Vertical fluxes and micrometeorology during aerosol particle formation events

Fluxes of aerosol particles with sizes larger than 10 nm together with fluxes of momentum, sensible and latent heat and CO₂ were measured 10 m above a Scots pine forest with the eddy covariance method. During days when nucleation events were observed particle size distribution measurements showed particle growth from 3 nm sizes to the Aitken mode. Analysis of the experimental data showed systematic differences in fluxes during the days when new particle production was observed compared to other days. During the nucleation events the particle flux measurements showed downward aerosol particle transport, i.e., indicating an elevated source, with respect to the measurement level, of particles larger than 10 nm. Furthermore the turbulence intensity and the heat fluxes were observed to be significantly higher. Evidences of mesoscale circulation were observed in wind speed records as well as in turbulent fluxes on nucleation days. The measurement results show that micrometeorology, the synoptic scale conditions and the particle formation are closely related.     

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.     

Physical characterization of aerosol particles during nucleation events

Particle concentrations and size distributions have been measured from different heights inside and above a boreal forest during three BIOFOR campaigns (14 April–22 May 1998, 27 July–21 August 1998 and 20 March–24 April 1999) in Hyytiälä, Finland. Typically, the shape of the background distribution inside the forest exhibited 2 dominant modes: a fine or Aitken mode with a geometric number mean diameter of 44 nm and a mean concentration of 1160 cm⁻³ and an accumulation mode with mean diameter of 154 nm and a mean concentration of 830 cm⁻³. A coarse mode was also present, extending up to sizes of 20 μm having a number concentration of 1.2 cm⁻³, volume mean diameter of 2.0 μm and a geometric standard deviation of 1.9. Aerosol humidity was lower than 50% during the measurements. Particle production was observed on many days, typically occurring in the late morning. Under these periods of new particle production, a nucleation mode was observed to form at diameter of the order of 3 nm and, on most occasions, this mode was observed to grow into Aitken mode sizes over the course of a day. Total concentrations ranged from 410–45 000 cm⁻³, the highest concentrations occurring on particle production days. A clear gradient was observed between particle concentrations encountered below the forest canopy and those above, with significantly lower concentrations occurring within the canopy. Above the canopy, a slight gradient was observed between 18 m and 67 m, with at maximum 5% higher concentration observed at 67 m during the strongest concentration increases.     

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.     

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.     

Observation of regional new particle formation in the urban atmosphere

Long-term measurements of fine particle number-size distributions were carried out over 9.5 yr (May 1997–December 2006), in the urban background atmosphere of Helsinki. The total number of days was 3528 with about 91.9% valid data. A new particle formation event (NPF) is defined if a distinct nucleation mode of aerosol particles is observed below 25 nm for several hours, and it shows a growth pattern. We observed 185 NPF events, 111 d were clear non-events and most of the days (around 83.5%) were undefined. The observed events were regional because they were observed at Hyytiälä (250 km north of Helsinki). The events occurred most frequently during spring and autumn. The observed formation rate was maximum during the spring and summer (monthly median 2.87 cm⁻³ s⁻¹) and the modal growth rate was maximum during late summer and Autumn (monthly median 6.55 nm h⁻¹). The events were observed around noon, and the growth pattern often continued on the following day. The observation of weak NPF events was hindered due to pre-existing particles from both local sources. It is clear that regional NPF events have a clear influence on the dynamic behaviour of aerosol particles in the urban atmosphere.     

Condensation particle counting below 2 nm seed particle diameter and the transition from heterogeneous to homogeneous nucleation

Particle detection by condensation particle counters (CPCs) is ultimately limited by the onset of homogeneous nucleation. At vapour supersaturations around the homogeneous nucleation limit the diameter of critical clusters is typically about 2 nm. It is widely assumed that only particles larger than critical clusters can be activated by vapour condensation and the general detection limit of CPCs is therefore currently accepted to be around 2 nm particle diameter. Using an expansion type CPC with n-propanol as working fluid we investigated the transition from heterogeneous to homogeneous nucleation, clearly showing that particles are activated much before the onset of homogeneous nucleation, even at particle diameters as small as 1.4 nm. For particle diameters below 2 nm we have usually found condensation particle counting to be influenced by the simultaneous presence of ions as generated in a bipolar diffusion charger. In this paper we illustrate how the presence of ions influences particle number concentration measurement and how ions can be removed in order to obtain accurate seed particle number concentrations for particle diameters down to 1 nm.     

Condensation particle counting below 2 nm seed particle diameter and the transition from heterogeneous to homogeneous nucleation

Particle detection by condensation particle counters (CPCs) is ultimately limited by the onset of homogeneous nucleation. At vapour supersaturations around the homogeneous nucleation limit the diameter of critical clusters is typically about 2 nm. It is widely assumed that only particles larger than critical clusters can be activated by vapour condensation and the general detection limit of CPCs is therefore currently accepted to be around 2 nm particle diameter. Using an expansion type CPC with n-propanol as working fluid we investigated the transition from heterogeneous to homogeneous nucleation, clearly showing that particles are activated much before the onset of homogeneous nucleation, even at particle diameters as small as 1.4 nm. For particle diameters below 2 nm we have usually found condensation particle counting to be influenced by the simultaneous presence of ions as generated in a bipolar diffusion charger. In this paper we illustrate how the presence of ions influences particle number concentration measurement and how ions can be removed in order to obtain accurate seed particle number concentrations for particle diameters down to 1 nm.     

State of mixing, shape factor, number size distribution, and hygroscopic growth of the Saharan anthropogenic and mineral dust aerosol at Tinfou, Morocco

The Saharan Mineral Dust Experiment (SAMUM) was conducted in May and June 2006 in Tinfou, Morocco. A H-TDMA system and a H-DMA-APS system were used to obtain hygroscopic properties of mineral dust particles at 85% RH. Dynamic shape factors of 1.11, 1.19 and 1.25 were determined for the volume equivalent diameters 720, 840 and 960 nm, respectively.
During a dust event, the hydrophobic number fraction of 250 and 350 nm particles increased significantly from 30 and 65% to 53 and 75%, respectively, indicating that mineral dust particles can be as small as 200 nm in diameter. Log-normal functions for mineral dust number size distributions were obtained from total particle number size distributions and fractions of hydrophobic particles. The geometric mean diameter for Saharan dust particles was 715 nm during the dust event and 570 nm for the Saharan background aerosol.
Measurements of hygroscopic growth showed that the Saharan aerosol consists of an anthropogenic fraction (predominantly non natural sulphate and carbonaceous particles) and of mineral dust particles. Hygroscopic growth and hysteresis curve measurements of the 'more' hygroscopic particle fraction indicated ammonium sulphate as a main component of the anthropogenic aerosol. Particles larger than 720 nm in diameter were completely hydrophobic meaning that mineral dust particles are not hygroscopic.     

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.     

自然云中冰晶生成的核化过程及雪晶对过冷云滴的撞冻

鉴于冰晶过程在自然降水形成中的作用十分重要,对冰晶形成的物理过程曾进行过大量研究。由于自然云中冰晶的生成受大气热力、动力学条件及微物理过程等多因子制约,因而在自然云中研究冰晶的形成过程有很大困难,至今有关冰晶生成的核化过程的外场研究仍极少。室内实验可以在控制某些云物理条件下进行,但有些条件(过冷云维持时间、过冷云滴谱等)很难进行逼真的模拟。雪晶对过冷云滴的撞冻是雪粒子的重要增长过程之一;有关雪晶对过冷云滴的撞冻效率,已持续进行多年的室内实验与理论研究。这些研究工作中,都对雪晶形状做了不同程度的简化,对自然云中的雪晶撞冻过程的研究仍极少。     

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.     

南京霾天颗粒物数浓度特征及其受气象条件影响分析

2013年12月,我国中东部地区爆发持续性霾污染过程。本研究利用空气动力学粒径谱仪和气溶胶粒径谱仪在线观测这次霾污染过程中13.6~20 000 nm颗粒物数浓度,结合气象参数和颗粒物化学组分对南京霾天颗粒物数浓度分布特征,及其与气象条件相关性进行分析。结果表明,霾天颗粒物主要分布在积聚模态,且500~1 000 nm和1 000~2 500 nm粒径段颗粒物数浓度的增多是造成霾天能见度低的主要原因;随着相对湿度的增大,13.6~100 nm粒径段颗粒物数浓度逐渐降低,而大于100 nm颗粒物数浓度升高;500~1 000 nm和1 000~2 500 nm粒径段颗粒物数浓度受相对湿度的影响尤为明显,并且这2个粒径段颗粒物受气态污染物(SO2,NOX)的二次转化影响较大。霾污染期间南京大气颗粒物主要来自南京东南和西北方向的污染源排放,颗粒物数浓度总体上与风速呈负相关关系;温度对颗粒物数浓度的影响主要集中在13.6~100 nm粒径段;边界层的高度与粒径100 nm颗粒物呈负相关性,边界层的抬升反而利于超细粒子的生成和增长;逆温层的强度对超细粒子的作用更为明显。     

区域冷锋降水微物理机制研究

20世纪利用一维层状云模式对2002年4月4~5日河南省冷锋降水过程进行了模拟。数值模拟结果显示,此次冷锋降水属于冷云降水过程,冷锋前后云中主要以冰相粒子为主,云中水质粒自上而下的空间分布依次为冰晶、雪、云水、霰、雨水。冷锋前后,各种水质粒有着不同的含量及数密度,但形成水质粒的主要微物理过程都表现为:冰晶数密度的增加主要依靠核化、繁生,大部分雪主要靠凝华、撞冻过冷云水和冰晶增长,霰的质量增加主要靠撞冻雪、过冷云水和雪自动转化而来,大部分的雨水是由霰融化而来,因而此次冷锋降水机制表现为“水汽—雪—霰—雨水”。     

Small-particle concentration fluctuations at a coastal site

Aerosol size spectra (d=10 nm–10 μm) were measured with an electrical aerosol spectrometer (EAS) at Mace Head on the west coast of Ireland. Several small aerosol particle (diameter 10–32 nm) concentration bursts were observed during the measurement period. Relationships between the events, air mass trajectories, tide height, and meteorological parameters are examined. Series of bursts were observed when a spectral transformation due to subsequent particle growth from 10 to 56–100 nm can be identified in an Eulerian experiment. Particle growth rates of between 1 and 3 nm/h were determined. These bursts appear in cold and comparatively clean arctic or polar air masses with temperature and relative humidity fluctuations, and do not correlate with low tide in some cases. These episodes, similar to those frequently found in the continental boundary layer, are thought to occur over a wide area and, for clear detection, require stable airflow for a few days. Elevated small-particle concentration events are more common during low tide or shortly after, and are typically associated with low wind speeds. Here, the increased shore exposure during low tide is thought to influence the nucleation and the subsequent growth of these aerosol particles. The occurrences of the bursts are found to depend on local wind direction. The highest d=10–32 nm particle concentrations appeared for wind sectors furthest from the tidal regions when the wind direction was 150–160°(south-easterly). Most of the events occurred during daytime when solar irradiation is most intense.     

MEASUREMENTS OF PARTICLE NUMBER SIZE DISTRIBUTIONS AND NEW PARTICLE FORMATION EVENTS DURING WINTER IN THE PEARL RIVER DELTA REGION, CHINA

Particle number size distribution(PNSD) between 10 nm and 20 μm were measured in the Pearl River Delta(PRD) region in winter 2011.The average particle number concentration of the nucleation mode(10-20 nm),Aitken mode(20-100 nm),accumulation mode(100 nm-1μm) and coarse mode(1-20 μm) particles were 1 552,7 470,4 012,and 19 cm-3,respectively.The volume concentration of accumulation mode particles with peak at 300 nm accounted for over 70% of the total volume concentration.Diurnal variations and dependencies on meteorological parameters of PNSD were investigated.The diurnal variation of nucleation mode particles was mainly influenced by new particle formation events,while the diurnal variation of Aitken mode particles correlated to the traffic emission and the growth process of nucleation mode particles.When the PRD region was controlled by a cold high pressure,conditions of low relative humidity,high wind speed and strong radiation are favorable for the occurrence of new particle formation(NPF) events.The frequency of occurrence of NPF events was 21.3% during the whole measurement period.Parameters describing NPF events,including growth rate(GR) and source rate of condensable vapor(Q),were slightly larger than those in previous literature.This suggests that intense photochemical and biological activities may be the source of condensable vapor for particle growth,even during winter in the PRD.     

Scavenging of atmospheric ions and aerosols by drifting snow in Antarctica

Measurements of the small-, intermediate-, and large-ion concentrations and the air–earth current density along with simultaneous measurements of the concentration and size distribution of aerosol particles in the size ranges 4.4–163 nm and 0.5–20 μm diameter are reported for a drifting snow period after the occurrence of a blizzard at a coastal station, Maitri, Antarctica. Ion concentrations of all categories and the air–earth current simultaneously decrease by approximately an order of magnitude as the wind speed increases from 5 to 10 ms^− 1. The rate of decrease is the highest for large ions, lowest for small ions and in-between the two for intermediate ions. Total aerosol number concentration decreases in the 4.4–163 nm size range but increases in the 0.5–20 μm size range with wind speed. The size distribution of the nanometer particles shows a dominant maximum at ~ 30 nm diameter throughout the period of observations and the height of the maximum decreases with wind speed. However, larger particles show a maximum at ~ 0.7 μm diameter but the height of the maximum increases with increasing wind speed. The results are explained in terms of scavenging of atmospheric ions and aerosols by the drifting snow particles.     

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.     

2009年石家庄地区不同天气条件下大气气溶胶分布特征

利用2009年石家庄地区的4次机载PMS探测资料,对不同天气条件下大气气溶胶的数浓度、平均直径垂直分布和谱分布及一次晴天条件下的水平分布进行分析。结果表明：PCASP 探头探测的0.1-3.0 μm气溶胶粒子最大数浓度的量级为102-104 cm-3之间,平均值量级为102-103 cm-3之间,平均直径最大值介于0.225-0.717 μm,平均值介于0.148-0.167 μm。晴天条件下,气溶胶的数浓度随高度递减,直径随高度变化不大;逆温层底气溶胶明显积累,气溶胶浓度在大气边界层内明显高于其他层次;阴天轻雾情况下边界层内的气溶胶数浓度大于雨天和晴天,雨天气溶胶浓度最低;晴天气溶胶数浓度的水平分布不均匀;在云中气溶胶浓度明显下降,在云外气溶胶浓度较高。不同天气条件和晴天不同高度情况下,石家庄地区气溶胶谱型呈单峰分布,小于0.3 μm的细粒子对气溶胶的数浓度贡献最大,且随着高度的增加谱宽变窄。     

Insignificant impact of freezing and compaction on iron solubility in natural snow

To explore the freezing effect on iron (Fe) solubility in natural environments, especially in Polar regions, event based freshly fallen snow samples were collected at Newark, New Jersey on the US East Coast for two consecutive winter seasons (2014–2015 and 2015–2016). These samples were analyzed for the concentrations of soluble iron (Fe_sol) using UV-Vis Spectroscopy and filterable iron (Fe_fil) and total iron (Fe_tot) using Atomic Absorption Spectroscopy. The average fractional solubility of the Fe_sol (the portion that passes through a 0.22 μm pore-size filter) with respect to the total Fe in the samples was 23.3?±?12.2%, with the majority of the soluble Fe being present as Fe(III). Approximately 48.5% of the total Fe existed as Fe_fil (the portion that passes through 0.45 μm pore size filter media). No significant correlation was found between the soluble ionic species and soluble Fe. Six snow events were kept frozen for 10 days, and analyzed in periodic intervals to study the post-freezing modification in Fe solubility. Events 1 and 2 showed increasing trend in the soluble Fe concentrations; however, the events 5, 6, 7, and 8 showed no noticeable increments. The pattern shown in Events 1 and 2 is associated with high fraction of Fe_fil and one unit pH drop, suggesting that the freeze-induced modification in Fe solubility could be linked with the amount of Fe_fil and the acidity change in the samples. To further investigate the freeze-induced compaction of particles, samples from three events 6, 7, and 10 were analyzed by SEM-STEM-EDS microscopy, and the results showed that due to freezing, in general, the particles in the ice-melt counterparts tend to compact and cluster and form larger aggregates compared to the particles in snow-melt. These results show, despite the freeze-induced compaction in snow was observed from STEM images, the snow freezing might not have significant effect in increasing Fe solubility from materials in the snow. These results further suggest that freezing process with fresh snow in high-latitude regions may not impose significant modification on Fe solubility in snow.