New aerosol particle formation via certain ion driven processes

Ions can speed up the formation of aerosol particles. The former studies have mainly concerned on the role of the ion charge itself. We have studied the possible (additional) role of the actual small air ion spectrum shape, and the quantitative role of ion–ion recombination pathway. By means of our ion evolution model, formation of new species (H₂SO₄)_n(NH₃)_m(HNO₃)_k via ion–ion recombination was investigated. The model shows how the generation rate of the new species depends on the concentrations of H₂SO₄ and NH₃, and how it depends on the tropospheric background aerosol situation. The rate can be up to a few new neutral complexes per cubic centimeter and per second. New particle generation via ion–ion recombination provides an extra channel, especially for the clean atmosphere. Former results have shown that such situations are often present in Antarctica. Our aerosol spectrum measurements reveal a number of similar non-Antarctic results. Sometimes, such situations are followed by aerosol bursts, which may be (partly) due to an ion–ion recombination channel.     

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.     

The influence of aerosol particle composition on cloud droplet formation

A difference in partitioning between cloud droplets and interstitial air for two chemical species (elemental carbon and sulphur) with different expected behaviour in nucleation scavenging was observed in clouds at Mt. Kleiner Feldberg (825 m asl), near Frankfurt, Germany. The fraction of sulphur incorporated in cloud droplets was always higher than the fraction of elemental carbon. This difference in partitioning has also been observed in fog but under different pollution conditions in the Po Valley, Italy. Both these studies were based on bulk samples. In the present study at Kleiner Feldberg, impactor samples of the particles in the interstitial air and the cloud droplet residuals were taken and a single particle analysis was done on the samples. It was found that, for a given particle size, the majority of particles forming cloud droplets were soluble and that insoluble particles preferentially remained in the interstitial air.     

New aerosol particle formation in different synoptic situations at Hyytiälä, Southern Finland

We examine the meteorological conditions favourable for new particle formation as a contribution to clarifying the responsible processes. Synoptic weather maps and satellite images over Southern Finland for 2003–2005 were examined, focusing mainly on air mass types, atmospheric frontal passages, and cloudiness. Arctic air masses are most favourable for new aerosol particle formation in the boreal forest. New particle formation tends to occur on days after passage of a cold front and on days without frontal passages. Cloudiness, often associated with frontal passages, decreases the amount of solar radiation, reducing the growth of new particles. When cloud cover exceeds 3–4 octas, particle formation proceeds at a slower rate or does not occur at all. During 2003–2005, the conditions that favour particle formation at Hyytiälä (Arctic air mass, post-cold-frontal passage or no frontal passage and cloudiness less than 3–4 octas) occur on 198 d. On 105 (57%) of those days, new particle formation occurred, indicating that these meteorological conditions alone can favour, but are not sufficient for, new particle formation and growth. In contrast, 53 d (28%) were classified as undefined days; 30 d (15%) were non-event days, where no evidence of increasing particle concentration and growth has been noticed.     

The investigations of aerosol particle formation in urban background area of Helsinki

In this study the possible conditions for new aerosol particle formation in a background area of Helsinki have been analysed. The measurements of aerosol particle size distribution, main gaseous pollutant compounds, UV spectra and meteorological parameters were performed during April–May 1993. The main interest was concentrated on the investigations of photochemical OH radical formation, the oxidation of gas phase SO₂ to H₂SO₄ and the formation of H₂SO₄---H₂O aerosol particles. The measurements were analysed using a model for OH radical formation and aerosol dynamics. The analysis of aerosol size distributions was carried out using positive matrix factorization. The main conclusion is that based on our model analysis no evidence of new particle formation in the vicinity of the measurement station was found. However, the high concentrations of aerosol particles in the ultrafine size range indicate that some other particle formation pathways are to be considered.     

Annual and interannual variation in boreal forest aerosol particle number and volume concentration and their connection to particle formation

We investigated size-resolved submicrometre aerosol particle number and volume concentration time series as well as aerosol dynamic parameters derived from Differential Mobility Particle Sizer (DMPS) measurements at five background stations in the Nordic boreal forest area. The stations in question were Aspvreten, Hyytiälä and Utö in southern Finland and Sweden, and Värriö and Pallas in the Finnish Lapland. The objective of our investigation was to identify and quantify annual and interannual variation observable in the time series. We found that the total number and mass concentrations were much lower at the Lapland stations than at the southern stations and that the total particle number was strongly correlated to particle formation event frequency. The annual total number concentration followed the annual distribution of particle formation events at the southern stations but much less clearly at the Lapland stations. The volume concentration was highest during summer, in line with higher condensation growth rates; this is in line with the assumption that a large part of the particle volume is produced by oxidized plant emissions. The decrease of sulphate emissions in Europe was not visible in our data set. Aerosol dynamic parameters such as condensation sink, condensation sink diameter and the power law exponent linking coagulation losses and condensation sink are presented to characterize the submicron Nordic background aerosol.     

Modelling of aerosol processes in plumes

A modelling platform for studying photochemical gaseous and aerosol phase processes from localized (e.g., point) sources has been presented. The current approach employs a reactive plume model which extends the regulatory model RPM‐IV by incorporating aerosol processes and heterogeneous chemistry. The physics and chemistry of elemental carbon, organic carbon, sulfate, nitrate, ammonium material of aerosols are treated and attributed to the PM size distribution. A modified version of the carbon bond IV chemical mechanism is included to model the formation of organic aerosol. Aerosol dynamics modeled include mechanisms of nucleation, condensation, dry deposition and gas/particle partitioning of organic matter. The model is first applied to a number of case studies involving emissions from point sources and sulfate particle formation in plumes. Model calculations show that homogeneous nucleation is an efficient process for new particle formation in plumes, in agreement with previous field studies and theoretical predictions. In addition, the model is compared with field data from power plant plumes with satisfactory predictions against gaseous species and total sulphate mass measurements. Finally, the plume model is applied to study secondary organic matter formation due to various emission categories such as vehicles and the oil production sector.     

The acid catalyzed nitration of methanol: formation of methyl nitrate via aerosol chemistry

The aqueous phase acid-catalyzed reaction of methanol (CH₃OH) with nitric acid (HNO₃) to yield methyl nitrate (CH₃ONO₂) under atmospheric conditions has been investigated using gas-phase infrared spectroscopy. Reactions were conducted in aqueous sulfuric acid solutions (50.5–63.6 wt.%) with [CH₃OH] = 0.00005–0.005 M and [HNO₃] = 0.02–0.21 M, at 278.2–328.6 K. Methyl nitrate production rates increased linearly with CH₃OH and HNO₃ concentrations and exponentially with sulfuric acid weight percent within the regime studied. Rates increased linearly with nitronium ion concentration, indicating that the reaction involves as the nitrating agent under these conditions. At 298 K, the rate of methyl nitrate production can be calculated from k _obs [CH₃OH][HNO₃], where k _obs  = 2.337 × 10⁻¹³(exp(0.3198*wt.% H₂SO₄)) when the solubility of CH₃ONO₂ in acidic solution is approximated by H* for pure water. The temperature dependence of the rate coefficient is related to solution composition, with activation energies of 59 and 49 kJ/mol at 51.1 and 63.6 wt.% H₂SO₄, respectively, when k is calculated from rate. The temperature dependence has also been parameterized for application to the atmosphere, but the small quantities of present in aerosol particles will result in methyl nitrate production rates too small to be of significance under most atmospheric conditions. An erratum to this article can be found at     

气溶胶对云中水成物粒子荷电情况的影响

利用已有的二维雷暴云起电模式,加入气溶胶模块,建立一个完善的雷暴云起电模式.结合SEET个例,初步探讨了气溶胶浓度对雷暴云内各种水成物粒子荷电情况的影响.发现气溶胶的浓度与雷暴云内云滴、霰粒、冰雹以及雨滴等水成物粒子在空间所携带的最大电荷面密度值以及电荷量有很好的正相关性;同时气溶胶粒子浓度的增加使得雨滴在空间携带电荷量达到峰值的时间有一定提前.     

A closure study of sub-micrometer aerosol particle hygroscopic behaviour

The hygroscopic properties of sub-micrometer aerosol particles were studied in connection with a ground-based cloud experiment at Great Dun Fell, in northern England in 1995. Hygroscopic diameter growth factors were measured with a Tandem Differential Mobility Analyser (TDMA) for dry particle diameters between 35 and 265 nm at one of the sites upwind of the orographic cloud. An external mixture consisting of three groups of particles, each with different hygroscopic properties, was observed. These particle groups were denoted less-hygroscopic, more-hygroscopic and sea spray particles and had average diameter growth factors of 1.11–1.15, 1.38–1.69 and 2.08–2.21 respectively when taken from a dry state to a relative humidity of 90%. Average growth factors increased with dry particle size. A bimodal hygroscopic behaviour was observed for 74–87% of the cases depending on particle size. Parallel measurements of dry sub-micrometer particle number size distributions were performed with a Differential Mobility Particle Sizer (DMPS). The inorganic ion aerosol composition was determined by means of ion chromatography analysis of samples collected with Berner-type low pressure cascade impactors at ambient conditions. The number of ions collected on each impactor stage was predicted from the size distribution and hygroscopic growth data by means of a model of hygroscopic behaviour assuming that only the inorganic substances interacted with the ambient water vapour. The predicted ion number concentration was compared with the actual number of all positive and negative ions collected on the various impactor stages. For the impactor stage which collected particles with aerodynamic diameters between 0.17–0.53 μm at ambient relative humidity, and for which all pertinent data was available for the hygroscopic closure study, the predicted ion concentrations agreed with the measured values within the combined measurement and model uncertainties for all cases but one. For this impactor sampling occasion, the predicted ion concentration was significantly higher than the measured. The air mass in which this sample was taken had undergone extensive photochemical activity which had probably produced hygroscopically active material other than inorganic ions, such as organic oxygenated substances.     

On the distribution of physical and chemical particle properties in the atmospheric aerosol

Consideration of sources and growth dynamics of aerosols has led to the conclusion that there may be a distribution or variation of chemical composition and physical structure among atmospheric aerosol particles as a function of size, and within a narrow size range as well. A mathematical representation of these particle properties in terms of an additional dimension to the number size distribution is described. Examples of the relevance of this aspect of aerosol characterization for physical and chemical processes in the atmosphere are discussed. A review of the available techniques shows that several methods are available which can and have provided quantitative results on the distribution of particle properties. Examples of data from the literature have been selected and are presented as three-dimensional distributions illustrating the wide range of particle properties which may exist in narrow size intervals. An evaluation of these results reiterates the value of taking the distribution of particle properties in the atmosphere into account for sampling and modeling purposes.     

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.     

Regional model for formation,dynamics and Long-range transport of atmospheric aerosol: Study of atmospheric aerosol properties in Europe

This paper provides performance evaluation of the EMEP (Cooperative Programme for the Monitoring and Evaluation of the Long-range Transmission of Air Pollutants in Europe) model, formulated in [1], and presents model calculation results. A satisfactory agreement is found between calculated and observed PM₁₀ and PM_2.5 concentrations (i.e., particulate matter with diameters smaller than 10 and 2.5 μm) and their chemical composition for different parts of Europe for the years 2001–2004. The model manages to reproduce observed regional gradients of background PM₁₀ and PM_2.5, with spatial correlations being 0.70 and 0.80, respectively, while the temporal correlation coefficients between modeled and measured daily PM vary mostly between 0.4 and 0.8 at EMEP sites. The agreement between calculated and observed aerosol number concentrations is worse than for mass concentrations. Model calculated PM₁₀ and PM_2.5 concentrations and chemical composition in Europe for the year 2004 are presented, as well as their interannual variations in the period 2000–2004. Further, contributions of different sources to PM₁₀ and PM_2.5 are estimated. Model results show that in 2004, background PM₁₀ and PM_2.5 exceeded EU critical levels and WHO recommended guidelines in a number of European regions. They also show that the transboundary transport contributes considerably to PM pollution in the European countries.     

Numerical model of the cloud particle isotope composition formation

A non-stationary numerical model for isotope composition formation of cloud particles is developed. The improved model consists of three blocks: hydrothermodynamic, microphysical, and isotope. The latter block contains equations for calculation of isotope content in water vapor and in the cloud particles. The results of the study show that the developed approach can be applied to widen resources for interpretation of surface measurements of hail.     

Application of particle induced X-ray emission to aerosol long-range transport studies—transport pathways of pollution aerosol over the Atlantic ocean and Europe

Particle induced X-ray emission analysis (PIXE) has been applied to aerosol long-range transport studies. The combination of a size fractionating sampler and a multi-element technique has enabled the identification of the transport pathways of individual constituents over the Atlantic Ocean and Europe. Chemical and size distribution data were obtained for aerosols collected at different sampling sites for the ground layer and the free atmosphere. Evaluation of these data under the aspect of air mass history extended the elemental determination in long range transport. A statistical technique was introduced and used to succeed in the semi-quantitative determination of transported pollutants.