On the formation and growth of atmospheric nanoparticles

In this paper we summarize recent experimental, theoretical and observational results on the formation and growth of atmospheric nanoparticles. During the last years significant progress has occurred to explain atmospheric nucleation and initial steps of the growth. Due to climatic and health effects of fine and ultrafine particles the formation and growth of new aerosol particles is of growing interest. The question “How and under which conditions does the formation of new atmospheric aerosol particles take place?” has exercised the minds of scientists since the time of John Aitken, who in the late 1880s built the first apparatus to measure the number of dust and fog particles. However, only during the last 15–20 years has the measurement technology developed to such a level that size distributions of nanometer-size particles and concentrations of gases participating in particle formation can be measured in the atmosphere. Also from a theoretical point of view atmospheric nucleation mechanisms have not been resolved: several mechanisms such as ion-induced (or ion mediated) nucleation, ternary and kinetic (barrier-less) nucleation have been suggested. In the most recent theory, the activation of existing neutral and/or ion clusters has been suggested.     

Charging state of atmospheric nanoparticles during the nucleation burst events

In this work, the charging state of atmospheric nanoparticles was estimated through simultaneous measurements of aerosol size distribution and air ions mobility distribution with the aim to elucidate the formation mechanisms of atmospheric aerosols. The measurements were performed as a part of the QUEST 2 campaign at a boreal forest station in Finland. The overlapping part of the measurement ranges of the particle size spectrometers and air ion mobility spectrometers in the mass diameter interval of 2.6–40 nm was used to assess the percentage of charged particles (charging probability). This parameter was obtained as the slope of the linear regression line on the scatterplot of the measured concentrations of total (neutral + charged) and charged particles for the same diameter interval. Charging probabilities as a function of particle diameter were calculated for different days and were compared with the steady state charging probabilities of the particles in the bipolar ion atmosphere. For the smallest particles detectable by the particle size spectrometers (2.6–5 nm), the high percentages of negatively charged particles were found during the nanometer particle concentration bursts. These values considerably exceeded the values for the steady charging state and it was concluded that negative cluster ions preferably act as condensation nuclei. This effect was found to be the highest in the case of comparatively weak nucleation bursts of nanoparticles, when the rate of the homogeneous nucleation and the concentration of freshly nucleated particles were low. The nucleation burst days were classified according to the concentration of the generated smallest detectable new particles (weak and strong bursts). Approximately the same classification was obtained based on the charge asymmetry on particles with respect to the charge sign (polarity). The probabilities of negative and positive charge on the particles with the diameter of 5–20 nm were found to be nearly equal and they approximately agree with the values corresponding to the steady state charge distribution for negative particles known from lab experiments. It means that the steady charging state was reached during the growing time of particles up to 5 nm. The natural charging state of particles with a diameter between 2.5 and 4.5 nm was estimated by means of a special DMPS setup. Results were found to be in good correlation with the data by the particle size spectrometers and air ion mobility spectrometers.     

On radiative forcing of sulphate aerosol produced from ion-promoted nucleation mechanisms in an atmospheric global model

A significant fraction of the total number of particles present in the atmosphere is formed by nucleation in the gas phase. Nucleation and the subsequent growth process influence both number concentration of particles and their size distribution besides chemical and optical properties of atmospheric aerosols. Sulphate aerosol nucleation mechanisms promoted by ions have been evaluated here in a tropospheric interactive chemistry-aerosol module for mass and number concentration in a global atmospheric model. The indirect radiative forcing of sulphate particles is assessed in this model; indirect radiative forcing is different for ion-induced (IIN) and ion-mediated (IMN) mechanisms. The indirect radiative forcing in 10-year simulation runs has been calculated as ?1.42?W/m² (IIN) and ?1.54?W/m² (IMN). The 5% emission of primary sulphate particles in simulations changes the indirect radiative forcing from ?1.42 to ?1.44?W/m² for IIN case, and from ?1.54 to ?1.55 W/m² for the IMN case. More precisely, owing to greater nucleation rates, IMN mechanisms produces greater cooling than the IIN mechanisms in the backdrop that both mechanisms produce almost identical distribution of CDNC in their pre-industrial runs. The inclusion of primary particles in simulations with IIN and IMN mechanisms increases both CDNC and the indirect radiative forcing.     

大气冰核:研究进展与挑战

大气冰核参与初始冰晶的异质形成,影响冰云的微物理过程和辐射性质。阐明大气冰核浓度、来源、性质及活化成冰的微观机制,是深入认识气溶胶与云相互作用的关键。本文梳理了近年来国内外在冰核测量技术、冰核活化机制、外场观测及其参数化方案等几个方面取得的进展,明晰了冰核研究存在的挑战。此外,本文也指出了我国加强大气冰核研究的必要性和迫切性。     

气溶胶影响云和降水的机理和观测研究进展

气溶胶对云和降水的影响,对于气候系统、大气环境以及水循环至关重要。气溶胶粒子作为云凝结核和大气冰核影响云的微物理过程,进而影响雨、雪、雹和其他形式的降水。近年来,在理解气溶胶的化学成分,气溶胶微物理特性以及气溶胶作为云凝结核和大气冰核影响云降水等方面已取得重大进展。本文对于气溶胶的概念、来源以及气溶胶的直接和间接效应进行了简要概述,重点总结了国内外在气溶胶影响云和降水的机理研究方面的成果,回顾了近年来利用卫星、地面观测设备、机载探测设备等对气溶胶和云进行遥感观测和直接观测所获得的观测事实并讨论了其可能的物理机制,在总结前人研究成果的基础上对未来的研究方向进行了讨论。     

Relevance of ion-induced nucleation of sulfuric acid and water in the lower troposphere over the boreal forest at northern latitudes

The relevance of ion-induced nucleation of sulfuric acid and water (IINSW) in the troposphere over the boreal forest at northern latitudes is investigated by combining two existing and previously published models (MALTE — model to predict new aerosol formation in the lower troposphere; PARNUC — a parameterized steady-state model of neutral and ion-induced nucleation of sulfuric acid and water for atmospheric conditions). Simulations were performed for 4 days with observed new particle formation at ground level by using input data from the SMEAR II station in Hyytiälä, Finland. The selected days were chosen to cover a wide range of values of the parameters most relevant for IINSW. The results showed that ion-induced nucleation of sulfuric acid and water can contribute up to 15% to the total amount of newly formed particles in the size range of 3–10 nm inside the mixed layer at the Hyytiälä site. The importance of IINSW seemed to increase in the free troposphere above the boundary layer, however, lack of measurements in the vertical structure of the input parameters suggest that the model results are burdened with high uncertainties.     

Relationship of heterogeneous nucleation and condensational growth on aerosol nanoparticles

Heterogeneous nucleation and condensation of dibutylphthalate, octadecane, octadecanol, and octadecanoic acid vapors at various pressures on insoluble AgCl and Ag nanoparticles in a turbulent mixing condensation nuclei counter (TMCNC) have been studied theoretically. A method to interpret the particle size distributions measured with a DMA and estimate the parameters for nucleation on single particles is proposed. Based on this semi-empirical method, the Gibbs free energy is calculated and a rate of heterogeneous nucleation on single particles is estimated directly from the experimental “condensation spectra” of inactive and active CN using the DMA data. In some cases, the dependence of the Gibbs nucleation energy on the vapor supersaturation had two maximums and one minimum, instead of one maximum as described by Gibbs' classical thermodynamics of phase transitions. This phenomenon, called “double barrier nucleation” (DBN) is caused by the surface heterogeneity of nano-CN; this is first experimental verification of DBN that had been previously predicted theoretically. Two types of heterogeneity may be present: topographic or energetic. Focusing on energetic heterogeneity, a theoretical model of DBN for spherical geometry is developed. The surface heterogeneity for insoluble nano-sized CN is shown to be critical to explaining the unusual transformation of a monomodal size distribution of inactive CN into a bimodal distribution of activated CN when coagulation is excluded. Future studies will be directed toward more data for further refining the theory and developing a model that simultaneously accounts for both types of surface heterogeneity of nano-CN.     

Development of particle size and composition distributions with a novel aerosol dynamics model

An aerosol dynamics model, AEROFOR2, is developed in the context of the BIOFOR project focussing on boreal forest aerosol. It is the second version of a Lagrangian type box model AEROFOR for investigating the formation and growth of particles under clear sky atmospheric conditions. Particles can consist of soluble and insoluble material and the particle population can be externally or internally mixed. AEROFOR2 includes gas phase chemistry and aerosol dynamics, and calculates the number and composition distributions of particles as functions of time. Observed growth rates of the nucleation mode particles after a typical nucleation event are 2–3 nm/h. The model simulations predict that 3·10⁷ molecules cm⁻³ of insoluble organic vapour and less than 6·10⁶ molecules cm⁻³ of soluble vapour condensing onto particles are enough to make them grow in good agreement with the observed growth rates. Then the source rate of the organic vapour must be an order of 10⁵ molecules cm⁻³ s⁻¹, and its saturation vapour density should be below 10⁶ molecules cm⁻³. If the aerosol was initially an internal mixture of soluble (70%) and insoluble (30%) constituents it transformed to an externally mixed aerosol during the simulation. By applying the externally‐mixed aerosol based on measured soluble volume fractions, it was concluded that the modelled soluble fraction of the nucleation mode was too low in comparison with the measurements, and thus, a part of the condensable organic vapour must be water soluble.     

Aerosol bacteria over the Southern Ocean during ACE-1

Individual bacterial cells occur in many samples that were collected at Cape Grim, Tasmania and during the Lagrangian “B” experiment of the Aerosol Characterization Experiment 1 (ACE-1) campaign that was conducted above the Southern Ocean. They are present in samples from altitudes as high as 5.4 km. Morphologically, almost all bacteria are rod-shaped, about 1 μm long or smaller, have one polar flagellum, and contain inclusions that are rich in P and K. Their morphological features suggest that these bacteria are motile, marine species. It seems likely that the cells became airborne by the same bubble-bursting mechanism that ejects sea-salt aerosol particles into the atmosphere; however, the bacteria and sea-salt particles are typically not aggregated with one another. The estimated number ratio of bacteria and the dominant aerosol species, sea salt, varies in the samples and averages about 1%. The aerosol bacteria seem to represent an important atmospheric reservoir of P and organic compounds; on the other hand, since they are externally mixed with sea salt, they are unlikely to be effective as cloud condensation nuclei.     

Effects of air masses and synoptic weather on aerosol formation in the continental boundary layer

Nucleation of near nm sized aerosol particles and subsequent growth to ∼100 nm in 1–2 days has in recent years been frequently observed in the continental boundary layer at several European locations. In 1998–99, this was the focus of the BIOFOR experiment in Hyytiälä in the boreal Finnish forest. Nucleation occurred in arctic and to some extent in polar air masses, with a preference for maritime air in transition to continental air masses, and never in sub‐tropical air. The air masses originated north of the BIOFOR experiment by paths from the southwest to northeast sector. The nucleation was also associated with cold air advection behind cold fronts, never warm air advection. This may relate to low pre‐existing aerosol concentration, low cloudiness and large diurnal amplitudes in the continental boundary layer associated with cold air advection and clear skies. Arctic and polar air together with cold air advection did not always lead to nucleation. The most important limiting meteorological factors were cold front passages and high cloudiness, probably through reduced photochemistry and wet scavenging of precursor gases and new aerosol particles. The preference for nucleation to occur in arctic air masses, which seldom form in the summer, suggests a meteorological explanation for the annual cycle of nucleation, which has a minimum in summer. The connection to cold‐air outbreaks suggests that the maximum in nucleation events during spring and autumn may be explained by the larger latitudinal temperature gradients and higher cyclone activity at that time of the year. Nucleation was observed on the same days over large parts (1000‐km distance) of the same air mass. This suggests that the aerosol nucleation spans from the microphysical scale to the synoptic scale, perhaps connected through boundary layer and mesoscale processes.     

A review of global stratospheric aerosol: Measurements, importance, life cycle, and local stratospheric aerosol

Stratospheric aerosol, noted after large volcanic eruptions since at least the late 1800s, were first measured in the late 1950s, with the modern continuous record beginning in the 1970s. Stratospheric aerosol, both volcanic and non-volcanic are sulfuric acid droplets with radii (concentrations) on the order of 0.1–0.5 µm (0.5–0.005 cm^− 3), increasing by factors of 2–4 (10–10³) after large volcanic eruptions. The source of the sulfur for the aerosol is either through direct injection from sulfur-rich volcanic eruptions, or from tropical injection of tropospheric air containing OCS, SO₂, and sulfate particles. The life cycle of non-volcanic stratospheric aerosol, consisting of photo-dissociation and oxidation of sulfur source gases, nucleation/condensation in the tropics, transport pole-ward and downward in the global planetary wave driven tropical pump, leads to a quasi steady state relative maximum in particle number concentration at around 20 km in the mid latitudes. Stratospheric aerosol have significant impacts on the Earth's radiation balance for several years following volcanic eruptions. Away from large eruptions, the direct radiation impact is small and well characterized; however, these particles also may play a role in the nucleation of near tropopause cirrus, and thus indirectly affect radiation. Stratospheric aerosol play a larger role in the chemical, particularly ozone, balance of the stratosphere. In the mid latitudes they interact with both nitrous oxides and chlorine reservoirs, thus indirectly affecting ozone. In the polar regions they provide condensation sites for polar stratospheric clouds which then provide the surfaces necessary to convert inactive to active chlorine leading to polar ozone loss. Until the mid 1990s the modern record has been dominated by three large sulfur-rich eruptions: Fuego (1974), El Chichón (1982) and Pinatubo (1991), thus definitive conclusions concerning the trend of non-volcanic stratospheric aerosol could only recently be made. Although anthropogenic emissions of SO₂ have changed somewhat over the past 30 years, the measurements during volcanically quiescent periods indicate no long term trend in non-volcanic stratospheric aerosol.     

Transformation of Aerosol Chemical Properties due to Transport Over a City

The change of the chemical composition of the near-ground level atmospheric aerosol was studied during two summer episodes by a Lagrangian type of experimental approach. Bulk and single-particle chemical analyses of ions and elements in the particulate phase were deployed. N(-III) and N(V) components were also measured in the gas-phase. The measurements were completed by particle size distributions.Secondary inorganic aerosols (SIA) and fine particles of ≈0.2–0.4 μm size were still elevated 50 km downwind of the city. The direct comparison of transport over the city in contrast to transport over the surrounding areas showed that SIA was formed from emission from the city within less than 3 h. Relative increases, i.e., enrichment during transport were observed for primary and secondary aerosol components. The degree of mixing on the individual particle level increased significantly during transport in the area. In particular, newly emitted carbonaceous particles became internally mixed within hours with pre-existing sulphate particles. Mostly due to secondary aerosol formation the average particle size (mass median diameter) of major constituents of the aerosol was significantly decreased while being transported over 13 h. Given recent insights which link fine particles number and mass concentrations with health risks, the results suggest that rural populations in areas which frequently are located within an urban plume might run an elevated health risk relative to populations in areas not affected by urban plumes.     

The effect of clouds on aerosol growth in the rural atmosphere

Measurements of accumulation mode aerosol in the atmospheric boundary layer under cloudy and cloud-free conditions, and in the lower free troposphere under cloud-free conditions, were conducted over the rural northwest of England. Normalised size distributions in the cloud-free boundary layer (CFBL) and the cloud-free free troposphere (CFFT) exhibited almost identical spectral similarities with both size distributions possessing a concentration peak mode-radius of ≈0.05 μm or less. By comparison, aerosol distributions observed in cloudy air exhibited a distinctive log-normal distribution with mode-radii occurring at ≈0.1 μm concomitant with a local minimum at ≈0.05 μm. The consistent and noticeable difference in spectral features observed between cloudy and cloud-free conditions suggest that a greater amount of gas-to-particle conversion occurs on cloudy days, presumably through in-cloud aqueous phase oxidation processes, leading to larger sized accumulation mode particles. Apart from the distinct difference between cloudy and cloud-free aerosol spectra on cloudy days, aerosol concentration and mass were observed to be significantly enhanced above that of the ambient background in the vicinity of clouds. Volatility analysis during one case of cloud processing indicated an increase in the relative contribution of aerosol mass volatile at temperatures characteristic of sulphuric acid, along with a smaller fraction of more volatile material (possibly nitric acid and/or organic aerosol). Growth-law analysis of possible growth mechanisms point to aqueous phase oxidation of aerosol precursors in cloud droplets as being the only feasible mechanism capable of producing the observed growth. The effect of cloud processing is to alter the cloud condensation nuclei (CCN) supersaturation spectrum in a manner which increases the availability of CCN at lower cloud supersaturations.     

Characteristic features of air ions at Mace Head on the west coast of Ireland

Coastal nucleation events and behavior of cluster ions were characterized through the measurements of air ion mobility distributions at the Mace Head research station on the west coast of Ireland in 2006. We measured concentrations of cluster ions and charged aerosol particles in the size range of 0.34–40 nm. These measurements allow us to characterize freshly nucleated charged particles with diameters smaller than 3 nm. The analysis shows that bursts of intermediate ions (1.6–7 nm) are a frequent phenomenon in the marine coastal environment. Intermediate ion concentrations were generally close to zero, but during some nucleation episodes the concentrations increased to several hundreds per cm³. Nucleation events occurred during most of the measurement days. We classified all days into one of seven classes according to the occurrence and type of new particle formation. Nucleation events were observed during 207 days in 2006, most prominently in the spring and summer months. Rain-induced events, in turn, were observed during 132 days. Particle formation and growth events mostly coincided with the presence of low tide. Also small cluster ions (0.34–1.6 nm) were characterized. Average concentrations of small ions were 440 cm^− 3 for the negative ions and 423 cm^− 3 for the positive ions. Average mean mobilities of small ions were 1.86 cm²V^− 1s^− 1 and 1.49 cm²V^− 1s^− 1 for the negative and positive polarities, respectively. Concentrations of small ions were observed to be strongly dependent on the variations of meteorological parameters including wind speed and direction.     

Modelling the formation of H2SO4–H2O particles in rural, urban and marine conditions

The factors which affect the formation of new sulphuric acid particles in different atmospheric conditions are investigated. An atmospheric chemistry gas phase box model coupled to a three mode integral aerosol dynamics model is used. The simulations show the dependence of the concentration of nucleation mode particles on initial pre-existing particles, the intensity of UV radiation, the emissions of dimethylsulphide (DMS) and the ratio of emissions of hydrocarbons (HC) and NO_x present in the atmosphere. Eight different basic cases are simulated in urban, rural and marine conditions. The effects of pre-existing particles as a sink of sulphuric acid are clearly seen. The increased UV radiation is also seen to enhance particle formation via sulphuric acid route significantly.     

Impact of the Bergeron–Findeisen process on the release of aerosol particles during the evolution of cloud ice

The paper focuses on the redistribution of aerosol particles (APs) during the artificial nucleation and subsequent growth of ice crystals in a supercooled cloud. A significant number of the supercooled cloud droplets during icing periods (seeding agents: C₃H₈, CO₂) did not freeze as was presumed prior to the experiment but instead evaporated. The net mass flux of water vapour from the evaporating droplets to the nucleating ice crystals (Bergeron–Findeisen mechanism) led to the release of residual particles that simultaneously appeared in the interstitial phase. The strong decrease of the droplet residuals confirms the nucleation of ice particles on seeding germs without natural aerosol particles serving as ice nuclei. As the number of residual particles during the seedings did not drop to zero, other processes such as heterogeneous ice nucleation, spontaneous freezing, entrainment of supercooled droplets and diffusion to the created particle-free ice germs must have contributed to the experimental findings. During the icing periods, residual mass concentrations in the condensed phase dropped by a factor of 1.1–6.7, as compared to the unperturbed supercooled cloud. As the Bergeron–Findeisen process also occurs without artificial seeding in the atmosphere, this study demonstrated that the hydrometeors in mixed-phase clouds might be much cleaner than anticipated for the simple freezing process of supercooled droplets in tropospheric mid latitude clouds.     

Physicochemical properties of fine aerosols at Plan d'Aups during ESCOMPTE

The physical and chemical properties of aerosol particles were investigated at Plan d'Aups, one of the ESCOMPTE sites located in the St. Baume mountain area (700 m a.s.l.), 50 km east of Marseilles (France). The site is ideally located for assessing the vertical and horizontal extent of the pollution plume from the Marseilles–Berre area.Our study showed that polluted air masses from the Marseilles–Berre area are advected to Plan d'Aups in the early afternoon. Average daily concentration of particles reaches up to 40 μg m⁻³ while 1-h average particle number concentration is greater than 30,000 cm⁻³. Most of the particle mass is composed of SO₄²⁻ and organic carbon (OC). The chemical properties of the particles revealed that an additional source, possibly from the industrial area of Gardanne, contributes to the aerosol mass. This last source is characterised by significant emissions of elements, such as Zn, V, Al and Si.In addition to transport, we found that gas-to-particle conversion takes place at the interface between the free troposphere and the boundary layer. We estimated that on average, 30% of the particle number is accounted for by direct nucleation. This is potentially a major aerosol source to the free troposphere.     

Evaluation of a new aerosol model with a Brownian diffusion technique

Measurements in Alaska in sub-polar night conditions have indicated that the size distribution of atmospheric aerosols varies significantly and systematically depending upon the type of air mass. Atmospheric aerosol particles are small and numerous in warm Pacific marine air mass systems and large and sparse in cold, Arctic-derived air mass systems. In a previous paper this was hypothesized to be associated with the progressive loss of the smallest particles by attachment to cloud droplets under the driving influence of thermal Brownian motion. A theory involving two parameters, (mean particle radius), and n₀ (aerosol number concentration) was developed to describe the process. In the previous paper, the relationship where ν is the Junge power law exponent (ν 3) was derived and has recently been confirmed to acceptable accuracy with the use of a simple experiment which employed diffusive separation. The diffusion experiment has also allowed us to estimate that the fraction of time, φ, that the aerosol-laden polar air masses coexist in the presence of cloud is 0.01 < φ < 0.1. The submicron aerosol particles in Arctic-derived air masses flowing into central Alaska are deduced to have residence times on the order of 10 days.     

Tests for individual Sulfate－Containing Particles in Urban Atmosphere in Beijing

Thin film methods and X ray energy dispersive technique were applied to analyze sulfate-containing particles in Beijing in order to examine their features and sources. Atmospheric aerosol particles were collected on electron mi-croscope meshes according to two size ranges: coarse particles (r>0.5μm) and fine particles (0.5μm≥r≥0.1μm) by using a two-stage impactor. It was found fiat more than seventy percent of the fine particles and about twenty percent of the coarse particles were sulfate-containing particles. These particles were formed mainly through heterogeneous nucleation. The element composition analyses revealed that the atmospheric aerosol particles in Beijing were domi-nated by crustal particles and construction dust.     

青藏高原大气气溶胶研究进展

文中综述了近30年来青藏高原大气气溶胶的研究现状,包括青藏高原大气气溶胶光学厚度、气溶胶面密度等的时空变化特征,大气气溶胶化学成分分析及气候效应的研究等。大多利用卫星、激光雷达及地面采样等资料分析研究气溶胶。青藏高原大气气溶胶研究已经取得了显著进展。文中主要综述了该领域的研究成果,并对其今后的研究进行了展望。