Impact and growth phenomena observed with sub-micrometer atmospheric aerosol particles collected on polished silicon at low coverage

The processes occurring during the initial stages of size-selected sampling of atmospheric aerosol matter were explored by means of high-resolution scanning electron microscopy and energy dispersive X-ray spectrometry. The final four stages of a Berner impactor served to collect particles with aerodynamic diameters between 60 nm and 1 μm on polished silicon substrates at sampling times between 10 s and 16 min. In the single-particle impact regime (fractional coverage below 5%), most of the particles produced circular black tracks, of which 15 to 30% contained cores of carbonaceous nanoparticles. At a fractional coverage above about 10%, initially generated deposits became increasingly active as centres of preferred aerosol collection. As a result, the number of black spots remained almost constant, but the area per spot increased rapidly. At this stage of fractional coverage, structured aerosol matter became visible within large black areas of random shape. The deposits showed clear evidence for the onset of phase separation between carbon nanoparticles and material rich in sulphur, probably a mixture of alkaline and alkaline earth sulphates. After some time of sample storage in air the low-coverage sulphate matter tended to attain a fractal pattern. At a fractional coverage of several hundred per cent, large amorphous or crystalline objects had grown, but 30% or more of the nominal impact area still did not contain any aerosol matter. Moreover, carbon nanoparticles were found to be phase separated from the newly grown, very uniform aerosol material. The observations imply that sub-micrometer aerosol matter collected in impactors has lost memory of the original particle morphology.     

Atmospheric mineral particles collected at Qira in the Taklamakan Desert, China

Aerosol particles were collected in the situation of the widespread dust suspension on 21 February 1991 at Qira in the southern edge of the Taklamakan Desert, western China. The collected particles were examined by a transmission electron microscope equipped with an energy-dispersive X-ray (EDX) analyzer in order to obtain the size and elemental composition of individual mineral particles.On the basis of EDX analyses for 386 particles, mineral particles were present in high number fractions (>99%) of particles in the radius range of 0.1–4 μm. Particles mainly composed of silicates comprised 76% of mineral particles. “Ca-rich” particles were detected in 7% of all the particles. Ca in the particles would be present not only as CaCO₃ but also as an internal mixture of CaCO₃ and CaSO₄. Particles containing halite (NaCl) were detected in number proportions of about 10% and were mainly present in the radius range of 0.5 μm. Some halite particles would be modified by chemical reactions with sulfuric acid.     

Fine particulate (PM2.5) composition in Atlanta, USA: assessment of the particle concentrator-Brigham Young University organic sampling system, PC-BOSS, during the EPA supersite study

Aerosol concentrations of carbonaceous material, sulfate, and nitrate for samples obtained using a newly designed PC-BOSS are reported. The results indicated that PM_2.5 composition in Atlanta was dominated by sulfate and organic material, with low concentrations of particulate nitrate. Observed average particulate component concentrations for the 26-day study period were: sulfate, 12.2 μg/m³ (17.0 μg/m³ as ammonium sulfate); non-volatile organic material, 11.4 μg OM/m³ (assumes organic material, OM, is 61% C); semi-volatile organic compounds (SVOC) lost from particles during sampling, 5.3 μg OM/m³; filter retained nitrate, 0.1 μg/m³ (0.2 μg/m³ as ammonium nitrate); nitrate lost from particles, 0.3 μg/m³ (0.4 μg/m³ as ammonium nitrate); and soot (elemental carbon), 1.5 μg/m³. The PC-BOSS particle concentrator efficiency was obtained by comparison of the PC-BOSS sulfate data with sulfate data obtained from the Federal Reference Method (FRM) sampler. A modification of the PC-BOSS design to allow independent determination of this parameter is recommended.     

Size resolved chemical mass balance of aerosol particles over rural Hungary

The mass size distribution of atmospheric aerosol particles was determined by means of an electric low pressure impactor (ELPI) in rural air in Hungary. The particles captured on different stages of the impactor were chemically analyzed by capillary zone electrophoresis to quantify ionic components as well as by catalytic combustion method to detect total carbon in the samples. The results show that fine aerosol consists mainly of ammonium sulfate and organic carbon. These two species have rather different size distributions since very small particles are composed almost of carbon compounds. The analysis of fine aerosol samples collected simultaneously on filters indicates that an important part of organics is soluble in water. The mass balance of fine particles as a function of their size is estimated by taking into account the liquid water adsorbed by ammonium sulfate and by converting the mass of carbon to the mass of carbon compounds. Finally, the size resolved mass balance of fine aerosol particles is presented and discussed as a function of the origin of air masses.     

Single-particle characterization of atmospheric aerosols collected at Gosan, Korea, during the Asian Pacific Regional Aerosol Characterization Experiment field campaign using low-Z (atomic number) particle electron probe X-ray microanalysis

A quantitative energy-dispersive electron probe X-ray microanalysis (ED-EPMA), namely low-Z (atomic number) particle EPMA, was used to characterize the chemical compositions of the individual aerosol particles collected at the Gosan supersite, Jeju Island, Korea, as a part of the Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia). On 4-10 April 2001 just before a severe dust storm arrived, seven sets of aerosol samples were obtained by a seven-stage May cascade impactor with a flow rate of 20 L/min. Overall 11,200 particles on stages 1-6 with cutoff diameters of 16, 8, 4, 2, 1, and 0.5 microm, respectively, were examined and classified based on their secondary electron images and X-ray spectra. In general, sea salt particles were the most frequently encountered, followed by mineral dust, organic carbon (OC)-like, (NH4)2SO4/NH4HSO4-containing, elemental carbon (EC)-like, Fe-rich, and K-rich particles. Sea salt and mineral dust particles had a higher relative abundance on stages 1-5, whereas OC-like, (NH4)2SO4/NH4HSO4-containing, Fe-rich, and K-rich particles were relatively abundant on stage 6. The analysis on relative number abundances of various particle types combined with 72-hr backward air mass trajectories indicated that a lot of reacted sea salt and reacted mineral dust (with airborne NOx and SO2 or their acidic products) and OC-like particles were carried by the air masses passing over the Yellow Sea (for sample "10 April") and many NH4HSO4/ (NH4)2SO4-containing particles were carried by the air masses passing over the Sea of Japan and Korea Strait (for samples "4-9 April"). It was concluded that the atmosphere over Jeju Island was influenced by anthropogenic SO2 and NOx, organic compounds, and secondary aerosols when Asian dust was absent.     

Light Scattering Characteristics of Aerosols as a Function of Relative Humidity: Part I—A Comparison of Measured Scattering and Aerosol Concentrations Using the Theoretical Models

ABSTRACT

The Southeastern Aerosol and Visibility Study (SEAVS) was undertaken to characterize the size-dependent composition, thermodynamic properties, and optical characteristics of the ambient atmospheric particles in the southeastern United States. The field portion of the study was carried out from July 15 to August 25, 1995.

As part of the study a relative humidity controlled inlet was built to raise or lower the relative humidity to predetermined levels before the aerosol was passed into an integrating nephelometer or particle-sizing device. Five other integrating nephelometers were operated in various configurations, two of which were fitted with a 2.5 μm inlet. Fine particle (<2.5 μm) samplers were operated to measure concentrations of sulfate, nitrate, and ammonium ions, organic and elemental carbon, and fine soil. Mass size distributions were measured with an eight-stage, single orifice cascade impactor.     

Aerosol ion characteristics during the Big Bend Regional Aerosol and Visibility Observational study

The ionic compositions of particulate matter with aerodynamic diameter < or = 2.5 microm (PM2.5) and size-resolved aerosol particles were measured in Big Bend National Park, Texas, during the 1999 Big Bend Regional Aerosol and Visibility Observational study. The ionic composition of PM2.5 aerosol was dominated by sulfate (SO4(2-)) and ammonium (NH4+). Daily average SO4(2-) and NH4+ concentrations were strongly correlated (R2 = 0.94). The molar ratio of NH4+ to SO4(2-) averaged 1.54, consistent with concurrent measurements of aerosol acidity. The aerosol was observed to be comprised of a submicron fine mode consisting primarily of ammoniated SO4(2-) and a coarse particle mode containing nitrate (NO3-). The NO3- appears to be primarily associated with sea salt particles where chloride has been replaced by NO3-, although formation of calcium nitrate (Ca(NO3)2) is important, too, on several days. Size-resolved aerosol composition results reveal that a size cut in particulate matter with aerodynamic diameter < or = 1 microm would have provided a much better separation of fine and coarse aerosol modes than the standard PM2.5 size cut utilized for the study. Although considerable nitric acid exists in the gas phase at Big Bend, the aerosol is sufficiently acidic and temperatures sufficiently high that even significant future reductions in PM2.5 SO4(2-) are unlikely to be offset by formation of particulate ammonium nitrate in summer or fall.     

Black carbon,mass and elemental measurements of airborne particles in the village of Serowe,Botswana

Absorption of sunlight by sub-micron particles is an important factor in calculations of the radiation balance of the earth and thus in climate modelling. Carbon-containing particles are generally considered as the most important in this respect. Major sources of these particles are generally considered to be bio-mass burning and vehicle exhaust. In order to characterise size fractionated particulate matter in a rural village in Botswana with respect to light absorption and elemental content experiments were performed, in which simultaneous sampling was made with a dichotomous impactor and a laboratory-made sampler, made compatible with black carbon analysis by reflectometry. The dichotomous impactor was equipped with Teflon filters and the other sampler with glass fibre filters. Energy dispersive X-ray fluorescence was used for elemental analysis of both kinds of filters. It appeared that Teflon filters were the most suitable for the combination of mass-, elemental- and black carbon measurements. The black carbon content in coarse (2.5–10 μm) and fine (<2.5 μm) particles was determined separately and related to elemental content and emission source. The results show that the fine particle fraction in the aerosol has a much higher contribution of black particles than the coarse particle fraction. This observation is valid for the village in Botswana as well as for a typical industrialised city in Sweden, used as a reference location.     

Characterization of size segregated particles collected over Alaska and the CAnadian high Arctic,AGASP-II flights 204–206

Ten aircraft-collected cascade impactor samples from the North American Arctic were analyzed using analytical electron microscopy. Morphological, mineralogical and elemental information were obtained from individual particles, as well as compositional data and size distribution estimates of the bulk aerosol. Categorization of carbonaceous material into organic-type and combustion-type carbon particles was performed in this study. This was accomplished through the use of a new ultra-thin window X-ray spectrometer, which can directly detect carbon X-rays emitted from particles, and through interpretation of morphological and electron diffraction data. Verification of graphite as a specific carbon mineral phase present in Arctic soot particles was performed in this manner.Several classes of particles were present in most of the aerosol samples and size fractions. These included liquid H₂SO₄ droplets, which were always present in the highest numbers, and crustal-type and composite SO₄⁻² particles. A small fraction (0–30%) of a random sampling of SO²⁻₄particles from all impactor stages were found to contain detectable nitrogen, suggesting that partial neutralization by NH₃ may have occurred in this minority of the SO²⁻₄ droplets. Particles rich in non-combustion carbon and thought to be composed of organic material were also observed in most samples. Haze samples collected off the coast of Alert, NWT, show moderate loadings of H₂SO₄ droplets. Judging from these loadings and those from higher-altitude samples, ambient aerosol particle concentrations must have been considerably higher in the haze. The extent to which local activity at Alert has influenced these haze samples is not known, although a major contribution is not expected. Stratospheric samples did not contain several classes of particles thought to have major anthropogenic source inputs to the Arctic, such as black carbon and coal-fired combustion spheres. The lightest particle loadings in any samples were collected in the upper troposphere near the tropopause, where condensation nuclei counts during sampling fell to as low as 10 cm⁻³.     

Characteristics of Individual Particles at a Rural Site in the Eastern United States

To determine the nature of aerosol particles in a rural area of the eastern United States, aerosol samples were collected at Deep Creek Lake, Maryland, on various substrates and analyzed by a scanning electron microscope (SEM) and a transmission electron microscope (TEM). SEM analysis of particles larger than 2.5 μm collected on Nuclepore filters revealed the following: clay minerals, quartz, gypsum, and calcite comprised 50 percent of the particles analyzed; spores, pollen, and plant debris comprised 25 percent; 9 percent were fly ash; 11 percent were sulfates; 5 percent were unidentified. Particles ranging from 0.3 to 2 μm were collected in a cascade impactor on grid-supported carbon films and analyzed by TEM for decomposition rate as well as for reaction with the barium chloride and nitron (C₂₀H₁₆N₄) films that were applied after sampling. The TEM analyses indicated that as much as 95 percent of the particles in the 0.3- to 2-μm diameter range were pure ammonium sulfate or acidic ammonium sulfate; they contained essentially no insoluble or nonvolatile matter. About 5 percent of the particles were fly ash spheres. When replicas of particles collected on Nucleopore filters were analyzed by TEM, we observed agglomerates of particles smaller than 0.1 μm.     

Size distribution and anthropogenic sources apportionment of airborne trace metals in Kanazawa, Japan

Aerosol samples were collected from Kanazawa, Japan to examine the size distribution of 12 elements and to identify the major sources of anthropogenic elements. Key emission sources were identified and, concentrations contributed from individual sources were estimated as well. Concentrations of elements V, Ca, Cd, Fe, Ba, Mg, Mn, Pb, Sr, Zn, Co and Cu in aerosols were determined with ICP-MS. The results showed that Ca, Mg, Sr, Mn, Co and Fe were mainly associated with coarse particles (>2.1 μm), primarily from natural sources. In contrast, the elements Zn, Ba, Cd, V, Pb and Cu dominated in fine aerosol particles (<2.1 μm), implying that the anthropogenic origin is the dominant source. Results of the factor analysis on elements with high EF_Crust values (>10) showed that emissions from waste combustion in incinerators, oil combustion (involving waste oil burning and oil combustion in both incinerators and electricity generation plants), as well as coal combustion in electricity generation plants were major contributors of anthropogenic metals in the ambient atmosphere in Kanazawa. Quantitatively estimated sum of mean concentrations of anthropogenic elements from the key sources were in good agreement with the observed values. Results of this study elucidate the need for making pollution control strategy in this area.     

Aerosols near by a coal fired thermal power plant: Chemical composition and toxic evaluation

Industrial processes discharge fine particulates containing organic as well as inorganic compounds into the atmosphere which are known to induce damage to cell and DNA, both in vitro and in vivo. Source and area specific studies with respect to the chemical composition, size and shape of the particles, and toxicity evaluations are very much limited. This study aims to investigate the trace elements associated with the aerosol particles distributed near to a coal burning thermal power plant and to evaluate their toxicity through Comet assay. PM₁₀ (particles determined by mass passing an inlet with a 50% cut-off efficiency having a 10-μm aerodynamic diameter) samples were collected using respirable dust samplers. Twelve elements (Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, Se, Hg, and As) were analyzed using ICP-AES. Comet assay was done with the extracts of aerosols in phosphate buffered saline (PBS). Results show that Fe and Zn were found to be the predominant elements along with traces of other analyzed elements. Spherical shaped ultrafine particles of <1 μm aerodynamic diameter were detected through scanning electron microscope. PM₁₀ particles near to the coal burning power plant produced comets indicating their potential to induce DNA damage. DNA damage property is found to be depending upon the chemical characteristics of the components associated with the particles besides the physical properties such as size and shape.     

Programmable Instrument for Controlling Atmospheric Sampling

The University of Arizona and the Pima County Air Pollution Control District conducted a comparison study of the following aerosol samplers: a standard high-volume sampler, a high-volume sampler fitted with a size selective inlet, and a dichotomous virtual impactor. Over sixty samples were collected with the colocated samplers during the first six months of 1981. The concentration (μg/m³) of suspended particulate matter and of sulfate was determined for all the samples, while the concentration of four lithophilic elements (Ca, Fe, Mg, and K) was determined on one third of the samples. Well-defined linear relationships for suspended particulate matter and sulfate were found to exist between each of the three sample collection methods over the concentrafion range encountered in this study. For these samples, there were significant differences in the particulate mass and large particle lithophilic element concentrations collected by each device. However, sulfate values obtained from the three samplers were in excellent agreement with each other. This suggests that the inlet collection efficiency for large particles differs significantly for these three sampling devices. Since the size selective inlet and the dichotomous virtual impactor samplers are each designed for collection of inhalable particles (particles of 15 μm aerodynamic diameter and smaller), they would have been expected to measure approximately equivalent particle mass concentrations. Thus, these differences are important to those interested in selecting a method for measuring airborne particle mass concentrations.     

Seasonal variation of the size distribution of urban particulate matter and associated organic pollutants in the ambient air

Size-segregated samples of urban particulate matter (<0.95, 0.95–1.5, 1.5–3.0, 3.0–7.5, >7.5 μm) were collected in Thessaloniki, northern Greece, during winter and summer of 2007–2008, in order to study the size distribution of organic compounds such as polycyclic aromatic hydrocarbons (PAHs), aliphatic hydrocarbons (AHs) including n-alkanes and the isoprenoids pristane and phytane, organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). All organic compounds were accumulated in the particle size fraction <0.95 μm particularly in the cold season. Particulate matter displayed a bimodal normalized distribution in both seasons with a stable coarse mode located at 3.0–7.5 μm and a fine mode shifting from 0.95–1.5 μm in winter to <0.95 μm in summer. Unimodal normalized distributions, predominant at 0.95–1.5 μm size range, were found for most organic compounds in both seasons, suggesting gas-to-particle transformation after emission. A second minor mode at larger particles (3.0–7.5 μm) was observed for C₁₉ and certain OCPs suggesting redistribution due to volatilization and condensation.     

Estimation of actinic flux and photolysis rate constant of NO2 from aerosol size data

Aerosol mass measurements made using Andersen cascade impactor at different locations in an urban area were used to study the variation in power-law exponent in the Junge-type number distribution. The discrete mass size data were inverted by modified Twomey algorithm to obtain continuous mass size distribution from which number distributions were derived. These were used for evaluating actinic fluxes and hence NO₂ photolysis rate constants employing a radiative transfer model with delta-Eddington approximation.Results of the spatial variation of Junge power-law exponent over the urban region are presented. The relative magnitude of photolysis rate constants over regions with differing aerosol emission characteristics are illustrated. Parametric studies indicated the importance of considering fractional elemental carbon content of the aerosols in the atmosphere. Results of a limited validation study of the model are also presented using quartz crystal microbalance impactor data at one of the sites.     

The contribution of biological particles to observed particulate organic carbon at a remote high altitude site

Although a significant fraction of atmospheric particulate mass is organic carbon, the sources of particulate organic carbon (POC) are not always apparent. One potential source of atmospheric POC is biological particles, such as bacteria, pollen, and fungal spores. Measurements of POC and biological particles, including bacteria, fungal spores, and pollen, were made as part of the Storm Peak Aerosol and Cloud Characterization Study in Steamboat Springs, CO in March–April 2008. Biological particles were identified and characterized using several methods. The results suggest that biological particles could account for an average of 40% of the organic carbon mass in particles with aerodynamic diameters less than 10 μm. These estimates of POC mass from biological particles are highly uncertain; however, the results suggest that biological particles could be a significant source of organic aerosol in the background continental atmosphere and further observations are needed to better constrain these estimates.     

Phase transition behaviour of sodium oleate aerosol particles

Field measurements have shown that organic surfactants are significant components of atmospheric aerosols. While fatty acids, among other surfactants, are prevalent in the atmosphere, the influence of these species on the chemical and physical properties of atmospheric aerosols remains not fully characterized. In order to assess the phase in which particles may exist, a detailed study of the deliquescence of a model surfactant aerosol has been carried out. Sodium oleate was chosen as a surfactant proxy relevant in atmospheric aerosol. Sodium oleate micelle aerosol particles were generated nebulizing a sodium oleate aqueous solution. In this study, the water uptake and phase transition of sodium oleate aerosol particles have been studied in a room temperature aerosol flow tube system (AFT) using Fourier transform infrared (FTIR) spectroscopy. Aerosol morphology and elemental composition were also analysed using scanning electron microscopy/energy dispersive X-ray analysis (SEM/EDX) techniques. The particles are homogeneously distributed as ellipsoidal-shape aggregates of micelles particles with an average size of ∼1.1 μm. The deliquescence by the sodium oleate aerosol particles was monitored by infrared extinction spectroscopy, where the dried aerosol particles were exposed to increasing relative humidity as they passed through the AFT. Observations of the infrared absorption features of condensed phase liquid water enable to determine the sodium oleate deliquescence phase transition at 88±2%.     

Aerosol properties,in-canopy gradients,turbulent fluxes and VOC concentrations at a pristine forest site in Amazonia

Aerosol physical and chemical properties were measured in a forest site in central Amazonia (Cuieiras reservation, 2.61S; 60.21W) during the dry season of 2004 (Aug–Oct). Aerosol light scattering and absorption, mass concentration, elemental composition and size distributions were measured at three tower levels (Ground: 2 m; Canopy: 28 m, and Top: 40 m). For the first time, simultaneous eddy covariance fluxes of fine mode particles and volatile organic compounds (VOC) were measured above the Amazonian forest canopy. Aerosol fluxes were measured by eddy covariance using a Condensation Particle Counter (CPC) and a sonic anemometer. VOC fluxes were measured by disjunct eddy covariance using a Proton Transfer Reaction Mass Spectrometer (PTR-MS). At nighttime, a strong vertical gradient of phosphorus and potassium in the aerosol coarse mode was observed, with higher concentrations at Ground level. This suggests a source of primary biogenic particles below the canopy. Equivalent black carbon measurements indicate the presence of light-absorbing aerosols from biogenic origin. Aerosol number size distributions typically consisted of superimposed Aitken (76 nm) and accumulation modes (144 nm), without clear events of new particle formation. Isoprene and monoterpene fluxes reached respectively 7.4 and 0.82 mg m^?2 s^?1 around noon. An average fine particle flux of 0.05 ± 0.10 10⁶ m^?2 s^?1 was calculated, denoting an equilibrium between emission and deposition fluxes of fine mode particles at daytime. No significant correlations were found between VOC and fine mode aerosol concentrations or fluxes.     

Detection of Asian dust aerosols using meteorological satellite data and suspended particulate matter concentrations

The advection and dispersion of Asian dust events from China to the Pacific Ocean around Japan during 2000–2002 were investigated using the meteorological satellite data of NOAA/AVHRR and GMS-5/VISSR. Aerosol vapour index images, taking the brightness temperature difference between 11 and 12 μm, are very effective for monitoring the Asian dust phenomenon in the East Asia region, with their capacity for detection during the day or night. We discuss the dust events, focusing on the advection patterns shown in satellite images, which are classified into three types as ‘dry slot’, ‘high-pressure wedge’ and ‘travelling high’, based on synoptic patterns. The results are compared with suspended particulate matter concentrations measured at Japanese surface stations and with ground-based observations of Sakurajima volcano by a web camera system at Kagoshima in Kyushu, Japan. We found that the passage of cold fronts caused a rapid increase of suspended particulate matter (SPM) concentrations, which exceeded 100 μg m⁻³, and that deep low-pressure complexes strengthened the dust phenomenon. The ‘high-pressure wedge’ type is seen much more clearly in satellite images than the ‘travelling high’ type, but SPM concentrations and visibility were similar in both owing to the differences in the vertical distribution of the dust and in viewing conditions.     

Variation of particle number and mass concentration in various size ranges of ambient aerosols in Eastern Germany

There is an ongoing debate on the question which size fraction of particles in ambient air may be responsible for short-term responses of the respiratory system as observed in several epidemiological studies. However, the available data on ambient particle concentrations in various size ranges are not sufficient to answer this question.Therefore, on 180 days during the winter 1991/92 daily mean size distributions of ambient particles were determined in. Erfurt, a city in Eastern Germany. In the range 0.01–0.3 μm particles were classified by an electrical mobility analyzer and in the range 0.1–2.5 μm by an optical particle counter. From the derived size distributions, number and mass concentrations were calculated.The mean number concentration over this period of time was governed by particles smaller than 0.1 μm (72%), whereas the mean mass concentration was governed by particles in the size range 0.1–0.5 pm (83%). The contribution of particles larger than 0.5 μm to the overall number concentration was negligible and so was the contribution of particles smaller than 0.1 μm to the overall mass concentration. Furthermore, total number and mass concentrations in the range 0.01–2.5 μm were poorly correlated.The results suggest that particles larger than 2.5 μm (or even larger than 0.5 μm) are rare in the European urban environment so that the inhalation of these particles is probably not relevant for human health. Since particle number and mass concentrations can be considered poorly correlated variables, more insight into health-related aspects of particulate air pollution will be obtained by correlating respiratory responses with mass and number concentrations of ambient particles below 0.5 μm.