大气气溶胶酸度的研究进展

大气气溶胶的环境效应、气候效应和健康效应均与气溶胶的物理化学性质直接相关,其中大气气溶胶酸度是其重要的性质之一。大气气溶胶酸度对酸沉降、灰霾的形成具有重要作用,并影响大气非均相化学反应,相关研究已成为国际研究的热点。对国内外学者近年来在大气气溶胶酸度对大气环境与人体健康的影响、大气气溶胶酸度的影响因素与变化规律、大气气溶胶酸度/酸化缓冲能力的测定与计算方法、大气气溶胶酸性成分采集系统等方面的研究进展作了较系统的综述,并对大气气溶胶酸度研究未来的发展进行了展望。     

A 3-mode parameterization of below-cloud scavenging of aerosols for use in atmospheric dispersion models

Atmospheric aerosols are subject to below-cloud scavenging by precipitation. The scavenging coefficient depends on the aerosol size significantly. The traditional bulk parameterization represents the mean wet scavenging coefficient for the whole aerosol size range. This parameterization significantly overestimates the scavenging of aerosol mass by a heavy rain or a long-duration medium rain. In this study, we present a 3-mode parameterization of the mean scavenging coefficient for each aerosol mode instead of representation for the whole aerosol size range. The new parameterization takes into account the aerosol number size distribution, the rain droplet size distribution and the spectral collision efficiency between the aerosol particle and the rain droplet. Comparing the calculation of mass depletion due to below-cloud scavenging, the 3-mode parameterization agrees well with the size-resolved explicit method. The new parameterization can be easily implemented in atmospheric dispersion models.     

Study on the aerosol optical properties and their relationship with aerosol chemical compositions over three regional background stations in China

The special and temporal characteristics of aerosol optical depth (AOD) and Angstrom wavelength exponent (Alpha) and their relationship with aerosol chemical compositions were analyzed by using the data of CE318 sun-photometer and aerosol sampling instruments at Lin'an, Shangdianzi and Longfengshan regional atmospheric background stations. Having the highest AOD among the three stations, Lin'an shows two peaks in a year. The AOD at Shangdianzi station shows a single annual peak with an obvious seasonal variation. The AOD at Longfengshan station has obvious seasonal variation which peaks in spring. The Alpha analysis suggests that the aerosol sizes in Lin'an, Longfengshan and Shangdianzi change from fine to coarse categories. The relationship between the aerosol optical depths of the Lin'an and Longfengshan stations and their chemical compositions is not significant, which suggests that there is not a simple linear relationship between column aerosol optical depth and the near surface chemical compositions of atmospheric aerosols. The aerosol optical depth may be affected by the chemical composition, the particle size and the shape of aerosol as well as the water vapor in the atmosphere.     

Vertical distributions of aerosols under different weather conditions: Analysis of in-situ aircraft measurements in Beijing,China

In this study, aerosol vertical distributions of 17 in-situ aircraft measurements during 2005 and 2006 springs are analyzed. The 17 flights are carefully selected to exclude dust events, and the analyses are focused on the vertical distributions of aerosol particles associated with anthropogenic activities. The results show that the vertical distributions of aerosol particles are strongly affected by weather and meteorological conditions, and 3 different types of aerosol vertical distributions corresponding to different weather systems are defined in this study. The measurement with a flat vertical gradient and low surface aerosol concentrations is defined as type-1; a gradual decrease of aerosols with altitudes and modest surface aerosol concentrations is defined as type-2; a sharp vertical gradient (aerosols being strongly depressed in the PBL) with high surface aerosol concentrations is defined as type-3. The weather conditions corresponding to the 3 different aerosol types are high pressure, between two high pressures, and low pressure systems (frontal inversions), respectively. The vertical mixing and horizontal transport for the 3 different vertical distributions are analyzed. Under the type-1 condition, the vertical mixing and horizontal transport were rapid, leading to strong dilution of aerosols in both vertical and horizontal directions. As a result, the aerosol concentrations in PBL (planetary boundary layer) were very low, and the vertical distribution was flat. Under the type-2 condition, the vertical mixing was strong and there was no strong barrier at the PBL height. The horizontal transport (wind flux) was modest. As a result, the aerosol concentrations were gradually reduced with altitude, with modest surface aerosol concentrations. Under the type-3 condition, there was a cold front near the region. As a result, a frontal inversion associated with weak vertical mixing appeared at the top of the inversion layer, forming a very strong barrier to prevent aerosol particles being exchanged from the PBL height to the free troposphere. As a result, the aerosol particles were strongly depressed in the PBL height, producing high surface aerosol concentrations. The measured vertical aerosol distributions have important implications for studying the effects of aerosols on photochemistry. The J[O₃] values are reduced by 11%, 48%, and 50%, under the type-1, type-2, and type-3 conditions, respectively. This result reveals that atmospheric oxidant capacity (OH concentrations) is modestly reduced under the type-1 condition, but is significantly reduced under the type-2 and type-3 conditions. This result also suggests that the effect of aerosol particles on surface solar flux is an integrated column effect, and detailed vertical distributions of aerosol particles are very important for assessing the impacts of aerosol on photochemistry.     

Electrostatic enhancement of collection efficiency of the fibrous filter pretreated with ionic surfactants

A study of the electrostatic enhancement of collection efficiency of filters pretreated with ionic surfactants has been carried out in controlled conditions with monodisperse aerosols. Cationic surfactant (dimethyl dioctadecylammonium bromide [DDAB]) and anionic surfactant (sodium oleate [SO]) were used to pretreat polypropylene fibrous filters as the positively and negatively charged filters, respectively. The effects of aerosol size, aerosol charge state, face velocity, aerosol type, and relative humidity (RH) were considered to elucidate their influence on the aerosol penetration. Results indicate that penetration through surfactant-pretreated filters was lower than that through untreated filters, and pretreatment of the filter with surfactant was observed not to affect the structure of the filter. The electrofieldmeter direct-measured the very clear electric field of filter when treating ionic surfactants. The results proved that pretreatment with surfactant caused filters to become charged. Comparing penetration through surfactant-pretreated filters with that through untreated filters with neutral aerosol, the penetration reduction factor of the surfactant-pretreated filters was in the range 1.3-2.2. Comparing aerosol penetration through the surfactant-pretreated filters with singly charged aerosol with that through untreated filters with uncharged aerosol indicates that the former decreases by a factor of 1.8-48.8. The surface fiber charges of the DDAB- and SO-pretreated filters were calculated to be 2.02 x 1(-10) C/m and -1.53 x 10(-1) degrees C/m. Moreover, the aerosol penetrations through the surfactant-pretreated filters increased with the face velocity. Surfactant-pretreated filters performed better against solid aerosol than against liquid aerosol. RH has no effect on aerosol penetration through the surfactant-pretreated filters. Regression equations for Coulombic and dielectrophoretic single-fiber efficiencies in terms of the dimensionless parameters could be fitted by the experimental measurements of surfactant-pretreated filters in this work.     

Characteristics of aerosol types from AERONET sunphotometer measurements

By using observations from the Aerosol Robotic Network (AERONET), aerosol types are classified according to dominant size mode and radiation absorptivity as determined by fine-mode fraction (FMF) and single-scattering albedo (SSA), respectively. The aerosol type from anthropogenic sources is significantly different with regard to location and season, while dust aerosol is observed persistently over North Africa and the Arabian Peninsula. For four reference locations where different aerosol types are observed, time series and optical properties for each aerosol type are investigated. The results show that aerosol types are strongly affected by their sources and partly affected by relative humidity. The analysis and methodology of this study can be used to compare aerosol classification results from satellite and chemical transport models, as well as to analyze aerosol characteristics on a global scale over land for which satellite observations need to be improved.     

Optical characteristics of southeast Asia's regional aerosols and their sources

The dominant optical characteristics of Southeast Asia (SEA)'s regional aerosols were determined from the cluster analysis of the 26 AERONET aerosol inversion products, including aerosol light scattering/absorption indicators and aerosol size/shape parameters retrieved from 2003 to 2007. The data sets were acquired from four stations: Bac Giang in Vietnam and Mukdahan, Pimai, and Silpakorn University in Thailand. The cluster analysis showed agreement among the aerosol optical characteristics, land cover/uses, season as the surrogate of the prevailing winds, and observations from the literature. The results of this study showed that during the northeast prevailing winds from mid-September to December, the high aerosol exposure events were most frequently observed over the upwind station and less often over the downwind stations. This aerosol exhibited a single scattering albedo (SSA) of approximately 0.95 (440 nm), a relatively low refractive index, and a larger fine-mode size, suggesting it had the characteristics of urban/industrial aerosols reported in the literature. These aerosol sources were upwind from Bac Giang, probably in eastern China. From January to April, the aerosol exhibited a lower SSA of approximately 0.90, a higher refractive index, and a smaller fine-mode size, suggesting biomass burning smoke reported in the literature. The SEA urban aerosol exhibited a mean SSA of approximately 0.90 (440 nm) or lower, and the coarse-mode aerosol, possibly road dust or soil dust, played a role from October to January when seasonal winds are strongest. The results from a canonical discriminant function analysis suggest that the dominant SEA aerosol clusters tended to be separated by a canonical function positively correlated with SSA, the fine-mode asymmetry factor, and the overall fine-mode size and negatively correlated with the refractive index.     

Aerosol light-scattering in The Netherlands

The relation between the (midday) aerosol light-scattering and the concentrations of nitrate and sulfate has been assessed at a site near the coast of the North Sea in The Netherlands. Midday was selected for the measurements because this is the time at which the aerosol is most effective in the scattering of solar radiation. Automated thermodenuders were used for the hourly measurement of the concentration of nitrate and sulfate with a lower detection limit of 0.1 μ m⁻³. The site is operational since October 1993. The first-year average dry aerosol light-scattering (measured with an integrating nephelometer at a wavelength of 525 nm) was 0.71 × 10⁻⁴ m^1̄. In arctic marine air the aerosol light-scattering was a factor of 10 lower than the average value, in polluted continental air it was up to a factor of 10 higher. The ratio of the total aerosol light-scattering to the concentration of sulfate was 20 m² g⁻¹. The contribution of nitrate to the aerosol light-scattering was higher than that of sulfate in the winter and of about equal magnitude in the summer period. In November and December of 1993, the humidity dependence of the aerosol light-scattering was investigated. Two types of (continental) aerosol were found with respect to the humidity behavior. One type showed a significant increase in light-scattering at the deliquescence points of ammonium nitrate and ammonium sulfate, with that of ammonium nitrate the most pronounced. The second type of continental aerosol did not show deliquescence, but followed the typical humidity dependence of aerosol in a supersaturated droplet state. In this latter aerosol type, nitrate dominated over sulfate. It was concluded from the study that the aerosol light-scattering in The Netherlands, in particular its humidity dependence, is governed by (ammonium) nitrate.     

Analysis and simulation of wintertime light scattering by the urban aerosol in Dallas-Fort Worth

Wintertime atmospheric light scattering in Dallas, TX, was estimated through the use of aerosol models. Input data for the aerosol models were provided by measurements of aerosol chemistry, physical particle size distributions, and distributions of particulate sulfur by particle size, and by predictions by an atmospheric simulation model. Light scattering measurements provided a basis for testing the aerosol models. The SCAPE thermodynamic equilibrium model was used to estimate the amount of liquid water associated with particles and the ELSIE Mie scattering model was applied to estimate the resulting light scattering. The calculations were based on aerosol properties measured in Dallas during December 1994 and February 1995, and changes in scattering due to hypothetical changes in the aerosol were predicted. The predicted light scattering was compared to scattering measured by an Optec nephelometer; agreement was within 20% in every case.     

Aerosols and associated precipitation patterns in Atlanta

The role of aerosol concentrations on summer precipitation was examined in Atlanta, Georgia for the period 2003–2004. Each day of the week was examined to ascertain their aerosol concentrations. Thursday had the highest median 2.5 μm particulate matter (PM 2.5) concentrations at two of three Environmental Protection Agency stations. Monday and Thursday had the largest area of significantly different precipitation when compared to other days of the week. All but the southeast quadrant of the metropolitan area had a significant difference in precipitation on high versus low aerosol days. High aerosol days had greater instability (higher average convective available potential energy and lower convective inhibition), and a slightly more shallow mixing layer when compared to low aerosol days. Most of metropolitan Atlanta had higher precipitation amounts on high aerosol days and was significantly different from low aerosol days.     

Analysis and Simulation of Wintertime Light Scattering by the Urban Aerosol in Dallas-Fort Worth

ABSTRACT

Wintertime atmospheric light scattering in Dallas, TX, was estimated through the use of aerosol models. Input data for the aerosol models were provided by measurements of aerosol chemistry, physical particle size distributions, and distributions of particulate sulfur by particle size, and by predictions by an atmospheric simulation model. Light scattering measurements provided a basis for testing the aerosol models. The SCAPE thermodynamic equilibrium model was used to estimate the amount of liquid water associated with particles and the ELSIE Mie scattering model was applied to estimate the resulting light scattering. The calculations were based on aerosol properties measured in Dallas during December 1994 and February 1995, and changes in scattering due to hypothetical changes in the aerosol were predicted. The predicted light scattering was compared to scattering measured by an Optec nephelom-eter; agreement was within 20% in every case.     

Precipitation scavenging coefficient: influence of measured aerosol and raindrop size distributions

Precipitation scavenging coefficients, widely used in pollution studies, are derived from microphysical parameterisations of aerosol particles and raindrop populations and parameterisations of their interactions. The present study investigates the effects of measured aerosol and raindrop size distributions in a microphysical polydisperse framework. The interactions between aerosol and raindrops parameterised as collision efficiency are explicitly included to account for Brownian diffusion, inertial impaction and interception. Estimated values of the polydisperse scavenging coefficients exhibit variations of orders of magnitude depending on the aerosol type and almost no variation with the raindrop size distributions. For practical use, linear relationships between the scavenging coefficients and rain intensity for different aerosol types are derived.     

Evaluation of a reactive plume model with power plant plume data—application to the sensitivity analysis of sulfate and nitrate formation

A reactive plume model that treats secondary aerosol formation is used to investigate the major physical and chemical processes that affect the rate of sulfate and nitrate aerosol formation in power plant plumes. The reactive plume model is evaluated with experimental data collected in three power plant plumes, and model performance is shown to be quite satisfactory. One of these case studies is used to perform singleparameter and multi-parameter analyses of the sensitivity of sulfate and nitrate aerosol concentrations to various meteorological, air quality and chemical kinetic parameters. The results suggest that sulfate aerosol concentrations are most sensitive to relative humidity and temperature at high relative humidity, whereas nitrate aerosol concentrations are most sensitive to temperature, particularly at low relative humidity. The importance of the NO_x/reactive hydrocarbon chemistry to sulfate and nitrate aerosol formation is examined.     

Aerosol light absorption measurement techniques: Analysis and intercomparisons

A controlled study was carried out to evaluate three measurement techniques used for the determination of aerosol light absorption coefficients from aerosol samples collected on various filter substrates. These techniques were found to agree within about 10–30% when applied to a range of filter loading obtained for a laboratory generated calibration aerosol. Microphysical properties of the calibration aerosol were used to model its optical effects using Mie theory. The measured and modeled optical properties were found to differ by less than 30%. Qualitative and quantitative agreement of these techniques indicate that they provide a reasonable indirect method for the determination of atmospheric aerosol absorption coefficients and the related concentration of elemental carbon aerosol.     

Interpretation of Meteorological Pollutant Roses in Areas Subject to Nocturnal Drainage Winds

The composition of aerosol particle products formed from the photochemical reaction of terpenes with NO_x and the chemical reaction of terpenes with ozone was determined using direct insertion probe/high resolution mass spectrometry. Samples of the aerosol particles generated from these gas phase reactions were collected on stainless steel disks using a specially-designed impactor. The samples were analyzed using computer-controlled high resolution mass spectrometry. The photochemical reaction of limonene with NO_x produced more than 30 reaction products in the aerosol phase. The major products identified included aldehydes, alcohols, acids, peroxides, and nitrate esters of alcohols, acids, and peroxides. In addition, there was evidence of dimeric and possibly trimeric reaction products. The composition of aerosol particle products formed from the dark reaction of ozone with limonene was determined and found similar to those products generated in the photochemical reaction, excluding the nitrated species. Aerosol concentrations were monitored using nephelometry which indicated a conversion of terpene to aerosol of 50% or greater for both the limonene and terpinolene reaction systems. The results show that direct insertion probe high resolution mass spectrometric technique has the capability for determining the composition of very polar and high molecular weight materials in aerosol particles. The composition of terpene aerosol particle products and the mass spectral data obtained from their analysis can be used in further studies to determine the importance of terpene aerosol particle formation in ambient air.     

Gas-to-particle conversion in the atmosphere: I. Evidence from empirical atmospheric aerosols

Condensable vapours such as sulphuric acid form aerosol in the atmosphere by the competing mechanisms of condensation on existing aerosol and the nucleation of new aerosol. Observational and theoretical evidence for the relative magnitudes of the competing processes is reviewed, and a number of general conclusions are made. Condensation is sensitive to the sticking probability of sulphuric acid molecules on aerosol particles, but there is now good evidence that it should be close to unity. In this case, equilibration timescales between acid vapour and the aerosol in most of the atmosphere are of the order of minutes or less, so that the acid concentration on such timescales given simply by the production rate times the equilibration time. When the acid concentration exceeds a threshold, nucleation will occur. The atmospheric aerosol therefore follows a history of initial formation in a nucleation burst followed by growth and coagulation with final removal by precipitation. This leads to the inverse correlation between aerosol number concentration and mass concentration found by Clarke (1992. Journal of Atmospheric Chemistry 14, 479–488) in the free troposphere. Binary homogeneous nucleation of sulphuric acid/water droplets, for which various simplified rates are compared, may dominate in such regions, but other mechanisms are possible elsewhere. A detailed analysis is performed of the number concentrations, removal rates, and masses of the components of the different types of global aerosols proposed empirically by Jaenicke (1993. Tropospheric Aerosols, Aerosol-Cloud-Climate Interaction. Academic Press, New York). There is a striking correlation between number concentrations in the nucleation and accumulation modes; and the giant aerosol mode, which if it is present dominates the mass, has little effect on the gas-to-particle conversion process. The mass of the atmospheric aerosol is therefore uncorrelated with the magnitude of molecular aerosol removal by condensation.     

Sensitivity of modelled sulphate and nitrate aerosol to cloud,pH and ammonia emissions

A Lagrangian dispersion model has been used to predict daily sulphate aerosol in 2006 at five UK rural measurement sites and hourly nitrate aerosol in April 2003 at Harwell (UK). The sensitivity of aqueous phase sulphate production to the meteorological input has been investigated. Large differences were found between cloud fraction and cloud liquid water output from the regional and mesoscale Met Office Unified Model. The impact on the sulphate aerosol was relatively small, with the mesoscale meteorology giving better results.Sulphate aerosol production in the aqueous phase was found to be very sensitive to modelled cloud pH. As the cloud becomes acidic sulphate production is greatly limited, conversely if the cloud is basic large amounts of sulphate aerosol are produced. A fixed model pH of 5.8 was found to produce better results than allowing the model to calculate pH which resulted in large over-predictions of measured sulphate aerosol in some episodes.Nitrate aerosol was not sensitive to cloud variables or pH, but showed a slight increase with 30% more ammonia emissions, and a slight decrease with 30% less ammonia.Sulphate production in model runs with fixed pH was not sensitive to changing ammonia emissions, however the sulphate production with modelled pH was very sensitive to plus or minus 30% ammonia. This work suggests that good modelling of ammonia is essential to correct estimation of aqueous phase sulphate aerosol if cloud pH is modelled. It is concluded that modelling to estimate the effect of reduced ammonia emission scenarios on future ambient aerosol levels should also take into account the neutralising effect of ammonia in cloud and hence the effect on aqueous phase production of sulphate.     

Seasonal variations of monosaccharide anhydrides in PM1 and PM2.5 aerosol in urban areas

The concentrations of monosaccharide anhydrides (levoglucosan, mannosan, galactosan) in PM1 and PM2.5 aerosol samples were measured in Brno and ?lapanice in the Czech Republic in winter and summer 2009. 56 aerosol samples were collected together at both sites to investigate the different sources that contribute to aerosol composition in studied localities. Daily PM1 and PM2.5 aerosol samples were collected on pre-fired quartz fibre filters.The sum of average atmospheric concentration of levoglucosan, mannosan and galactosan in PM1 aerosol in ?lapanice and Brno during winter was 513 and 273 ng m^?3, while in summer the sum of average atmospheric concentration of monosaccharide anhydrides (MAs) was 42 and 38 ng m^?3, respectively. The sum of average atmospheric concentration of MAs in PM1 aerosol formed 71 and 63% of the sum of MA concentration in PM2.5 aerosol collected in winter in ?lapanice and Brno, whereas in summer the sum of average atmospheric concentration of MAs in PM1 aerosol formed 45 and 43% of the sum of MA concentration in PM2.5 aerosol in ?lapanice and Brno, respectively.In winter, the sum of MAs contributed significantly to PM1 mass ranging between 1.37% and 2.67% of PM1 mass (Brno – ?lapanice), while in summer the contribution of the sum of MAs was smaller (0.28–0.32%). Contribution of the sum of MAs to PM2.5 mass is similar both in winter (1.37–2.71%) and summer (0.44–0.55%).The higher concentrations of monosaccharide anhydrides in aerosols in ?lapanice indicate higher biomass combustion in this location than in Brno during winter season. The comparison of levoglucosan concentration in PM1 and PM2.5 aerosol shows prevailing presence of levoglucosan in PM1 aerosol both in winter (72% on average) and summer (60% on average).The aerosol samples collected in ?lapanice and Brno in winter and summer show comparable contributions of levoglucosan, mannosan and galactosan to the total amount of monosaccharide anhydrides in both aerosol size fractions. Levoglucosan was the most abundant monosaccharide anhydride with a relative average contribution to the total amount of MAs in the range of 71–82% for PM1 aerosols and 52–79% for PM2.5 aerosols.     

The design of an aerosol test tunnel for occupational hygiene investigations

An aerosol test tunnel which provides large working sections is described and its performance evaluated. Air movement within the tunnel is achieved with a powerful D.C. motor and centrifugal fan. Test dusts are dispersed and injected into the tunnel by means of an aerosol generator. A unique divertor valve allows aerosol laden air to be either cleaned by a commercial pulse jet filtration unit or recycled around the tunnel to obtain a high aerosol concentration. The tunnel instrumentation is managed by a microcomputer which automatically controls the airspeed and aerosol concentration.     

Dynamic Calibration of an Acid Aerosol Analyzer

A method is described for dynamic calibration of an acid aerosol analyzer based on a commercial modification of the Thomas Autometer and manufactured by the Instrument Development Company. This automated instrument removes acid aerosol from an air stream by sonic impaction, and the sulfuric acid collected is determined conductometrically. An all-glass aerosol generator based on the reaction of water vapor with sulfur trioxide vapor released from fuming sulfuric acid was built for the calibration. Air samples were withdrawn for instrument calibration before and after the concentration of the acid aerosol was determined by titration. The apparent particle size as determined by an Andersen sampler ranged from 2.0 microns to less than 0.68 micron and exhibited a sharp peak with mass median diameter at 1.3 microns in the distribution curve. The size of the aerosol, within certain limits, could be controlled by humidity. Data indicated a linear response with an aerosol collection efficiency of 80 percent in the important respirable size range.