentrations of 10(-4.5) to 10(-0.5) micrograms per cubic metre). We present a particle growth model that quantitatively reproduces our measurements. Furthermore, we implement a parameterization of the first steps of growth in a global aerosol model and find that concentrations of atmospheric cloud concentration nuclei can change substantially in response, that is, by up to 50 per cent in comparison with previously assumed growth rate parameterizations.

New particle formation driven by acid-base chemistry was initiated in the CLOUD chamber at CERN by introducing atmospherically relevant levels of gas-phase sulfuric acid and dimethylamine (DMA). Ammonia was also present in the chamber as a gas-phase contaminant from earlier experiments. The composition of particles with volume median diameters (VMDs) as small as 10 nm was measured by the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS). Particulate ammonium-to-dimethylaminium ratios were higher than the gas-phase ammonia-to-DMA ratios, suggesting preferential uptake of ammonia over DMA for the collected 10-30 nm VMD particles. This behavior is not consistent with present nanoparticle physicochemical models, which predict a higher dimethylaminium fraction when NH3 and DMA are present at similar gas-phase concentrations. Despite the presence in the gas phase of at least 100 times higher base concentrations than sulfuric acid, the recently formed particles always had measured base : acid ratios lower than 1 : 1. The lowest base fractions were found in particles below 15 nm VMD, with a strong size-dependent composition gradient. The reasons for the very acidic composition remain uncertain, but a plausible explanation is that the particles did not reach thermodynamic equilibrium with respect to the bases due to rapid heterogeneous conversion of SO2 to sulfate. These results indicate that sulfuric acid does not require stabilization by ammonium or dimethylaminium as acid-base pairs in particles as small as 10 nm.

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 super-saturations 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 Kohler- 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.

From May 2008 to March 2009 aerosol emissions were measured using the eddy covariance method covering the size range 0.25 to 2.5 mu m diameter (D-p) from a 105m tower, in central Stockholm, Sweden. Supporting chemical aerosol data were collected at roof and street level. Results show that the inorganic fraction of sulfate, nitrate, ammonium and sea salt accounts for approximately 15% of the total aerosol mass < 1 mu m D-p (PM1) with water soluble soil contributing 11% and water insoluble soil 47%. Carbonaceous compounds were at the most 27% of PM1 mass. It was found that heating the air from the tower to 200 degrees C resulted in the loss of approximately 60% of the aerosol volume at 0.25 mu m D-p whereas only 40% of the aerosol volume was removed at 0.6 mu m D-p. Further heating to 300 degrees C caused very little additional losses < 0.6 mu m D-p. The chemical analysis did not include carbonaceous compounds, but based on the difference between the total mass concentration and the sum of the analyzed non-carbonaceous materials, it can be assumed that the non-volatile particulate material (heated to 300 degrees C) consists mainly of carbonaceous compounds, including elemental carbon. Furthermore, it was found that the nonvolatile particle fraction < 0.6 mu m D-p correlated (r(2) = 0.4) with the BC concentration at roof level in the city, supporting the assumption that the non-volatile material consists of carbonaceous compounds. The average diurnal cycles of the BC emissions from road traffic (as inferred from the ratio of the incremental concentrations of nitrogen oxides (NOx) and BC measured on a densely trafficked street) and the fluxes of non-volatile material at tower level are in close agreement, suggesting a traffic source of BC. We have estimated the emission factors (EFs) for non-volatile particles < 0.6 mu m D-p to be 2.4 +/- 1.4 mg veh(-1) km(-1) based on either CO2 fluxes or traffic activity data. Light (LDV) and heavy duty vehicle (HDV) EFs were estimated using multiple linear regression and reveal that for non-volatile particulate matter in the 0.25 to 0.6 mu m D-p range, the EFHDV is approximately twice as high as the EFLDV, the difference not being statistically significant.

The aerosol particle number concentration is a key parameter when estimating impacts of aerosol particles on climate and human health. We use a three-dimensional chemical transport model with detailed microphysics, PMCAMx-UF, to simulate particle number concentrations over Europe in the year 2030, by applying emission scenarios for trace gases and primary aerosols. The scenarios are based on expected changes in anthropogenic emissions of sulfur dioxide, ammonia, nitrogen oxides, and primary aerosol particles with a diameter less than 2.5 mu m (PM2.5) focusing on a photochemically active period, and the implications for other seasons are discussed. For the baseline scenario, which represents a best estimate of the evolution of anthropogenic emissions in Europe, PMCAMx-UF predicts that the total particle number concentration (N-tot) will decrease by 30-70% between 2008 and 2030. The number concentration of particles larger than 100 nm (N-100), a proxy for cloud condensation nuclei (CCN) concentration, is predicted to decrease by 40-70% during the same period. The predicted decrease in N-tot is mainly a result of reduced new particle formation due to the expected reduction in SO2 emissions, whereas the predicted decrease in N-100 is a result of both decreasing condensational growth and reduced primary aerosol emissions. For larger emission reductions, PMCAMx-UF predicts reductions of 60-80% in both N-tot and N-100 over Europe. Sensitivity tests reveal that a reduction in SO2 emissions is far more efficient than any other emission reduction investigated, in reducing N-tot. For N-100, emission reductions of both SO2 and PM2.5 contribute significantly to the reduced concentration, even though SO2 plays the dominant role once more. The impact of SO2 for both new particle formation and growth over Europe may be expected to be somewhat higher during the simulated period with high photochemical activity than during times of the year with less incoming solar radiation. The predicted reductions in both N-tot and N-100 between 2008 and 2030 in this study will likely reduce both the aerosol direct and indirect effects, and limit the damaging effects of aerosol particles on human health in Europe