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.     

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.     

Large aerosol particles in cirrus type clouds

Research flights in November 1990 over the central parts of the United States, Wyoming and Colorado, were aimed to the investigation of the properties and microstructure of cirrus clouds (mainly cirrocumulus lenticularis). Among the other parameters measured on board the NCAR Saberliner were the concentration and size distribution of submicron particles and, in some cases, the particle deliquescence. For coarse insoluble particles found inside and outside of cloud elements, size distributions and morphology information were obtained by evaluating inertial impactor samples with an optical microscope and scanning electron microscope. In addition, the coarse particle composition was determined by x-ray energy spectrum analysis. The following conclusions from these measurements are:The large and coarse particle size distribution can be roughly simulated by a log-normal function with the modus around r=0.5 μm. Particle concentrations are very variable between several tenths and several particles per cm³. Particle volume distribution features a distinct maximum around 0.75 μm without a broad plateau which was observed in the case of sampling at lower altitude. Aerosol composition heterogeneity at cirrus cloud level is well documented by the evaluation of the fine particle sampling taken with the UMR sampling system. This heterogeneity can be partly explained by the interaction between aerosol and cloud elements, which is documented by the measured particle size distribution curves inside and outside of cloud elements. Assuming that particle deliquescence is caused by H₂SO₄ and/or by (NH₄)₂SO₄, particle soluble mass fractions were found to be around 30% in the first case and about 40% in the second. The most frequently occurring elements in large and coarse particles at cirrus cloud level were Si, Cl, Ba, S, Ca and C.     

Numerical study of the oxidation process of dimethylsulfide in the marine atmosphere

A box model, involving simple heterogeneous reaction processes associated with the production of non-sea-salt sulfate (nss-SO ₄ ^2– ) particles, is used to investigate the oxidation processes of dimethylsulfide (DMS or CH₃SCH₃) in the marine atmosphere. The model is applied to chemical reactions in the atmospheric surface mixing layer, at intervals of 15 degrees latitude between 60° N and 60° S. Given that the addition reaction of the hydroxyl radical (OH) to the sulfur atom in the DMS molecule is faster at lower temperature than at higher temperature and that it is the predominant pathway for the production of methanesulfonic acid (MSA or CH₃SO₃H), the results can well explain both the increasing tendency of the molar ratio of MSA to nss-SO ₄ ^2– toward higher latitudes and the uniform distribution with latitude of sulfur dioxide (SO₂). The predicted production rate of MSA increases with increasing latitude due to the elevated rate constant of the addition reaction at lower temperature. Since latitudinal distributions of OH concentration and DMS reaction rate with OH are opposite, a uniform production rate of SO₂ is realized over the globe. The primary sink of DMS in unpolluted air is caused by the reaction with OH. Reaction of DMS with the nitrate radical (NO₃) also reduces DMS concentration but it is less important compared with that of OH. Concentrations of SO₂, MSA, and nss-SO ₄ ^2– are almost independent of NO _x concentration and radiation field. If dimethylsulfoxide (DMSO or CH₃S(O)CH₃) is produced by the addition reaction and further converted to sulfuric acid (H₂SO₄) in an aqueous solution of cloud droplets, the oxidation process of DMSO might be important for the production of aerosol particles containing nss-SO ₄ ^2– at high latitudes.     

Analytical electron microscope studies of size-segregated particles collected during AGASP-II,flights 201–203

Cascade impactor samples were collected over the Alaskan Arctic during the first three research flights of AGASP-II. These samples were analyzed using analytical electron microscopy to determine the morphology, mineralogy and elemental composition of individual particles. For analytical considerations, a typical impactor sample was run for approximately 20 min, thus giving excellent time resolution of discrete events.Samples collected during flights 201 and 202 consisted of stratospheric aerosol and lower-altitude haze samples. Stratospheric samples were characterized by moderate loadings of H₂SO₄ droplets with relatively few particles of other types. Samples collected in tropospheric haze layers generally exhibited light-to-moderate particle loadings. H₂SO₄ was again the most prevalent species, with crustal and anthropogenic particles also observed. One sample taken over south-central Alaska near the end of flight 203 showed high concentrations of solid crustal particles, with relatively little associated H₂SO₄. Giant particles larger than 5 m were occasionally observed in this aerosol. The composition of this material closely matches that of bulk ash from the Mt. Augustine volcano, which erupted 9–13 days before collection of this sample. This brings forth the possibility that pockets of ash-rich aerosol existed over parts of south and central Alska during the AGASP-II field mission. There is no evidence that these volcanic aerosols were present in the AGASP study area north of the Brooks Range.     

The effects of in-cloud mass production on atmospheric light scatter

Direct physical measurements of particle mass and number concentration indicate an increase in overall aerosol mass resulting from cloud processing, most likely through aqueous-phase chemistry (e.g., SO₂ oxidation). Measurements conducted in the Pennines of Northern England reveal an average increase of 14 to 20% in dry aerosol mass (0.003<particle diameter<0.9 μm) after aerosol passage through an orographic cloud. The rate of in-cloud mass production is most sensitive to changes in upwind particle size distributions, SO₂ concentration, and cloud water acidity. Newly-formed mass appears in size range between 200 and 600 nm and enhances the bimodality of the particle number distribution after cloud processing. Furthermore, the cloud-produced mass is estimated to increase total light scattering, b_sp, by 18 to 24%. The scattering efficiency of the dry, cloud-generated aerosol is 5.0±0.3 m² g⁻¹ and increases to 7.4±0.7 m² g⁻¹ when adjusted to 90% relative humidity by incorporating particle hygroscopicity data.     

Observation of DMSO and CH3S(O)OH from the gas phase reaction between DMS and OH

Products and mechanisms have been investigated for the reactions between dimethylsulfide (DMS) and dimethylsulfoxide (DMSO) and the hydroxyl radical (OH) in the presence of NO_x. All of the experiments were performed in a 480 L reaction chamber, applying Fourier transform infrared spectroscopy (FT-IR) and ion chromatography as the analytical techniques.In addition to the sulfur containing products that are known to be produced from the gas phase reaction between DMS and OH (SO₂, dimethylsulfone, methylsulfonyl peroxynitrate, methanesulfonic acid, H₂SO₄), DMSO and methanesulfinic acid (CH₃S(O)OH) were also observed as products. Only SO₂, DMSO₂ and methylsulfonyl peroxynitrate were found as sulfur containing products in the reaction between DMSO and OH. Based on these new results we propose a mechanism for the atmospheric oxidation of DMS and DMSO by OH radical.     

Model Simulations on the Variability of Particulate MSA to Non-Sea-Salt Sulfate Ratio in the Marine Environment

A box model was constructed to investigate connections between the particulate MSA to non-sea-salt sulfate ratio, R, and DMS chemistry in a clean marine boundary layer. The simulations demonstrated that R varies widely with particle size, which must be taken into account when interpreting field measurements or comparing them with each other. In addition to DMS gas-phase chemistry, R in the submicron size range was shown to be sensitive to the factors dictating sulfate production via cloud processing, to the removal of SO₂ from the boundary layer by dry deposition and sea-salt oxidation, to the entrainment of SO₂ from the free troposphere, to the relative concentration of sub- and supermicron particles, and to meteorology. Three potential explanations for the increase of R toward high-latitudes during the summer were found: larger MSA yields from DMS oxidation at high latitudes, larger DMSO yields from DMS oxidation followed by the conversion of DMSO to MSA at high latitudes, or lower ambient H₂O₂ concentrations at high latitudes leading to less efficient sulfate production in clouds. Possible reasons for the large seasonal amplitude of R at mid and high latitudes include seasonal changes in the partitioning of DMS oxidation to the OH and NO₃ initiated pathways, seasonal changes in the concentration of species participating the DMS-OH reaction pathway, or the existence of a SO₂ source other than DMS oxidation in the marine boundary layer. Even small anthropogenic perturbations were shown to have a potential to alter the MSA to non-sea-salt sulfate ratio.     

On the growth of nitric and sulfuric acid aerosol particles under stratospheric conditions

We present a theory for the formation of frozen aerosol particles in the Antarctic stratosphere, the coldest region of the Earth's stratosphere. The theory is applied specifically to the formation of polar stratospheric clouds. We suggest that the condensed ices are composed primarily of nitric acid and water with small admixtures of other compounds such as H₂SO₄ and HCl in solid solution. Our assumed particle formation mechanism is in agreement with the magnitude and seasonal behavior of the optical extinctions observed in the winter polar stratosphere. Physical chemistry and thermodynamic considerations suggest that at temperatures between about 200 and 185 K, stratospheric particulates are composed primarily of frozen nitric acid solutions with a composition near that of the trihydrate. Available data suggest the particles are amorphous solid solutions and not in the crystalline hydrate form. At lower temperatures (i.e., below the forst point of pure water) cirrus-like ice clouds can form.     

Sources,transport, and sinks of SO<Subscript>2</Subscript> over the equatorial Pacific during the Pacific Atmospheric Sulfur Experiment

The Pacific Atmospheric Sulfur Experiment (PASE) is the first sulfur-budget field experiment to feature simultaneous flux measurements of DMS marine emissions and SO₂ deposition to the ocean surface. We make use of these data to constrain a 1-D chemical transport model to study the production and loss pathways for DMS and SO₂ over the equatorial Pacific. Model results suggest that OH is the main sink for DMS in the boundary layer (BL), and the average DMS-to-SO₂ conversion efficiency is ~73%. In an exploratory run involving the addition of 1 pptv of BrO as a second oxidant, a 14% increase in the DMS flux is needed beyond that based on OH oxidation alone. This BrO addition also reduces the DMS-to-SO₂ conversion efficiency from 73% to 60%. The possibility of non-DMS sources of marine sulfur influencing the estimated conversion efficiency was explored and found to be unconvincing. For BL conditions, SO₂ losses consist of 48% dry deposition, while transport loss to the BuL and aerosol scavenging each account for another 19%. The conversion of SO₂ to H₂SO₄ consumes the final 14%. In the BuL, cloud scavenging removes 85% of the SO₂, thus resulting in a decreasing vertical profile for SO₂. The average SO₂ dry deposition velocity from direct measurements (i.e., 0.36 cm sec⁻¹) is approximately 50% of what is calculated from the 1-D model and the global GEOS-Chem model. This suggests that the current generation of global models may be significantly overestimating SO₂ deposition rates over some tropical marine areas. Although the specific mechanism cannot be determined, speculation here is that the dry deposition anomalous results may point to the presence of a micro-surface chemical phenomenon involving partial saturation with either S(IV) and/or S(VI) DMS oxidation products. This could also appear as a pH drop in the ocean’s surface microfilm layer in this region. Finally, we propose that the enhanced SO₂ level observed in the lower free troposphere versus that in the upper BuL during PASE is most likely the result of transported DMS/SO₂-rich free-tropospheric air parcels from the east of the PASE sampling area, rather than an inadequate representation in the model of local convection.     

The scavenging of nitrate by clouds and precipitation

A model with spectral microphysics was developed to describe the scavenging of nitrate aerosol particles and HNO₃ gas. This model was incorporated into the dynamic framework of an entraining air parcel model with which we computed the uptake of nitrate by cloud drops whose size distribution changes with time because of condensation, collision-coalescence and break-up. Significant differences were found between the scavenging behavior of nitrate and our former results on the scavenging behavior of sulfate. These reflect the following chemical and microphysical differences between the two systems:

1. nitrate particles occur in a larger size range than sulfate particles.
2. HNO₃ has a much greater solubility than SO₂ and is taken up irreversibly inside the drops in contrast to SO₂.
3. nitric acid in the cloud water is formed directly on uptake of HNO₃ gas whereas on uptake of SO₂ sulfuric acid is formed only after the reaction with oxidizing agents such as e.g., H₂O₂ or O₃.
4. nitrate resulting from uptake of HNO₃ is confined mainly to small drops, whereas sulfate resulting from uptake of SO₂ is most concentrated in the largest, oldest drops, which have had the greatest time for reaction.

Sensitivity studies showed that the nitrate concentration of small drops is significantly affected by the mass accommodation coefficient.     

Modelling of the nighttime nitrogen and sulfur chemistry in size resolved droplets of an orographic cloud

A chemistry module has been incorporated into a Lagrangian type model that computes the dynamics and microphysics of an orographical cloud formed in moist air flowing over the summit of Great Dun Fell (GDF) in England. The cloud droplets grow on a maritime aerosol which is assumed to be an external mixture of sea-salt particles and ammonium-sulfate particles. The dry particle radii are in the range 10 nm<r<1 µm. The gas-phase chemical reaction scheme considers reactions of nitrogen compounds that are important at night. The treatment of scavenging of gases into the aqueous phase in the model takes into account the different solubilities and accommodation coefficients. The chemistry in the aqueous phase focusses on the oxidation of S(IV) via different pathways.Sensitivity analyses have been performed to investigate deviations from gas-liquid equilibria according to Henry's law and also to study the influence of iron and of nitrogen compounds on the aqueous-phase oxidation of dissolved SO₂. When addressing these questions, special attention has been given to the dependence on the droplet size distribution and on the chemical composition of the cloud condensation nuclei on which the droplets have formed. It was found that the oxidation of S(IV) via a chain reaction of sulfur radicals can be important under conditions where H₂O₂ is low. However, major uncertainties remain with respect to the interaction of iron with the radical chain. It was shown that mixing of individual cloud droplets, which are not in equilibrium according to Henry's law, can result in a bulk sample in equilibrium with the ambient air. The dependence of the aqueous-phase concentrations on the size of the cloud droplets is discussed for iron, chloride and NO₃.     

Modelling multiphase chemistry in deliquescent aerosols and clouds using CAPRAM3.0i

Modelling studies were performed with the multiphase mechanism RACM-MIM2ext/CAPRAM 3.0i to investigate the tropospheric multiphase chemistry in deliquesced particles and non-precipitating clouds using the SPACCIM model framework. Simulations using a non-permanent cloud scenario were carried out for two different environmental conditions focusing on the multiphase chemistry of oxidants and other linked chemical subsystems. Model results were analysed by time-resolved reaction flux analyses allowing advanced interpretations. The model shows significant effects of multiphase chemical interactions on the tropospheric budget of gas-phase oxidants and organic compounds. In-cloud gas-phase OH radical concentration reductions of about 90 % and 75 % were modelled for urban and remote conditions, respectively. The reduced in-cloud gas-phase oxidation budget increases the tropospheric residence time of organic trace gases by up to about 30 %. Aqueous-phase oxidations of methylglyoxal and 1,4-butenedial were identified as important OH radical sinks under polluted conditions. The model revealed that the organic C₃ and C₄ chemistry contributes with about 38 %/48 % and 8 %/9 % considerably to the urban and remote cloud / aqueous particle OH sinks. Furthermore, the simulations clearly implicate the potential role of deliquescent particles to operate as a reactive chemical medium due to an efficient TMI/HO_x,y chemical processing including e.g. an effective in-situ formation of OH radicals. Considerable chemical differences between deliquescent particles and cloud droplets, e.g. a circa 2 times more efficient daytime iron processing in the urban deliquescent particles, were identified. The in-cloud oxidation of methylglyoxal and its oxidation products is identified as efficient sink for NO₃ radicals in the aqueous phase.     

Chemical ionisation mass spectrometer for measurements of OH and Peroxy radical concentrations in moderately polluted atmospheres

A new version of an atmospheric pressure chemical ionisation mass spectrometer has been developed for ground based in situ atmospheric measurements of OH and total peroxy (HO₂ + organic peroxy) radicals. Based on the previously developed principle of chemical conversion of OH radicals to H₂SO₄ in reaction with SO₂ and detection of H₂SO₄ using an ion molecule reaction with NO₃^─, the new instrument is equipped with a turbulent chemical conversion reactor allowing for measurements in moderately polluted atmosphere at NO concentrations up to several ppb. Unlike other similar devices, where the primary NO₃^─ ions are produced using radioactive ion sources, the new instrument is equipped with a specially developed corona discharge ion source. According to laboratory measurements, the overall accuracy and detection limits are estimated to be, respectively, 25% and 2 × 10⁵ molecule cm^-3 for OH and 30% and 1 × 10⁵ molecule cm^-3 for HO₂ at 10 min integration times. The detection limit for measurements of OH radicals under polluted conditions is 5 × 10⁵ molecules cm^-3 at 10 min integration times. Examples of ambient air measurements during a field campaign near Paris in July 2007 are presented demonstrating the capability of the new instrument, although with reduced performance due to the employment of non isotopic SO₂.     

The Cloud Ice Mountain Experiment (CIME) 1998: experiment overview and modelling of the microphysical processes during the seeding by isentropic gas expansion

The second field campaign of the Cloud Ice Mountain Experiment (CIME) project took place in February 1998 on the mountain Puy de Dôme in the centre of France. The content of residual aerosol particles, of H₂O₂ and NH₃ in cloud droplets was evaluated by evaporating the drops larger than 5 μm in a Counterflow Virtual Impactor (CVI) and by measuring the residual particle concentration and the released gas content. The same trace species were studied behind a round jet impactor for the complementary interstitial aerosol particles smaller than 5 μm diameter. In a second step of experiments, the ambient supercooled cloud was converted to a mixed phase cloud by seeding the cloud with ice particles by the gas release from pressurised gas bottles. A comparison between the physical and chemical characteristics of liquid drops and ice particles allows a study of the fate of the trace constituents during the presence of ice crystals in the cloud.In the present paper, an overview is given of the CIME 98 experiment and the instrumentation deployed. The meteorological situation during the experiment was analysed with the help of a cloud scale model. The microphysics processes and the behaviour of the scavenged aerosol particles before and during seeding are analysed with the detailed microphysical model ExMix. The simulation results agreed well with the observations and confirmed the assumption that the Bergeron–Findeisen process was dominating during seeding and was influencing the partitioning of aerosol particles between drops and ice crystals. The results of the CIME 98 experiment give an insight on microphysical changes, redistribution of aerosol particles and cloud chemistry during the Bergeron–Findeisen process when acting also in natural clouds.     

A multifunctional HTDMA system with a robust temperature control

The hygroscopicity of atmospheric aerosols significantly influences their size distribution, cloud condensation nuclei ability, atmospheric residence time, and climate forcing. In order to investigate the hygroscopic behavior of aerosol particles and serious haze in China, a Hygroscopic Tandem Differential Mobility Analyzers (HTDMA) system was designed and constructed at Fudan University. It can function as a scanning mobility particle sizing system to measure particle size distribution in the range of 20--1000 nm in diameter, as well as a hygroscopicity analyzer for aerosol particles with diameters between 20--400 nm in the range of 20%--90% RH (relative humidity). It can also measure the effect of uptake of inorganic acids or semi-VOCs on the hygroscopic behavior of aerosols, such as typical inorganic salts in atmospheric dust or their mixtures. The performance tests show that the system measured particle size of the standard polystyrene latex spheres (PSLs) is 197 nm, which is in excellent agreement with the certified diameter D=199±6 nm, as well as a standard deviation of the repeated runs SD=8.9x10^-4. In addition, the measured hygroscopic growth factors of the model compounds, (NH₄)₂SO₄ and NaNO₃, agree with the Kohler theoretical curves. The results indicate that the HTDMA system is an excellent and powerful tool for studying the hygroscopic behavior of submicron aerosols and meets the demand required for laboratory research and fieldwork on atmospheric aerosols in China.     

Study of metal aerosol systems as a sink for atmospheric SO2

The chemical removal of SO₂ in the presence of different aerosol systems has been investigated in laboratory experiments using a dynamic flow reactor. The aerosols consisted of wetted particles containing one of the following substances: MnCl₂, Mn(NO₃)₂, MnSO₄, CuCl₂, Cu(NO₃)₂, CuSO₄, FeCl₃, NaCl. The SO₂ removal rate R was measured as a function of the SO₂ gas phase concentration (SO₂)_g, the spatial metal concentration C_Me, and the relative humidity rH in the reactor. A first-order dependence with regard to (SO₂)_g was observed for each type of aerosol. For the Mn(II) and Cu(II) aerosols R was found to be a non-linear function of C_Me except for MnSO₄ and Cu(NO₃)₂ particles. The removal rate showed a significant increase with the relative humidity particularly when rH was close to the deliquescence point of the wetted particles. Among the Mn(II) and Cu(II) aerosols investigated Mn(NO₃)₂ was found to be most efficient for the chemical removal of SO₂ at atmospheric background conditions, especially in haze and fog droplets. The results further indicate that the catalytic oxidation of S(IV) in such aerosol systems may be as efficient as its oxidation by H₂O₂ in cloud water.     

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。     

Diffusion aerosol spectrometer

The diffusion aerosol spectrometer for the measurements of particle size spectra and concentration levels is described. It includes three principal parts: (i) a block of diffusion batteries for measuring the particles, whose size does not exceed 0.15 μm, (ii) the particle amplifier for growing the particles passing through the diffusion batteries up to optically distinguishable sizes and (iii) the laser aerosol spectrometer, which counts the amplified particles and may also serve for independent measurements of particle size spectra within submicron size range. The tandem including: diffusion batteries+laser aerosol spectrometer allows for detecting particles of radius >3 nm at maximal concentration up to 2×10⁴ particles/cm³. The tandem is managed either by PC or manually. The instrument is designed for studying aerosols in the atmosphere and for ecological measurements.