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Heterogeneous ice nucleation of viscous secondary organic aerosol produced from ozonolysis of α-pinene

There are strong indications that particles containing secondary organic aerosol (SOA) exhibit amorphous solid or semi-solid phase states in the atmosphere. This may facilitate heterogeneous ice nucleation and thus influence cloud properties. However, experimental ice nucleation studies of biogenic SOA are scarce. Here, we investigated the ice nucleation ability of viscous SOA particles. The SOA particles were produced from the ozone initiated oxidation of α-pinene in an aerosol chamber at temperatures in the range from −38 to −10 °C at 5–15 % relative humidity with respect to water to ensure their formation in a highly viscous phase state, i.e. semi-solid or glassy. The ice nucleation ability of SOA particles with different sizes was investigated with a new continuous flow diffusion chamber. For the first time, we observed heterogeneous ice nucleation of viscous α-pinene SOA for ice saturation ratios between 1.3 and 1.4 significantly below the homogeneous freezing limit. The maximum frozen fractions found at temperatures between −39.0 and −37.2 °C ranged from 6 to 20 % and did not depend on the particle surface area. Global modelling of monoterpene SOA particles suggests that viscous biogenic SOA particles are indeed present in regions where cirrus cloud formation takes place. Hence, they could make up an important contribution to the global ice nucleating particle budget.
Assessing atmospheric dust modelling performance of WRF-Chem over the semi-arid and arid regions around the Mediterranean

In this study we aim at optimizing the WRF-Chem model performance for the purpose of operational forecasting of dust transport over the eastern Mediterranean. For this reason, we compare the model output to observations in order to assess its capacity to realistically reproduce the aerosol optical depth (AOD), focusing on three key regions: North Africa, the Arabian Peninsula and the eastern Mediterranean. Three sets of four simulations each have been performed for the six-month period of spring and summer 2011. Each simulation set uses a different dust emission parametrisation and for each parametrisation, the dust emissions are multiplied with various coefficients in order to tune the model performance. Our approach is based on the model assessment across spatial and temporal scales by comparing its outputs to AOD observations from satellites and ground-based stations, as well as airborne measurements of aerosol extinction coefficients over the Sahara. Tuning the model performance by applying a coefficient to dust emissions may reduce the model AOD bias over a region, but may increase it in other regions. Concerning dust transport over the eastern Mediterranean, the model was shown to realistically reproduce the major transport events, however failing to capture the regional background AOD. Model assessment over the entire domain and simulation period shows that the model presents temporal and spatial variability similar to observed AODs, regardless of the applied dust emission parametrisation. However, when focusing on specific regions, the model’s skill may vary significantly. Further comparison of the model simulations to airborne measurements of the vertical profiles of extinction coefficients over North Africa suggests that the model may realistically reproduce the total atmospheric column AOD. Finally, we show that the inclusion of a finer dust mode (less than 1 μm) in the model presents the advantage of relaxing unrealistically large atmospheric dust loads and yet reproducing realistic AOD values.
Impacts of anthropogenic and natural sources on free tropospheric ozone over the Middle East

Significant progress has been made in identifying the influence of different processes and emissions on the summertime enhancements of free tropospheric ozone (O3) at northern midlatitude regions. However, the exact contribution of regional emissions, chemical and transport processes to these summertime enhancements is still not well quantified. Here we focus on quantifying the influence of regional emissions on the summertime O3 enhancements over the Middle East, using updated reactive nitrogen (NOx) emissions. We then use the adjoint of the GEOS-Chem model with these updated NOx emissions to show that the global total contribution of lightning NOx on middle free tropospheric O3 over the Middle East is about 2 times larger than that from global anthropogenic sources. The summertime middle free tropospheric O3 enhancement is primarily due to Asian NOx emissions, with approximately equivalent contributions from Asian anthropogenic activities and lightning. In the Middle Eastern lower free troposphere, lightning NOx from Europe and North America and anthropogenic NOx from Middle Eastern local emissions are the primary sources of O3. This work highlights the critical role of lightning NOx on northern midlatitude free tropospheric O3 and the important effect of the Asian summer monsoon on the export of Asian pollutants.
Long-resident droplets at the stratocumulus top

Turbulence models predict low droplet-collision rates in stratocumulus clouds, which should imply a narrow droplet size distribution and little rain. Contrary to this expectation, rain is often observed in stratocumuli. In this paper, we explore the hypothesis that some droplets can grow well above the average because small-scale turbulence allows them to reside at cloud top for a time longer than the convective-eddy time t*. Long-resident droplets can grow larger because condensation due to longwave radiative cooling, and collisions have more time to enhance droplet growth. We investigate the trajectories of 1 billion Lagrangian droplets in direct numerical simulations of a cloudy mixed-layer configuration that is based on observations from the flight 11 from the VERDI campaign. High resolution is employed to represent a well-developed turbulent state at cloud top. Only one-way coupling is considered. We observe that 70 % of the droplets spend less than 0.6t* at cloud top before leaving the cloud, while 15 % of the droplets remain at least 0.9t* at cloud top. In addition, 0.2 % of the droplets spend more than 2.5t* at cloud top and decouple from the large-scale convective eddies that brought them to the top, with the result that they become memoryless. Modeling collisions like a Poisson process leads to the conclusion that most rain droplets originate from those memoryless droplets. Furthermore, most long-resident droplets accumulate at the downdraft regions of the flow, which could be related to the closed-cell stratocumulus pattern. Finally, we see that condensation due to longwave radiative cooling considerably broadens the cloud-top droplet size distribution: 6.5 % of the droplets double their mass due to radiation in their time at cloud top. This simulated droplet size distribution matches the flight measurements, confirming that condensation due to longwave radiation can be an important mechanism for broadening the droplet size distribution in radiatively driven stratocumuli.
Experimental study of the aerosol impact on fog microphysics

Comprehensive field campaigns dedicated to fog life cycle observation were conducted during the winters of 2010–2013 at the SIRTA observatory in the suburb of Paris. In order to document their properties, in situ microphysical measurements collected during 23 fog events are examined here. They reveal large variability in number, concentration and size of both aerosol background before the fog onset and fog droplets according to the different cases. The objective of this paper is to evaluate the impact of aerosol particles on the fog microphysics. To derive an accurate estimation of the actual activated fog droplet number concentration N act, we determine the hygroscopicity parameter κ, the dry and the wet critical diameter and the critical supersaturation for each case by using an iterative procedure based on the κ-Köhler theory that combines cloud condensation nuclei (CCN), dry particle and droplet size distribution measurements. Resulting values of κ = 0.17 ± 0.05 were found typical of continental aerosols. Our study reveals low values of the derived critical supersaturation with a median of 0.043 % and large values for both wet and dry activation diameters. Consequently, the corresponding N act values are low with median concentrations of 53.5 cm−3 and 111 cm−3 within the percentile 75th. No detectable trend between the concentration of aerosol particles with diameter > 200 nm and N act was observed. In contrast the CCN data at 0.1 % supersaturation exhibits a strong correlation with these aerosol concentrations. We therefore conclude that the actual supersaturations reached during these fog episodes are too low and no simultaneous increase of aerosols > 200 nm and droplet concentrations can be observed. Moreover our analysis suggests that a high aerosol loading limits the supersaturation values. It is also found that the activated fraction mainly depends on the aerosol size while the hygroscopicity appears to be of a secondary importance. Although radiative fogs are usually associated with higher aerosol loading rather than to stratus lowering events, our analysis reveals that the activated particle concentrations at the beginning of the event are similar for both types of fog. However the evolution of the droplet concentration during the fog life cycle shows significant differences between both types of fog.
Temperature-dependent diffusion coefficient of H2SO4 in air: laboratory measurements using laminar flow technique

We report measurements of the diffusion coefficient of sulfuric acid in humidified air at a range of relative humidities (from ~4 to 70 %), temperatures (278, 288 and 298 K) and initial H2SO4 concentration (from 1 × 10e6 to 1 × 10e8 molec. cm−3). The diffusion coefficients were estimated from the sulfuric acid wall loss rate coefficients under laminar flow conditions. The flow conditions were verified with additional fluid dynamics model CFD-FLUENT simulations which also reproduced the loss rate coefficients very well at all three temperatures with the maximum difference of 7 % between the measured and simulated values. The concentration of H2SO4 was measured continuously with chemical ionization mass spectrometer (CIMS) at seven different positions along the flow tube. The wall losses of H2SO4 were determined from the slopes of fits to measured H2SO4 concentrations as a function of the position along the flow tube. The observed wall loss rate coefficients, and hence the diffusion coefficients, were independent of different initial H2SO4 concentrations and different total flow rates. However, the determined diffusion coefficients decreased with increasing relative humidity, as also seen in previous experiments, and had a rather strong power dependence of the diffusion coefficient with respect to temperature, around ∝T5.4, which is in disagreement with the expected temperature dependency of ~T1.75 observed for other gases and not tested before for sulfuric acid. The effect of relative humidity on the diffusion coefficient is likely due to stronger hydration of H2SO4 molecules and likely also due to the presence of trace impurities such as amines, possibly brought to the system by humidification. Clustering kinetics simulations using quantum chemical data suggest that also the strong temperature dependence of the observed diffusion coefficient might be explained by increased diffusion volume of H2SO4 molecules due to stronger clustering with base-impurities like amines.
Size-resolved morphological properties of the high Arctic summer aerosol during ASCOS-2008

The representation of aerosol properties and processes in climate models is fraught with large uncertainties. Especially at high northern latitudes a strong underprediction of aerosol concentrations and nucleation events is observed and can only be constrained by in situ observations based on the analysis of individual aerosol particles. To further reduce the uncertainties surrounding aerosol properties and their potential role as cloud condensation nuclei this study provides observational data resolved over size on morphological and chemical properties of aerosol particles collected in the summer high Arctic, north of 80° N. Aerosol particles were imaged with scanning and transmission electron microscopy and further evaluated with digital image analysis. In total, 3909 aerosol particles were imaged and categorized according to morphological similarities into three gross morphological groups: single particles, gel particles, and halo particles. Single particles were observed between 15 and 800 nm in diameter and represent the dominating type of particles (82 %). The majority of particles appeared to be marine gels with a broad Aitken mode peaking at 70 nm and accompanied by a minor fraction of ammonium (bi)sulfate with a maximum at 170 nm in number concentration. Gel particles (11 % of all particles) were observed between 45 and 800 nm with a maximum at 154 nm in diameter. Imaging with transmission electron microscopy allowed further morphological discrimination of gel particles in "aggregate" particles, "aggregate with film" particles, and "mucus-like" particles. Halo particles were observed above 75 nm and appeared to be ammonium (bi)sulfate (59 % of halo particles), gel matter (19 %), or decomposed gel matter (22 %), which were internally mixed with sulfuric acid, methane sulfonic acid, or ammonium (bi)sulfate with a maximum at 161 nm in diameter. Elemental dispersive X-ray spectroscopy analysis of individual particles revealed a prevalence of the monovalent ions Na+/K+ for single particles and aggregate particles and of the divalent ions Ca2+/Mg2+ for aggregate with film particles and mucus-like particles. According to these results and other model studies, we propose a relationship between the availability of Na+/K+ and Ca2+/Mg2+ and the length of the biopolymer molecules participating in the formation of the three-dimensional gel networks.
Limitations of passive remote sensing to constrain global cloud condensation nuclei

Aerosol–cloud interactions are considered a key uncertainty in our understanding of climate change (Boucher et al., 2013). Knowledge of the global abundance of cloud condensation nuclei (CCN) is fundamental to determine the strength of the anthropogenic climate perturbation. Direct measurements are limited and sample only a very small fraction of the globe so that remote sensing from satellites and ground-based instruments is widely used as a proxy for cloud condensation nuclei (Nakajima et al., 2001; Andreae, 2009; Clarke and Kapustin, 2010; Boucher et al., 2013). However, the underlying assumptions cannot be robustly tested with the small number of measurements available so that no reliable global estimate of cloud condensation nuclei exists. This study overcomes this limitation using a self-consistent global model (ECHAM-HAM) of aerosol radiative properties and cloud condensation nuclei. An analysis of the correlation of simulated aerosol radiative properties and cloud condensation nuclei reveals that common assumptions about their relationships are violated for a significant fraction of the globe: 71 % of the area of the globe shows correlation coefficients between CCN0.2 % at cloud base and aerosol optical depth (AOD) below 0.5, i.e. AOD variability explains only 25 % of the CCN variance. This has significant implications for satellite based studies of aerosol–cloud interactions. The findings also suggest that vertically resolved remote-sensing techniques, such as satellite-based high spectral resolution lidars, have a large potential for global monitoring of cloud condensation nuclei.
Effectiveness of replacing catalytic converters in LPG-fueled vehicles in Hong Kong

Many taxis and public buses are powered by liquefied petroleum gas (LPG) in Hong Kong. With more vehicles using LPG, they have become the major contributor to ambient volatile organic compounds (VOCs) in Hong Kong. An intervention program which aimed to reduce the emissions of VOCs and nitrogen oxides (NOx) from LPG-fueled vehicles was implemented by the Hong Kong government in September 2013. Long-term real-time measurements indicated that the program was remarkably effective in reducing LPG-related VOCs, NOx and nitric oxide (NO) in the atmosphere. Receptor modeling results further revealed that propane, propene, i-butane, n-butane and NO in LPG-fueled vehicle exhaust emissions decreased by 40.8 ± 0.1, 45.7 ± 0.2, 35.7 ± 0.1, 47.8 ± 0.1 and 88.6 ± 0.7 %, respectively, during the implementation of the program. In contrast, despite the reduction of VOCs and NOx, O3 following the program increased by 0.40 ± 0.03 ppbv (∼  5.6 %). The LPG-fueled vehicle exhaust was generally destructive to OH and HO2. However, the destruction effect weakened for OH and it even turned to positive contribution to HO2 during the program. These changes led to the increases of OH, HO2 and HO2 ∕ OH ratio, which might explain the positive O3 increment. Analysis of O3–VOCs–NOx sensitivity in ambient air indicated VOC-limited regimes in the O3 formation before and during the program. Moreover, a maximum reduction percentage of NOx (i.e., 69 %) and the lowest reduction ratio of VOCs ∕ NOx (i.e., 1.1) in LPG-fueled vehicle exhaust were determined to give a zero O3 increment. The findings are of great help to future formulation and implementation of control strategies on vehicle emissions in Hong Kong, and could be extended to other regions in China and around the world.
Climatology of the aerosol optical depth by components from the Multi-angle Imaging SpectroRadiometer (MISR) and chemistry transport models

The Multi-angle Imaging SpectroRadiometer (MISR) Joint Aerosol (JOINT_AS) Level 3 product has provided a global, descriptive summary of MISR Level 2 aerosol optical depth (AOD) and aerosol type information for each month over 16+ years since March 2000. Using Version 1 of JOINT_AS, which is based on the operational (Version 22) MISR Level 2 aerosol product, this study analyzes, for the first time, characteristics of observed and simulated distributions of AOD for three broad classes of aerosols: spherical nonabsorbing, spherical absorbing, and nonspherical – near or downwind of their major source regions. The statistical moments (means, standard deviations, and skewnesses) and distributions of AOD by components derived from the JOINT_AS are compared with results from two chemistry transport models (CTMs), the Goddard Chemistry Aerosol Radiation and Transport (GOCART) and SPectral RadIatioN-TrAnSport (SPRINTARS). Overall, the AOD distributions retrieved from MISR and modeled by GOCART and SPRINTARS agree with each other in a qualitative sense. Marginal distributions of AOD for each aerosol type in both MISR and models show considerable high positive skewness, which indicates the importance of including extreme AOD events when comparing satellite retrievals with models. The MISR JOINT_AS product will greatly facilitate comparisons between satellite observations and model simulations of aerosols by type.