Hygroscopic growth of aerosol particles and its influence on nucleation scavenging in cloud: Experimental results from Kleiner Feldberg

The hygroscopic growth of individual aerosol particles has been measured with a Tandem Differential Mobility Analyser. The hygroscopic growth spectra were analysed in terms of diameter change with increasing RH from 20% to 85%. The measurements were carried out during the GCE cloud experiment at Kleiner Feldberg, Taunus, Germany in October and November 1990.Two groups of particles with different hygroscopic growth were observed. The less-hygroscopic group had average growth factors of 1.11, 1.04 and 1.02 for particle diameters of 50, 150 and 300 nm, respectively. The more-hygroscopic group had average growth factors of 1.34, 1.34, and 1.37 for the same particle diameters. The average fraction of less-hygroscopic particles was about 50%. Estimates of the soluble fractions of the particles belonging to the two groups are reported.Hygroscopic growth spectra for total aerosol, interstitial aerosol and cloud drop residuals were measured. A comparison of these hygroscopic growths of individual aerosol particles provides clear evidence for the importance of hygroscopic growth in nucleation scavenging. The measured scavenged fraction of particles as a function of diameter can be explained by the hygroscopic growth spectra.     

Computer modelling of clouds at Kleiner Feldberg

The airflow, cloud microphysics and gas- and aqueous-phase chemistry on Kleiner Feldberg have been modelled for the case study of the evening of 1 November 1990, in order to calculate parameters that are not easily measured in the cloud and thus to aid the interpretation of the GCE experimental data-set. An airflow model has been used to produce the updraught over complex terrain for the cloud model, with some care required to ensure realistic modelling of the strong stable stratification of the atmosphere. An extensive set of measurements has been made self-consistent and used to calculate gas and aerosol input parameters for the model. A typical run of the cloud model has calculated a peak supersaturation of 0.55% which occurs about 20 s after entering cloud where the updraught is 0.6 m s^–1. This figure has been used to calculate the efficiency with which aerosol particles were scavenged; it is higher than that calculated by other methods, and produces a cloud with slightly too many droplets. A broad cloud droplet size spectrum has been produced by varying the model inputs to simulate turbulent mixing and fluctuations in cloud parameters in space and time, and the ability of mixing processes near cloud-base to produce a lower peak supersaturation is discussed. The scavenging of soluble gases by cloud droplets has been observed and departures from Henry's Law in bulk cloud-water samples seen to be caused by variation of pH across the droplet spectrum and the inability of diffusion to adjust initial distributions of highly soluble substances across the spectrum in the time available. Aqueous-phase chemistry has been found to play a minor role in the cloud as modelled, but circumstances in which these processes would be more important are identified.     

Microphysics of clouds at Kleiner Feldberg

During a field measuring campaign at Kleiner Feldberg (Taunus) in 1990, microphysical characteristics of clouds have been measured by Forward Scattering Spectrometer Probes (FSSP). The aim was to study the influence of aerosol and meteorological factors on droplet size and number. The results are: More mass in the accumulation size range of the aerosol leads to more droplets in stratocumulus clouds and to higher soluble masses in droplets of stratus clouds. However, the aerosol distribution was coarser in the stratus clouds compared to the stratocumulus clouds. Within the first 200 m from cloud base, the droplets grow while their number decreases. The growth results in a stable size of about 14 µm diameter over a large distance from cloud base in many stratocumulus clouds. Two types of mixing processes were observed: processes with reductions in the number of droplets (inhomogeneous mixing) and with reductions in the size of the droplets (homogeneous mixing).     

Multiphase chemistry and acidity of clouds at Kleiner Feldberg

The chemistry of cloud multiphase systems was studied within the Kleiner Feldberg Cloud Experiment 1990. The clouds encountered during this experimental campaign could be divided into two categories according to the origin of air masses in which the clouds formed. From the chemical point of view, clouds passing the sampling site during the first period of the campaign (26 October-4 November) were characterized by lower pollutant loading and higher pH, as compared to clouds during the final period of the experimental campaign (10–13 November). The study of multiphase partitioning of the main chemical constituents of the cloud systems and of atmospheric acidity within the multiphase systems themselves (gas + interstitial aerosol + liquid droplets) are presented in this paper. A general lack of gaseous NH₃ was found in these cloud systems, which caused a lack of buffer capacity toward acid addition. Evidence supports the hypothesis that the higher acidity of the cloud systems during this final period of the campaign was due to input of HNO₃. Our measurements, however, could not determine whether the observed input was due to scavenging of gaseous HNO₃ from the air feeding into the cloud, or to heterogeneous HNO₃ formation via NO₂ oxidation by O₃ to NO₃ and N₂O₅. Sulfate in cloud droplets mainly originated from aerosol SO ₄ ^2– scavenging, since S(IV) to S(VI) liquid phase conversion was inhibited due to both lack of H₂O₂ and low pH of cloud droplets, which made O₃ and metal catalyzed S(IV) oxidation inefficient.     

Deposition of trace substances via cloud interception on a coniferous forest at Kleiner Feldberg

A resistance model to calculate the deposition of cloud droplets on a coniferous forest and some improved parameterizations of the indispensable input parameters are described. The deposition model is adapted to the coniferous forest at the Kleiner Feldberg site and verified by the data of a drip water monitoring station below the forest canopy. The measurements of liqud water content, wind speed and trace substance compounds in cloud water of the Ground-based Cloud Experiment (GCE) at Kleiner Feldberg in 1990 are used to calculate the cloud water deposition fluxes and the deposition of trace substances via cloud water interception. The calculated deposition of trace substances via cloud water interceptions is three to six times higher than via rain during the experiment. On a long term data basis the yearly amount of cloud water deposition is 180 mm year^–1 at Kleiner Feldberg site (840 m a.s.l.) while the precipitation amount is 1030 mm year^–1. Due to higher trace substance concentrations in cloud water compared to rain the ionic deposition via cloud water interception and via precipitation were assessed to be of comparable magnitude.     

On the effect of the chemical composition of atmospheric aerosol particles on nucleation scavenging and the formation of a cloud interstitial aerosol

Nucleation scavenging and the formation of a cloud interstitial aerosol (CIA) were theoretically studied in terms of the chemical composition of atmospheric aerosol particles. For this study, we used our air-parcel cloud model, which includes the entrainment of air and detailed microphysics, for determining the growth and interaction of aerosol particles and drops. Maritime and remote continental aerosol particle spectrums were used whose size distributions were superpositions of three log-normal distributions, each of a prescribed chemical composition. Our results show (1) that the CIA exhibits a size distribution with a distinctive cut-off at a specific radius of the dry as well as of the wet particle size distribution. All particles above this limiting size become activated to cloud drops and, thus, are not present in the CIA spectrum. This limiting size was found to be independent of the chemical composition of the particles and only dependent on the prevailing supersaturation. Below this specific size, the CIA spectrum becomes depleted of dry aerosol particles in a manner which does depend on their chemical composition and on the supersaturation in the air. (2) The number of aerosol particles nucleated to cloud drops depends critically on the chemical composition of the particles and on the prevailing supersaturation.     

The chemical fractionation of atmospheric aerosol as a result of snow crystal formation and growth

The relationships between the physical and chemical properties of mixed-phase clouds were investigated at Storm Peak Laboratory (3220m MSL) located near the continental divide in northwestern Colorado. Interstitial aerosol particles, cloud droplets and snow crystals were concurrently collected when the laboratory was enveloped by a precipitating cloud. All samples were analyzed for trace elements, soluble anions, electrical conductivity and acidity.The results show average trace constituent concentration ratios of cloud water to snow water range from 0.4 to 26. All but six of the 32 elements and ions measured had ratios greater than one. This result suggests a chemical species dependency of in-cloud aerosol particle scavenging processes. Evidence of a decrease of in-cloud aerosol particle scavenging efficiency by snow due to increases in aerosol concentration is also presented.Differences between the chemical composition of cloud water and snow water are manifested most strongly when snow crystals grow by vapor deposition. In-cloud scavenging efficiencies by snow crystals for most aerosol particle chemical species are dependent on the growth of the snow crystals by accretion of cloud droplets. This chemical fractionation of the atmospheric aerosol by snow crystal formation and growth should be most active where narrow, continental cloud droplet size distributions and low liquid water contents are prevalent, enhancing the probability of snow crystal growth by diffusion.     

Incorporation of aerosol particles between 25 and 850 nm into cloud elements: measurements with a new complementary sampling system

The interpretation of the physico-chemical processes in clouds is facilitated by segregating in situ cloud elements from their carrier gas and small particles (interstitial aerosol). Thus, the present study focuses on the quantitative phase segregation of interstitial air from cloud phase by two complementary samplers with microphysical on-line analysis of the separated phases. An improved counterflow virtual impactor (CVI) was developed for the collection and subsequent evaporation of the condensed phase, releasing dissolved gaseous material and residual particles. This sampler operates in the size range of few micrometers up to 50 μm in cloud element diameter and is matched by an interstitial Round Jet Impactor sampling the gas phase with interstitial particles. Calibrations of both samplers verified the calculated cut sizes D₅₀ of 4, 5, and 6 μm and quantified the slope of the collection efficiency curves. Until this study no direct CVI measurements of the residual particle sizes far below the diameter of 0.1 μm were available. For the first time a CVI was connected to a Differential Mobility Particle Sizer (DMPS) scanning between 25 nm and 850 nm, thus, including the entire Aitken mode in the residual size analysis. Cloud studies on the Puy de Dôme, France, revealed residual particle sizes including Aitken mode (diameter D<100 nm) and accumulation mode (D>100 nm). A major feature of the CVI data is expressed by the fact that despite incomplete incorporation of accumulation mode particles in cloud elements there are contributions of particles with diameters smaller than 0.1 μm to the number of residual particles. Cloud entrainment from height levels above the maximum supersaturation as wells as the size-dependent chemical composition of the aerosol population most likely produced the S-shaped size-dependent partitioning of residual particles. Compared to earlier studies the 50% partitioning diameters dropped significantly below 100 nm to roughly 70 nm.     

Measurement of Ambient,Interstitial, and Residual Aerosol Particles on a Mountaintop Site in Central Sweden using an Aerosol Mass Spectrometer and a CVI

The Aerodyne aerosol mass spectrometer (Q-AMS) was coupled with a counterflow virtual impactor (CVI) for the first time to measure cloud droplet residuals of warm tropospheric clouds on Mt. Åreskutan in central Sweden in July 2003. Operating the CVI in different operational modes generated mass concentration and species-resolved mass distribution data for non-refractory species of the ambient, interstitial, and residual aerosol. The ambient aerosol measurements revealed that the aerosol at the site was mainly influenced by long-range transport and regional photochemical generation of nitrate and organic aerosol components. Four different major air masses were identified for the time interval of the experiment. While two air masses that approached the site from northeastern Europe via Finland showed very similar aerosol composition, the other two air masses from polar regions and the British Islands had a significantly different composition. During cloud events the larger aerosol particles were found to be activated into cloud droplets. On a mass basis the activation cut-off diameter was approximately 150 nm for nitrate and organics dominated particles and 200 nm for sulfate dominated particles. Generally nitrate and organics were found to be activated into cloud droplets with higher efficiency than sulfate. While a significant fraction of the nitrate in ambient particles was organic nitrates or nitrogen-containing organic species, the nitrate found in the cloud droplet residuals was mainly ammonium nitrate. After passage of clouds the ambient aerosol size distribution had shifted to smaller particle sizes due to the predominantly activation of larger aerosol particles without a significant change in the relative composition of the ambient aerosol.     

Aerosol-cloud chemical fractionation: Enrichment factor analysis of cloud water

A field study was conducted at a mountain-top site in northwestern Colorado. Supercooled cloud water, collected as a function of droplet size, was analyzed for anions, cations and trace elements. Enrichment factors (EF) of SO ₄ ^2– , K⁺, Na⁺ and Cl^– relative to crustal and marine reference elements (Al and Na) were calculated to determine whether chemical fractionation of the aerosol occurs during cloud droplet formation. The largest EF's for all ions were found for droplets less than 10–15 µm diameter. Ratios of the small to large droplet mean EF's ranged from 1 to 2, for SO ₄ ^2– relative to both Al and Na⁺, to 10 to 12 for Na⁺, Cl^– and K⁺, relative to Al. EF's of K⁺ and Cl^– in the bulk cloud water were in crustal and marine proportions, respectively. It was concluded that although bulk could chemistry may indicate a lack of enrichment of a species, this may not be true throughout the droplet size distribution. The higher enrichments in small droplets is likely a result of their formation on small aerosol particles whereas the large droplets form on the largest aerosol particles. This may suppress EF's in precipitation relative to the total aerosol.     

Observed changes in aerosol physical and optical properties before and after precipitation events

Precipitation scavenging of aerosol particles is an important removal process in the atmosphere that can change aerosol physical and optical properties. This paper analyzes the changes in aerosol physical and optical properties before and after four rain events using in situ observations of mass concentration, number concentration, particle size distribution, scattering and absorption coefficients of aerosols in June and July 2013 at the Xianghe comprehensive atmospheric observation station in China. The results show the effect of rain scavenging is related to the rain intensity and duration, the wind speed and direction. During the rain events, the temporal variation of aerosol number concentration was consistent with the variation in mass concentration, but their size-resolved scavenging ratios were different. After the rain events, the increase in aerosol mass concentration began with an increase in particles with diameter 0.8 μm [measured using an aerodynamic particle sizer(APS)], and fine particles with diameter 0.1 μm [measured using a scanning mobility particle sizer(SMPS)]. Rainfall was most efficient at removing particles with diameter ～0.6 μm and greater than 3.5 μm. The changes in peak values of the particle number distribution(measured using the SMPS) before and after the rain events reflect the strong scavenging effect on particles within the 100–120 nm size range. The variation patterns of aerosol scattering and absorption coefficients before and after the rain events were similar, but their scavenging ratios differed, which may have been related to the aerosol particle size distribution and chemical composition.     

气溶胶核化清除的化学效应 I：云滴化学非均匀性的研究

本文将水汽在云滴上凝结增长的物理过程与气溶胶、气体的化学过程相结合，对气溶胶核化清除的化学效应进行了研究。 计算结果表明:气溶胶的核化清除造成了云滴化学成分随云滴大小分布的非均匀性，这种非均匀性又对云滴内发生的气体吸收、液相氧化产生影响。 本文还比较了不同污染状况下，不同大小的云滴内气溶胶核化清除与液相氧化对云滴化学的相对贡献的差异。 因此，这种云滴化学的非均匀性(云微化学)的研究对于云化学的野外观测及数值模拟都是重要的。     

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.     

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.     

Characteristics of biomass burning aerosol and its impact on regional air quality in the summer of 2003 at Gwangju, Korea

The main objective of this study is to investigate the chemical characteristics of biomass burning aerosol and its impact on regional air quality during an agricultural waste burning period in early summer in the rural areas of Korea. A 12-h integrated intensive sampling of biomass burning aerosol in the fine and coarse modes was conducted on 2–20 June 2003 in Gwangju, Korea. The collected samples were analyzed for concentrations of mass, ionic, elemental, and carbonaceous species. Average concentrations of fine and coarse mass were measured to be 67.9 and 18.7 μg m^− 3 during the biomass burning period, 41.9 and 18.8 μg m^− 3 during the haze period, and 35.6 and 13.3 μg m^− 3 during the normal period, respectively. An exceptionally high PM_2.5 concentration of 110.3 μg m^− 3 with a PM_2.5/PM₁₀ ratio of 0.79 was observed on 6 June 2003 during the biomass burning period. The potassium ratio method was used to identify biomass burning samples. The average ratio of potassium in the fine mode to the coarse mode (FK/CK) was 23.8 during the biomass burning period, 6.0 during the haze period, and 4.7 during the normal period, respectively. A FK/CK ratio above 9.2 was considered a criterion for biomass burning event in this study. Particulate matter from the open field burning of agricultural waste has an adverse impact on visibility, human health, and regional air quality.     

Sulfate and methanesulfonate in the maritime aerosol at Cape Grim,Tasmania

High-volume aerosol filters, exposed in maritime air masses at Cape Grim since late 1976, were analysed for excess sulfate (not of seasalt origin) and methanesulfonate. The mean concentrations (standard errors) of 2.80(0.59) and 0.176(0.027) nmole/m³ respectively are about half those reported in a recent study of aerosol samples from various locations in the Atlantic and Pacific oceans.Methanesulfonate concentration varied seasonally by at least an order of magnitude with a summer maximum and winter minimum. No comparable cycle was found for excess sulfate.     

Microphysical and chemical characteristics of cloud droplet residuals and interstitial particles in continental stratocumulus clouds

During June and July 2003 the Sources and Origins of Atmospheric Cloud Droplets experiment (SOACED) was carried out on a mountain-top site in central Sweden. The main objective of the experiment was to characterise the microphysical and chemical properties of cloud droplet residuals and interstitial aerosol particles in continental clouds and to understand the processes controlling cloud properties at this location.Interstitial and residual aerosol size distributions, cloud liquid water content and species- and size-resolved aerosol mass concentrations are the main variables employed to address questions pertaining to the cloud droplet number concentration and scavenging efficiency during a stratocumulus cloud event observed on July 28, 2003. In this cloud event, about 56% of the aerosol mass was associated with organic species, whilst SO₄ accounted for 23% and NH₄ for 14%. NO₃ and Cl made up about 7% of the total mass.The partitioning of the aerosol particles between cloud droplets and interstitial air has been studied in terms of their microphysical properties. The scavenging efficiency, defined as the fraction of particles activated into cloud elements compared to the total amount of particles, was investigated as a function of size. The scavenging efficiency curves displayed different shapes during the cloud event, from an S-shaped curve, with low scavenging efficiency in the Aitken mode and larger scavenging efficiency in the accumulation mode, to more unusual shapes where Aitken-mode particles were either solely activated or activated in addition to accumulation-mode particles.This study suggests that alterations of the aerosol chemical composition occurred during the measurement period, changing the hygroscopic nature of the CCN and decreasing their activation diameter. It is also hypothesized that entrainment of drier air aloft may have introduced inhomogeneities in the supersaturation field and modified the S-shaped scavenging curves.     

我国不同背景地区大气冰核浓度特征及参数化

为深入了解我国不同背景地区大气冰核浓度特征,本文通过在我国不同地区进行大气冰核及气溶胶的采样观测。研究发现：观测期间,黄山光明顶的冰核浓度数值均值为2.208 L^-1;南京地区的冰核浓度数值均值为7.16 L^-1;泰山山顶的冰核浓度数值均值为3.455 L^-1;泰山山底的冰核浓度数值均值为4.818 L^-1;新疆地区无沙尘天气冰核浓度数值均值为11.27 L^-1;新疆有沙尘天气冰核浓度数值均值为51.812 5 L^-1。研究给出了不同背景地区的大气冰核浓度的温度谱和湿度谱的分布。同时,研究发现,冰核数浓度与粒径大于0.5μm的气溶胶粒子数浓度的相关性较高,也就是气溶胶粒子中大颗粒所占比例越高,冰核数浓度越高。此外,还建立了基于活化温度、过饱和度以及大于0.5μm气溶胶粒子数浓度的冰核参数化方案,它们可以分别适用于沙漠地表,相对清洁的背景区域和人为污染较多的城市背景。