Stable sulphate clusters as a source of new atmospheric particles

The formation of new atmospheric particles with diameters of 3-10 nm has been observed at a variety of altitudes and locations. Such aerosol particles have the potential to grow into cloud condensation nuclei, thus affecting cloud formation as well as the global radiation budget. In some cases, the observed formation rates of new particles have been adequately explained by binary nucleation, involving water and sulphuric acid, but in certain locations--particularly those within the marine boundary layer and at continental sites--observed ambient nucleation rates exceed those predicted by the binary scheme. In these locations, ambient sulphuric acid (H2SO4) levels are typically lower than required for binary nucleation, but are sufficient for ternary nucleation (sulphuric acid-ammonia-water). Here we present results from an aerosol dynamics model with a ternary nucleation scheme which indicate that nucleation in the troposphere should be ubiquitous, and yield a reservoir of thermodynamically stable clusters 1-3 nm in size. We suggest that the growth of these clusters to a detectable size (> 3 nm particle diameter) is restricted by the availability of condensable vapour. Observations of atmospheric particle formation and growth from a continental and a coastal site support this hypothesis, indicating that a growth process including ternary nucleation is likely to be responsible for the formation of cloud condensation nuclei.     

Marine aerosol formation from biogenic iodine emissions

The formation of marine aerosols and cloud condensation nuclei--from which marine clouds originate--depends ultimately on the availability of new, nanometre-scale particles in the marine boundary layer. Because marine aerosols and clouds scatter incoming radiation and contribute a cooling effect to the Earth's radiation budget, new particle production is important in climate regulation. It has been suggested that sulphuric acid derived from the oxidation of dimethyl sulphide is responsible for the production of marine aerosols and cloud condensation nuclei. It was accordingly proposed that algae producing dimethyl sulphide play a role in climate regulation, but this has been difficult to prove and, consequently, the processes controlling marine particle formation remains largely undetermined. Here, using smog chamber experiments under coastal atmospheric conditions, we demonstrate that new particles can form from condensable iodine-containing vapours, which are the photolysis products of biogenic iodocarbons emitted from marine algae. Moreover, we illustrate, using aerosol formation models, that concentrations of condensable iodine-containing vapours over the open ocean are sufficient to influence marine particle formation. We suggest therefore that marine iodocarbon emissions have a potentially significant effect on global radiative forcing.     

The case against climate regulation via oceanic phytoplankton sulphur emissions

More than twenty years ago, a biological regulation of climate was proposed whereby emissions of dimethyl sulphide from oceanic phytoplankton resulted in the formation of aerosol particles that acted as cloud condensation nuclei in the marine boundary layer. In this hypothesis--referred to as CLAW--the increase in cloud condensation nuclei led to an increase in cloud albedo with the resulting changes in temperature and radiation initiating a climate feedback altering dimethyl sulphide emissions from phytoplankton. Over the past two decades, observations in the marine boundary layer, laboratory studies and modelling efforts have been conducted seeking evidence for the CLAW hypothesis. The results indicate that a dimethyl sulphide biological control over cloud condensation nuclei probably does not exist and that sources of these nuclei to the marine boundary layer and the response of clouds to changes in aerosol are much more complex than was recognized twenty years ago. These results indicate that it is time to retire the CLAW hypothesis.     

An amorphous solid state of biogenic secondary organic aerosol particles

Secondary organic aerosol (SOA) particles are formed in the atmosphere from condensable oxidation products of anthropogenic and biogenic volatile organic compounds (VOCs). On a global scale, biogenic VOCs account for about 90% of VOC emissions and of SOA formation (90?billion kilograms of carbon per year). SOA particles can scatter radiation and act as cloud condensation or ice nuclei, and thereby influence the Earth's radiation balance and climate. They consist of a myriad of different compounds with varying physicochemical properties, and little information is available on the phase state of SOA particles. Gas-particle partitioning models usually assume that SOA particles are liquid, but here we present experimental evidence that they can be solid under ambient conditions. We investigated biogenic SOA particles formed from oxidation products of VOCs in plant chamber experiments and in boreal forests within a few hours after atmospheric nucleation events. On the basis of observed particle bouncing in an aerosol impactor and of electron microscopy we conclude that biogenic SOA particles can adopt an amorphous solid-most probably glassy-state. This amorphous solid state should provoke a rethinking of SOA processes because it may influence the partitioning of semi-volatile compounds, reduce the rate of heterogeneous chemical reactions, affect the particles' ability to accommodate water and act as cloud condensation or ice nuclei, and change the atmospheric lifetime of the particles. Thus, the results of this study challenge traditional views of the kinetics and thermodynamics of SOA formation and transformation in the atmosphere and their implications for air quality and climate.     

一种快速测量高粒径分辨率气溶胶活化率曲线的方法

基于扫描粒径的原理, 介绍了测量高粒径分辨率气溶胶活化率曲线的方法。给出了改进的数据反演算法, 能较好地反演出气溶胶和云凝结核的数浓度谱分布, 以及气溶胶分档活化率。在大气气溶胶的外场观测中对该方法进行了检验。     

Atmospheric science: marine aerosols and iodine emissions

O'Dowd et al. describe the formation of marine aerosols from biogenic iodine and the growth of these aerosols into cloud-condensation nuclei (CCN). Based on chamber and modelling results, the authors suggest that biogenic organic iodine compounds emitted from macroalgae may be responsible for coastal particle bursts and that production of these compounds in the open ocean could increase CCN there too. It has since been shown that coastal particles are more likely to be produced from the photooxidation of molecular iodine. Moreover, I contend that open-ocean particle production and cloud enhancement do not result from emissions of organic iodine at atmospheric levels. For iodine particles to affect cloud properties over the remote ocean, an additional source of iodine is necessary as organic precursors cannot be responsible.     

The test freezing temperature of C2―C6 dicarboxylic acid: The important indicator for ice nucleation processes

The importance of organic compounds as significant constituents of atmospheric aerosols, and cloud condensation nuclei （CCN）, as well as players influencing the tropospheric oxidation and atmospheric energy budget, have been increasingly recognized. Low molecular weight dicarboxylic acids （LMW-DCAs） are significant identified portions of atmospheric condensed matter including aerosols, fog and clouds. Besides the photochemical transformation of DCA, the implication of organic matter in ice nucleation processes has been considered. In this study, we investigated the freezing temperature of pure and mixed （C2-C6） DCA solutions in ultra-pure water and tap water solution droplets using a freezing nucleus counter at different pH, and in different water ionic conditions. The mean freezing temperature of different mixture of LMW-DCA in ultra-pure and tap water solution droplets ranged from -24.1±2.8 to -21.3±3.9℃ and -10.2±2.2 to -9.5±2.2℃, respectively. The mean freezing temperature of the control （ultra-pure and tap） water droplets （-22.6±3.5℃, 11.2±2.4℃） was also measured. The results, and their implications in atmospheric chemistry and physics of the atmosphere will be discussed.     

Morphology and dynamics of the upper cloud layer of Venus

Venus is completely covered by a thick cloud layer, of which the upper part is composed of sulphuric acid and some unknown aerosols. The cloud tops are in fast retrograde rotation (super-rotation), but the factors responsible for this super-rotation are unknown. Here we report observations of Venus with the Venus Monitoring Camera on board the Venus Express spacecraft. We investigate both global and small-scale properties of the clouds, their temporal and latitudinal variations, and derive wind velocities. The southern polar region is highly variable and can change dramatically on timescales as short as one day, perhaps arising from the injection of SO2 into the mesosphere. The convective cells in the vicinity of the subsolar point are much smaller than previously inferred, which we interpret as indicating that they are confined to the upper cloud layer, contrary to previous conclusions, but consistent with more recent study.     

Aerosol formation: atmospheric particles from organic vapours

Aerosol particles produced over forested areas may affect climate by acting as nuclei for cloud condensation, but their composition (and hence the chemical species that drive their production) remains an open question. Here we show, to our knowledge for the first time, that these newly formed particles (3-5 nm in diameter) are composed primarily of organic species, such as cis-pinonic acid and pinic acid, produced by oxidation of terpenes in organic vapours released from the canopy.     

Distribution and origin of aerosol and its transform relationship with CCN derived from the spring multi-aircraft measurements of Beijing Cloud Experiment (BCE)

The atmospheric aerosol distribution,source and relationship with cloud condensation nuclei(CCN) observed during the Beijing Cloud Experiment(BCE) are analyzed.The results show that the high number concentrations of aerosol mainly distributed below 4500 m,and the magnitude could reach to 103 cm 3.Above 4500 m,the aerosol number concentrations decreased to 101 cm 3 as the altitude increases,and the aerosol mean diameters were between 0.16 and 0.19 μm.Below 4500 m,the number size distributions of aerosol showed a bimodal(multimodal) mode,and an unimodal mode above it.Due to the different sources of aerosol,the conversion ratios of aerosol to CCN were less than 20% below 4500 m,and reached 50% above the level at 0.3% supersaturation.The back trajectories showed that aerosols at higher levels above 4500 m were strongly affected by large-size particles and those below 4500 m were strongly affected by local or regional pollution.Based on observations,a relationship between the CCN number concentration and aerosol number concentration is established.     

A satellite view of aerosols in the climate system

Anthropogenic aerosols are intricately linked to the climate system and to the hydrologic cycle. The net effect of aerosols is to cool the climate system by reflecting sunlight. Depending on their composition, aerosols can also absorb sunlight in the atmosphere, further cooling the surface but warming the atmosphere in the process. These effects of aerosols on the temperature profile, along with the role of aerosols as cloud condensation nuclei, impact the hydrologic cycle, through changes in cloud cover, cloud properties and precipitation. Unravelling these feedbacks is particularly difficult because aerosols take a multitude of shapes and forms, ranging from desert dust to urban pollution, and because aerosol concentrations vary strongly over time and space. To accurately study aerosol distribution and composition therefore requires continuous observations from satellites, networks of ground-based instruments and dedicated field experiments. Increases in aerosol concentration and changes in their composition, driven by industrialization and an expanding population, may adversely affect the Earth's climate and water supply.     

Suppression of crystal nucleation in polydisperse colloids due to increase of the surface free energy

The formation of small crystallites is governed by two competing factors: the free energy gained upon transferring constituent atoms, molecules or colloidal particles from the metastable liquid to the more stable solid, and the free energy needed to create the surface area of the crystallite. Because the ratio of surface area to bulk is large for small particles, small crystallites dissolve spontaneously under conditions where larger crystallites are stable and macroscopic crystal growth occurs only if spontaneously formed crystallites exceed a critical minimum size. On theoretical grounds, the probability of forming such critical crystal nuclei is expected to increase rapidly with supersaturation. However, experiments show that the rate of crystal nucleation in many systems goes through a maximum as the supersaturation is increased. It is commonly assumed that the nucleation rate peaks because, even though the probability of forming critical nuclei increases with increasing concentration, the rate of growth of such nuclei decreases. Here we report simulations of crystal nucleation in suspensions of colloidal spheres with varying size distributions that show that the probability that critical nuclei will form itself goes through a maximum as the supersaturation is increased. We find that this effect, which is strongest for systems with the broadest particle size distribution, results from an increase with supersaturation of the solid-liquid interfacial free energy. The magnitude of this effect suggests that vitrification at high supersaturations should yield colloidal glasses that are truly amorphous, rather than nano-crystalline.     

Complex organic matter in Titan's atmospheric aerosols from in situ pyrolysis and analysis

Aerosols in Titan's atmosphere play an important role in determining its thermal structure. They also serve as sinks for organic vapours and can act as condensation nuclei for the formation of clouds, where the condensation efficiency will depend on the chemical composition of the aerosols. So far, however, no direct information has been available on the chemical composition of these particles. Here we report an in situ chemical analysis of Titan's aerosols by pyrolysis at 600 degrees C. Ammonia (NH3) and hydrogen cyanide (HCN) have been identified as the main pyrolysis products. This clearly shows that the aerosol particles include a solid organic refractory core. NH3 and HCN are gaseous chemical fingerprints of the complex organics that constitute this core, and their presence demonstrates that carbon and nitrogen are in the aerosols.     

气溶胶对沙漠气候变化的影响

本文用数值实验讨论了尘埃气溶胶对沙漠区气候和夏季风气候变化的影响。结果表明,影响是明显的。气溶胶对太阳短波辐射的散射和吸收,可使地表和土壤温度下降,大气低层温度上升。通过流场、垂直运动和降水场的变化,300hPa 以下温度增高,100hPa 上温度降低。文中对气溶胶的影响机制也进行了讨论。     

Measurement of aerosol optical extinction using diode laser cavity ringdown spectroscopy

Accurate measurement of optical extinction of atmospheric aerosols is important for quantifying the direct climate effects of aerosols. A portable cavity ringdown spectrometer utilizing a modulated multimode blue diode laser (linewidth ～0.2 nm) is developed to measure the aerosol optical extinction. Laboratory generated ammonia sulfate particles (<1 μm in diameter) are characterized, with good agreements between the experimental measurements and Mie theory calculations. An optical extinction detection sensitivity of 0.24 Mm-1 (1σ) is achieved. Measurements of ambient aerosols are also carried out. This study demonstrates the feasibility of a compact, multimode diode laser cavity ringdown spectrometer for sensitive measurements of the optical extinction of atmospheric aerosols.     

利用CloudSat和MODIS数据研究气溶胶对层积云的影响

利用CloudSat的云雷达数据研究了太平洋东部副热带地区的层积云微物理特性。结果显示, CloudSat反演的云滴数浓度在垂直方向变化很小。结合CloudSat的云雷达数据和MODIS的气溶胶数据, 研究了气溶胶对层积云的微物理特性和液态水路径的影响。结果表明: 对于相同的液态水路径, 气溶胶增加可以使得云滴的尺度减小, 但总体上对云滴尺度的影响并不显著; 由于云中液态水路径本身变化极大, 导致气溶胶对液态水路径的影响很难和云中液态水路径本身的变化分离开。此外还发现: CloudSat反演的层积云液态水路径比MODIS反演的液态水路径偏高; 层积云内液态水路径的不均一性比环境气溶胶光学厚度的不均一性大。     

The impact of humidity above stratiform clouds on indirect aerosol climate forcing

Some of the global warming from anthropogenic greenhouse gases is offset by increased reflection of solar radiation by clouds with smaller droplets that form in air polluted with aerosol particles that serve as cloud condensation nuclei. The resulting cooling tendency, termed the indirect aerosol forcing, is thought to be comparable in magnitude to the forcing by anthropogenic CO2, but it is difficult to estimate because the physical processes that determine global aerosol and cloud populations are poorly understood. Smaller cloud droplets not only reflect sunlight more effectively, but also inhibit precipitation, which is expected to result in increased cloud water. Such an increase in cloud water would result in even more reflective clouds, further increasing the indirect forcing. Marine boundary-layer clouds polluted by aerosol particles, however, are not generally observed to hold more water. Here we simulate stratocumulus clouds with a fluid dynamics model that includes detailed treatments of cloud microphysics and radiative transfer. Our simulations show that the response of cloud water to suppression of precipitation from increased droplet concentrations is determined by a competition between moistening from decreased surface precipitation and drying from increased entrainment of overlying air. Only when the overlying air is humid or droplet concentrations are very low does sufficient precipitation reach the surface to allow cloud water to increase with droplet concentrations. Otherwise, the response of cloud water to aerosol-induced suppression of precipitation is dominated by enhanced entrainment of overlying dry air. In this scenario, cloud water is reduced as droplet concentrations increase, which diminishes the indirect climate forcing.     

Biosignatures as revealed by spectropolarimetry of Earthshine

Low-resolution intensity spectra of Earth's atmosphere obtained from space reveal strong signatures of life ('biosignatures'), such as molecular oxygen and methane with abundances far from chemical equilibrium, as well as the presence of a 'red edge' (a sharp increase of albedo for wavelengths longer than 700?nm) caused by surface vegetation. Light passing through the atmosphere is strongly linearly polarized by scattering (from air molecules, aerosols and cloud particles) and by reflection (from oceans and land). Spectropolarimetric observations of local patches of Earth's sky light from the ground contain signatures of oxygen, ozone and water, and are used to characterize the properties of clouds and aerosols. When applied to exoplanets, ground-based spectropolarimetry can better constrain properties of atmospheres and surfaces than can standard intensity spectroscopy. Here we report disk-integrated linear polarization spectra of Earthshine, which is sunlight that has been first reflected by Earth and then reflected back to Earth by the Moon. The observations allow us to determine the fractional contribution of clouds and ocean surface, and are sensitive to visible areas of vegetation as small as 10 per cent. They represent a benchmark for the diagnostics of the atmospheric composition, mean cloud height and surfaces of exoplanets.     

单分散二氧化硅体系制备中正硅酸乙酯水解与成核及颗粒生长的关系

用透射电镜对乙醇介质中氨催化下正硅酸乙酯（ＴＥＯＳ）水解制各单分散二氧化硅微粒过程中颗粒的生长过程进行了跟踪，通过对ＴＥＯＳ的水解速率与成核及颗粒生长速率间关系的研究，发现水解是整个反应的控制步骤，影响水解的因素也同样影响成核及颗粒的生长。     

博斯腾湖流域戈壁地区大气边界层高度特征研究

位于新疆博斯腾湖流域戈壁地区的大气边界层过程受湖泊和戈壁的共同作用, 大气边界层结构具有特殊性。利用2013 年5 月21 日至8 月28 日在博斯腾湖流域戈壁地区获得的大气边界层探测试验资料, 分析该地区大气边界层结构特征。结果显示, 博斯腾湖流域戈壁地区大气边界层最突出的特征是在夏季典型晴天时对流边界层异常深厚, 在所统计的100 天探空资料中, 有45 天大气边界层高度达3000 m 以上, 最高可达4400 m。同时, 探讨深厚对流边界层的形成机制, 认为博斯腾湖流域戈壁地区特殊的大气热力环境以及湖风切变等因素是形成深厚对流边界层的重要原因。