Particle Electron Probe X-ray Microanalysis Research Articles

Wavelet periodic and compositional characteristics of atmospheric PM2.5 in a typical air pollution event at Jinzhong city, China

To investigate the contributions of atmospheric particulate matter less than 2.5 μm in aerodynamic diameter (PM2.5) to heavy air pollution events in Fen-Wei Plain, China and identify their sources, a combination of wavelet analysis and low-atomic number (Z) particle electron probe X-ray microanalysis (EPMA) was utilized in a typical haze episode lasting 10 days (from Nov. 11 to 20, 2016) at Jinzhong, an inland city adjacent to Taiyuan, the capital of Shanxi Province. A 3-layer wavelet decomposition filtration was performed using the daubechies wavelet functions (db6) and the distribution of the real wavelet transformation coefficients and variance of wavelet series for various pollutants within 240 h was plotted. Five dominant periods of PM2.5 in mass concentration were observed, peaking at 101 h, 144 h, 50–51 h, 27–28 h, and 18 h in sequence from high to low in the wavelet variance chart. They were similar to those of PM10, SO2, and CO and partially overlapped with those of NO2, but different from those of O3, implying that PM2.5 have the same sources as PM10, SO2, and CO and have complicated relations with O3 and NO2. It was further found that the chemical compositions of PM2.5 in the dominant periods made great changes compared to the non-dominant periods. The relative number abundance of elemental carbon (EC) and droplets rich in CNOS (likely the mixture of carbonaceous matter with secondary aerosols such as NH4NO3 and (NH4)2SO4/NH4HSO4) in the first and second dominant period were significantly higher than that in other periods. It is concluded that coal and biomass combustion and secondary particles are still the main contributors to the wintertime heavy air pollution events in Fen-Wei Plain, suggesting that the wavelet analysis combined with low-Z particle EPMA is useful in examination of atmospheric particulate matter's origin, evolution, and roles played in haze events.

Nondestructive Characterization of Municipal-Solid-Waste-Contaminated Surface Soil by Energy-Dispersive X-ray Fluorescence and Low-Z (Atomic Number) Particle Electron Probe X-ray Microanalysis

ABSTRACT The long-term environmental impact of municipal solid waste (MSW) landfilling is still under investigation due to the lack of detailed characterization studies. A MSW landfill site, popularly known as Dhapa, in the eastern fringe of the metropolis of Kolkata, India, is the subject of present study. A vast area of Dhapa, adjoining the current core MSW dump site and evolving from the raw MSW dumping in the past, is presently used for the cultivation of vegetables. The inorganic chemical characteristics of the MSW-contaminated Dhapa surface soil (covering a 2-km stretch of the area) along with a natural composite (geogenic) soil sample (from a small countryside farm), for comparison, were investigated using two complementary nondestructive analytical techniques, energy-dispersive X-ray fluorescence (EDXRF) for bulk analysis and low-Z (atomic number) particle electron probe X-ray microanalysis (low-Z particle EPMA) for single-particle analysis. The bulk concentrations of K, Rb, and Zr remain almost unchanged in all the soil samples. The Dhapa soil is found to be polluted with heavy metals such as Cu, Zn, and Pb (highly elevated) and Ti, Cr, Mn, Fe, Ni, and Sr (moderately elevated), compared to the natural countryside soil. These high bulk concentration levels of heavy metals were compared with the Ecological Soil Screening Levels for these elements (U.S. Environment Protection Agency) to assess the potential risk on the immediate biotic environment. Low-Z particle EPMA results showed that the aluminosilicate-containing particles were the most abundant, followed by SiO2, CaCO3-containing, and carbonaceous particles in the Dhapa samples, whereas in the countryside sample only aluminosilicate-containing and SiO2 particles were observed. The mineral particles encountered in the countryside sample are solely of geogenic origin, whereas those from the Dhapa samples seem to have evolved from a mixture of raw dumped MSW, urban dust, and other contributing factors such as wind, precipitation, weather patterns, farming, and water logging, resulting in their diverse chemical compositions and the abundant observation of carbonaceous species. Particles containing C and P were more abundant in the Dhapa samples than in the countryside soil sample, suggesting that MSW-contaminated soils are more fertile. However, the levels of particles containing potentially toxic heavy metals such as Cr, Mn, Ni, Cu, Zn, and/or Pb in the Dhapa samples were significant, corroborated by their high bulk concentration levels (EDXRF), causing deep concern for the immediate environment and contamination of the food chain through food crops. IMPLICATIONS Raw MSW dumping over the past decades has made the topsoil of the Kolkata landfill site nutrient-rich, with elevated levels of carbonaceous species and essential elements such as P, K, Ca, etc., compared to the co-characterized natural soil. This may apparently encourage vegetable cultivation. However, the higher concentrations of heavy metals such as Cr, Cu, Zn, Pb, etc., in the surface soil could adversely affect the food chain and the immediate environment. The associations of minor elements such as Na, Mg, K, Ca, Ti, Fe, etc., with aluminosilicate-containing soil particles may be indicative of the soil chemical environment. Some soil remedial measures for heavy metal contaminants have to be implemented.

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

ABSTRACT 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 μm, 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. IMPLICATIONS A quantitative energy-dispersive electron probe X-ray microanalysis, called low-Z particle EPMA, was used to characterize aerosol particles collected at Jeju Island, Korea, on 4–10 April of 2001 during the intensive observation period of the Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia). The particle size distribution and chemical compositions of individual atmospheric particles over Jeju Island were obtained, and many environmentally important atmospheric particles containing sulfate, nitrate, sea salt, alminosilicate, and carbonaceous species in the size range of 0.5–16 μm were characterized. It was found that anthropogenic SO2 and NOx made great impacts on compositions of aerosol particles. The results helped better understand how air pollutants interacted with aerosol particles in the Asia-Pacific region.

Single-Particle Mineralogy of Chinese Soil Particles by the Combined Use of Low-Z Particle Electron Probe X-ray Microanalysis and Attenuated Total Reflectance-FT-IR Imaging Techniques

Our previous work on the speciation of individual mineral particles of micrometer size by the combined use of attenuated total reflectance FT-IR (ATR-FT-IR) imaging and a quantitative energy-dispersive electron probe X-ray microanalysis technique (EPMA), low-Z particle EPMA, demonstrated that the combined use of these two techniques is a powerful approach for looking at the single-particle mineralogy of externally heterogeneous minerals. In this work, this analytical methodology was applied to characterize six soil samples collected at arid areas in China, in order to identify mineral types present in the samples. The six soil samples were collected from two types of soil, i.e., loess and desert soils, for which overall 665 particles were analyzed on a single particle basis. The six soil samples have different mineralogical characteristics, which were clearly differentiated in this work. As this analytical methodology provides complementary information, the ATR-FT-IR imaging on mineral types, and low-Z particle EPMA on the morphology and elemental concentrations, on the same individual particles, more detailed information can be obtained using this approach than when either low-Z particle EPMA or ATR-FT-IR imaging techniques are used alone, which has a great potential for the characterization of Asian dust and mineral dust particles.

Single-particle characterization of indoor aerosol particles collected at an underground shopping area in Seoul, Korea

In this study, single-particle characterization of aerosol particles collected at an underground shopping area was performed for the first time. A quantitative single-particle analytical technique, low-Z particle electron probe X-ray microanalysis, was used to characterize a total of 7900 individual particles for eight sets of aerosol samples collected at an underground shopping area in Seoul, Korea. Based on secondary electron images and X-ray spectral data of individual particles, fourteen particle types were identified, in which primary soil-derived particles were the most abundant, followed by carbonaceous, Fe-containing, secondary soil-derived, and secondary sea-salt particles. Carbonaceous particles exist in three types: organic carbon, carbon-rich, and CNO-rich. A significant number of textile particles with chemical composition C, N, and O were encountered in some of the aerosol samples, which were from the textile shops and/or from clothes of passersby. Primary soil-derived particles showed seasonal variation, with peak values in spring samples, reflecting higher air exchange between indoor and outdoor environments in the spring. Secondary soil-derived, secondary sea-salt, and ammonium sulfate particles were frequently encountered in winter samples. Fe-containing particles, contributed from a nearby subway station, were in the range of about 19% relative abundances for all samples. In underground shopping areas, particulate matters can be a considerable health hazard to the workers, shoppers, passersby, and shop-keepers as they spend their considerable time in this closed microenvironment. However, no study on the characteristics of indoor aerosols in an underground shopping area has been reported to our knowledge. This work provides detailed information on characteristics of underground shopping area aerosols on a single particle level.

Characterization of Individual Atmospheric Aerosols Using Quantitative Energy Dispersive-Electron Probe X-ray Microanalysis: A Review

Great concerns about atmospheric aerosols are attributed to their multiple roles to atmospheric processes. For example, atmospheric aerosols influence global climate, directly by scattering or absorbing solar radiations and indirectly by serving as cloud condensation nuclei. They also have a significant impact on human health and visibility. Many of these effects depend on the size and composition of atmospheric aerosols, and thus detailed information on the physicochemical properties and the distribution of airborne particles is critical to accurately predict their impact on the Earth's climate as well as human health. A single particle analysis technique, named low-Z particle electron probe X-ray microanalysis (low-Z particle EPMA) that can determine the concentration of low-Z elements such as carbon, nitrogen and oxygen in a microscopic volume has been developed. The capability of quantitative analysis of low-Z elements in individual particle allows the characterization of especially important atmospheric particles such as sulfates, nitrates, ammonium, and carbonaceous particles. Furthermore, the diversity and the complicated heterogeneity of atmospheric particles in chemical compositions can be investigated in detail. In this review, the development and methodology of low-Z particle EPMA for the analysis of atmospheric aerosols are introduced. Also, its typical applications for the characterization of various atmospheric particles, i.e., on the chemical compositions, morphologies, the size segregated distributions, and the origins of Asian dust, urban aerosols, indoor aerosols in underground subway station, and Arctic aerosols, are illustrated.

Characterization of Summertime Aerosol Particles Collected at Subway Stations in Seoul, Korea Using Low-Z Particle Electron Probe X-ray Microanalysis

A quantitative single particle analytical technique, denoted low-Z particle electron probe X-ray microanalysis (low-Z particle EPMA), was applied to characterize particulate matters collected at two underground subway stations, Jegidong and Yangje stations, in Seoul, Korea. To clearly identify the source of the indoor aerosols in the subway stations, four sets of samples were collected at four different locations within the subway stations: in the tunnel; at the platform; near the ticket office; nearby outdoors. Aerosol samples collected on stages 2 and 3 (<TEX>$D_p$</TEX>: <TEX>$10-2.5\;{\mu}m$</TEX> and <TEX>$2.5-1.0\;{\mu}m$</TEX>, respectively) in a 3-stage Dekati <TEX>$PM_{10}$</TEX> impactor were investigated. Samples were collected during summertime in 2009. The major chemical species observed in the subway particle samples were Fe-containing, carbonaceous, and soil-derived particles, and secondary aerosols such as nitrates and sulfates. Among them, Fe-containing particles were the most popular. The tunnel samples contained 85-88% of Fe-containing particles, with the abundance of Fe-containing particles decreasing as the distances of sampling locations from the tunnel increased. The Fe-containing subway particles were generated mainly from mechanical wear and friction processes at rail-wheel-brake interfaces. Carbonaceous, soil-derived, and secondary nitrate and/or sulfate particles observed in the underground subway particles likely flowed in from the outdoor environment by human activities and the air-exchange between the subway system and the outdoors. In addition, since the platform screen doors (PSDs) limit air-mixing between the tunnel and the platform, samples collected at the platform at the Yangjae station (with PSDs) showed a marked decrease in the relative abundances of Fe-containing particles compared to the Jegidong station (without PSDs).

Characterization of Summertime Aerosol Particles Collected at Subway Stations in Seoul, Korea Using Low-Z Particle Electron Probe X-ray Microanalysis

Characterization of Summertime Aerosol Particles Collected at Subway Stations in Seoul, Korea Using Low-Z Particle Electron Probe X-ray Microanalysis

Source identification of particulate matter collected at underground subway stations in Seoul, Korea using quantitative single-particle analysis

Subway particle samples collected at four underground subway stations in Seoul, Korea were characterized by a single-particle analytical technique, low- Z particle electron probe X-ray microanalysis. To clearly identify indoor sources of subway particles, four sets of samples collected in tunnels, at platforms, near ticket offices, and outdoors were investigated. For the samples collected in tunnels, Fe-containing particles predominate, with relative abundances of 75–91% for the four stations. The amounts of Fe-containing particles decrease as the distance of sampling locations from the tunnel increases. In addition, samples collected at the platform in subway stations with platform screen doors (PSDs) that limit air-mixing between the platform and the tunnel showed marked decreases in relative abundances of Fe-containing particles, clearly indicating that Fe-containing subway particles are generated in the tunnel. PM 10 mass concentration levels are the highest in the tunnels, becoming lower as the distance of sampling locations from the tunnel increases. The extent of the decrease in PM 10 in stations with PSDs is also larger than that in stations without PSDs. The results clearly indicate that Fe-containing particles originating in tunnels predominate in the indoor microenvironment of subway stations, resulting in high indoor PM 10 levels, and that PSDs play a significant role in reducing Fe-containing particles at platforms and near ticket offices.

Single-Particle Characterization of Summertime Arctic Aerosols Collected at Ny-Ålesund, Svalbard

Single-particle characterization of summertime Arctic aerosols is useful to understand the impact of air pollutants on the polar atmosphere. In the present study, a quantitative single particle analytical technique, low-Z particle electron probe X-ray microanalysis, was used to characterize 8100 individual particles overall in 16 sets of aerosol samples collected at Ny-Alesund, Svalbard, Norway on 25-31 July, 2007. Based on their X-ray spectral and secondary electron image data of individual particles, 13 particle types were identified, in which particles of marine origin were the most abundant, followed by carbonaceous and mineral dust particles. A number of aged (reacted) sea salt (and mixture) particles produced by the atmospheric reaction of genuine sea-salts, especially with NO(x) or HNO(3), were significantly encountered in almost all the aerosol samples. They greatly outnumbered genuine sea salt particles, implying that the summertime Arctic atmosphere, generally regarded as a clean background environment, is disturbed by anthropogenic air pollutants. The main sources of airborne NO(x) (or HNO(3)) are probably ship emissions around the Arctic Ocean, industry emission from northern Europe and northwestern Siberia, and renoxification of NO(3)(-) within or on the melting snow/ice surface.

Elevated nitrogen-containing particles observed in Asian dust aerosol samples collected at the marine boundary layer of the Bohai Sea and the Yellow Sea

Abstract. Low-Z particle electron probe X-ray microanalysis (low-Z particle EPMA) shows powerful advantages for the characterization of ambient particulate matter in environmental and geological applications. By the application of the low-Z particle EPMA single particle analysis, an overall examination of 1800 coarse and fine particles (aerodynamic diameters: 2.5–10 μm and 1.0–2.5 μm, respectively) in six samples collected on 28 April–1 May 2006 in the marine boundary layer (MBL) of the Bohai Sea and Yellow Sea was conducted. Three samples (D1, D2, and D3) were collected along the Bohai Bay, Bohai Straits, and Yellow Sea near Korea during an Asian dust storm event while the other three samples (N3, N2, and N1) were collected on non-Asian dust (NAD) days. Based on X-ray spectral and secondary electron image data, 15 different types of particles were identified, in which soil-derived particles were encountered with the largest frequency, followed by (C, N, O)-rich droplets (likely the mixture of organic matter and NH4NO3), particles of marine origin, and carbonaceous, Fe-rich, fly ash, and (C, N, O, S)-rich droplet particles. Results show that during the Asian dust storm event relative abundances of the (C, N, O)-rich droplets and the nitrate-containing secondary soil-derived particles were markedly increased (on average by a factor of 4.5 and 2, respectively in PM2.5−10 fraction and by a factor of 1.9 and 1.5, respectively in PM1.0−2.5 fraction) in the MBL of the Bohai Sea and Yellow Sea, implying that Asian dust aerosols in springtime are an important carrier of gaseous inorganic nitrogen species, especially NOx (or HNO3) and NH3.

Attenuated Total Reflectance FT-IR Imaging and Quantitative Energy Dispersive-Electron Probe X-ray Microanalysis Techniques for Single Particle Analysis of Atmospheric Aerosol Particles

This work demonstrates the practical applicability of the combined use of attenuated total reflectance (ATR) FT-IR imaging and low-Z particle electron probe X-ray microanalysis (EPMA) techniques for the characterization of individual aerosol particles. These two single particle analytical techniques provide complementary information on the physicochemical characteristics of the same individual particles, that is, the low-Z particle EPMA for the information on the morphology and elemental concentration and the ATR-FT-IR imaging on the functional group, molecular species, and crystal structure. It was confirmed that the ATR-FT-IR imaging technique can provide sufficient FT-IR absorption signals to perform molecular speciation of individual particles of micrometer size when applied to artificially generated aerosol particles such as ascorbic acid and NaNO(3) aerosols. An exemplar indoor atmospheric aerosol sample was investigated to demonstrate the practical feasibility of the combined application of ATR-FT-IR imaging and low-Z particle EPMA techniques for the characterization of individual airborne particles.

Quantitative ED-EPMA combined with morphological information for the characterization of individual aerosol particles collected in Incheon, Korea

A quantitative single-particle analytical technique, called low- Z particle electron probe X-ray microanalysis, combined with the utilization of their morphological information on individual particles, was applied to characterize six aerosol samples collected in one Korean city, Incheon, during March 9–15, 2006. The collected supermicron aerosol particles were classified based on their chemical species and morphology on a single-particle basis. Many different particle types were identified and their emission source, transport, and reactivity in the air were elucidated. In the samples, particles in the “soil-derived particles” group were the most abundant, followed by “reacted sea-salts”, “reacted CaCO 3-containing particles”, “genuine sea-salts”, “reacted sea-salts + others”, “Fe-containing particles”, “anthropogenic organics”, (NH 4) 2SO 4, “K-containing particles”, and “fly ash”. The application of this single-particle analysis, fully utilizing their chemical compositional and morphological data of individual particles, clearly revealed the different characteristics of the six aerosol samples. For samples S3 and S5, which were sampled during two Asian dust storm events, almost all particles were of soil origin that had not experienced chemical modification and that did not entrain sea-salts during their long-range transport. For sample S1, collected at an episodic period of high PM 10 concentration and haze, anthropogenic, secondary, and soil-derived particles emitted from local sources were predominant. For samples S2, S4, and S6, which were collected on average spring days with respect to their PM 10 concentrations, marine originated particles were the most abundant. Sample S2 seems to have been strongly influenced by emissions from the Yellow Sea and Korean peninsula, sample S4 had the minimum anthropogenic influence among the four samples collected in the absence of any Asian dust storm event, and sample S6 seems to have entrained air pollutants that had been transported from mainland China over the Yellow Sea to Korea.

Morphological and chemical composition characteristics of summertime atmospheric particles collected at Tokchok Island, Korea

Determination of the chemical compositions of atmospheric single particles in the Yellow Sea region is critical for evaluating the environmental impact caused by air pollutants emitted from mainland China and the Korean peninsula. After ambient aerosol particles were collected by the Dekati PM10 cascade impactor on July 17–23, 2007 at Tokchok Island (approximately 50 km west of the Korean coast nearby Seoul), Korea, overall 2000 particles (on stage 2 and 3 with cut-off diameters of 2.5–10 μm and 1.0–2.5 μm, respectively) in 10 samples were determined by using low- Z particle electron probe X-ray microanalysis. X-ray spectral and secondary electron image (SEI) data showed that soil-derived and sea-salt particles which had reacted or were mixed with SO 2 and NO x (or their acidic products) outnumbered the primary and “genuine” ones (59.2% vs. 19.2% in the stage 2 fraction and 41.3% vs. 9.9% in the stage 3 fraction). Moreover, particles containing nitrate in the secondary soil-derived species greatly outnumbered those containing sulfate. Organic particles, mainly consisting of marine biogenic species, were more abundant in the stage 2 fraction than in the stage 3 fraction (11.6% vs. 5.1%). Their relative abundance was greater than the sum of carbon-rich, K-containing, Fe-containing, and fly ash particles, which exhibited low frequencies in all the samples. In addition, many droplets rich in C, N, O, and S were observed. They tended to be small, exhibiting a dark round shape on SEI, and generally included 8–20 at.% C, 0–12 at.% N, 60–80 at.% O, and 4–10 at.% S (sometimes with <3 at.% Mg and Na). They were attributed to be a mixture of carbonaceous matter, H 2SO 4, and NH 4HSO 4/(NH 4) 2SO 4, mostly from the reaction of atmospheric SO 2 with NH 3 under high relative humidity. The analysis of the relationship between the aerosol particle compositions and 72-h backward air-mass trajectories suggests that ambient aerosols at Tokchok Island are strongly affected not only by seawater from the Yellow Sea but also by anthropogenic pollutants emitted from China and the Seoul–Incheon metropolis, resulting in the dominance of complex secondary aerosol particles.

Chemical Compositions of Subway Particles in Seoul, Korea Determined by a Quantitative Single Particle Analysis

A novel single particle analytical technique, low-Z particle electron probe X-ray microanalysis, was applied to characterize seasonal subway samples collected at a subway station in Seoul, Korea. For all 8 samples collected twice in each season, 4 major types of subway particles, based on their chemical compositions, are significantly encountered: Fe-containing; soil-derived; carbonaceous; and secondary nitrate and/or sulfate particles. Fe-containing particles are generated indoors from wear processes at rail-wheel-brake interfaces while the others may be introduced mostly from the outdoor urban atmosphere. Fe-containing particles are the most frequently encountered with relative abundances in the range of 61-79%. In this study, it is shown that Fe-containing subway particles almost always exist either as partially or fully oxidized forms in underground subway microenvironments. Their relative abundances of Fe-containing particles increase as particle sizes decrease. Relative abundances of Fe-containing particles are higher in morning samples than in afternoon samples because of heavier train traffic in the morning. In the summertime samples, Fe-containing particles are the most abundantly encountered, whereas soil-derived and nitrate/sulfate particles are the least encountered, indicating the air-exchange between indoor and outdoor environments is limited in the summer, owing to the air-conditioning in the subway system. In our work, it was observed that the relative abundances of the particles of outdoor origin vary somewhat among seasonal samples to a lesser degree, reflecting that indoor emission sources predominate.

단일입자분석법을 이용한 지하상가에서 채취한 실내입자의 특성분석

A single particle analytical technique, named low-Z particle electron probe X-ray microanalysis, was applied to characterize four samples collected at an underground shopping area connected to Dongdeamun subway station, in January and May 2006. Based on the analysis of their chemical compositions of the samples, many distinctive particle types are identified and the major chemical species are observed to be soil-derived particles, iron-containing particles. sulfates. nitrates, and carbonaceous particles. which are encountered both in coarse and fine fractions. Carbonaceous particles exist in carbon-rich and organic. Soil derived particles such as aluminosilicates, AlSi/C, <TEX>$CaCO_3\;and\;SiO_2$</TEX> are more frequently encountered in spring samples than winter samples. Nitrate- and sulfate-con taming particles are more frequently encountered in winter samples, and those nitrate- and sulfate-containing particles mostly exist in the chemical forms of <TEX>$Ca(CO_3,\;NO_3),\;Ca(NO_3,\;SO_4),\;(Na,\;Mg)NO_3\;and\;(Mg,\;Na)(NO_3,\;SO_4)$</TEX>. Fe-containing particles which came from nearby subway platform are in the range of about 10% relative abundances for all the samples. It is observed that nitrate- and sulfate-containing particles and carbonaceous particles are much more frequently encountered in indoor aerosol samples than in outdoor aerosols, implying that <TEX>$NO_x,\;SO_x$</TEX>, and VOCs at the underground shopping area were more partitioned into aerosol phase.

Single-particle characterization of aerosol samples collected before and during an Asian dust storm in Chuncheon, Korea

Low- Z particle electron probe X-ray microanalysis, a single-particle analysis method, was used to characterize aerosol samples collected in Chuncheon, Korea, before and during a dust storm that occurred between 10 and 12 March, 2004. Four different samples were analyzed: just before the storm, peak time of the storm, late stage of the storm, and end of the storm. All four of the samples were found to have experienced chemical modifications during long-range transport due to elevated levels of nitrate and sulfate that resulted from atmospheric reactions with CaCO 3 and sea-salt particles. The sample collected just before the storm underwent the most extensive chemical modification during transport. For this particular sample, the overall relative abundances of reacted CaCO 3 and sea-salt particles were 9.8% and 44.2%, respectively. The sample collected at the peak time of the storm also experienced extensive chemical modification with overall relative abundances of reacted CaCO 3 and sea-salt particles at 4.3% and 23.3%, respectively. The backward trajectory analysis for this particular sample revealed two different types of air-masses arriving at the sampling site in Korea; one is high-altitude air-masses moving rapidly and carrying Asian dust particles and the other a slow-moving low-altitude air-mass from eastern China coastal areas. The single-particle characterization of this same sample showed that the Asian dust particles were mixed with sea-salts entrained over the Yellow Sea, as well as air pollutants from the eastern China coastal areas. However, as the Asian dust storm continued, soil-derived mineral particles became dominant in the samples that were collected at the late stage of the storm and at the end. For this specific Asian dust storm, the mixing of sea-salts and pollution with Asian dust particles was observed to occur just at the early stage of the storm.

Nitrogen and sulfur compounds in coastal Antarctic fine aerosol particles—an insight using non-destructive X-ray microanalytical methods

The capabilities of X-ray microanalytical methods, such as a near edge X-ray absorption fine structure (NEXAFS) investigation in conjunction with total reflection X-ray fluorescence (TXRF) analysis, as well as low- Z particle electron probe X-ray microanalysis (EPMA) to characterize fine Antarctic aerosol samples are demonstrated. Both techniques provided information on low- Z elements such as C, N and O. Size-segregated fine aerosol samples were collected at the Italian base at Terra Nova Bay (Antarctica) in February 2004. For comparative purposes, aerosol samples were also collected near the sea-shore in Alghero (Sardinia, Italy), in June 2004. The TXRF-NEXAFS measurements were carried out at the PGM monochromator beamline for undulator radiation in the PTB laboratory at the electron storage ring BESSY II. It was possible to quantify the molar ratio of ammonium and nitrate based on linear combinations of standard reference spectra of (NH 4) 2SO 4 and NaNO 3. Using TXRF-NEXAFS, the ammonium-to-nitrate ratio was determined in Antarctic fine aerosols collected from less than 2 m 3 of air, i.e. considerably lower than the sampling volumes usually used for ion chromatography analyses (30 m 3). This reduced sampling volume can enable the characterization of Antarctic aerosols to be done in higher temporal resolution. For Antarctic fine aerosols in the size range of 0.25–0.5 μm, nitrogen was observed to be present as almost entirely ammonium species. When the size of aerosol particles increases in the range of 0.25–2 μm, the content of ammonium decreases and yet the content of nitrate increases. An aerosol sample collected at Terra Nova Bay was investigated by the use of low- Z particle EPMA at a liquid nitrogen temperature in order to minimize beam damage of nitrogen-rich particles. Single-particle analytical results of 160 individual particles supported the TXRF-NEXAFS's observation that both ammonium-rich and nitrate-rich particles exist in the size range of 1–2 μm. Some particles were observed to contain both ammonium and nitrate species and yet pure ammonium nitrate particles were not encountered. The stoichiometry of the main chemical component of particles containing nitrogen and sulfur as major elements was found to be NH 4HSO 4.

Quantitative energy-dispersive electron probe X-ray microanalysis of individual particles

An electron probe X-ray microanalysis (EPMA) technique using an energy-dispersive X-ray detector with an ultrathin window, designated low-Z particle EPM, has been developed. The low-Z particle EPMA allows the quantitative determination of concentrations of low-Z elements, such as C, N, and O, as well as higher-Z elements that can be analyzed by conventional energy-dispersive EPMA. The quantitative determination of low-Z elements (using full Monte Carlo simulations, from the electron impact to the X-ray detection) in individual environmental particles has improved the applicability of single-particle analysis, especially in atmospheric environmental aerosol research; many environmentally important atmospheric particles, e.g. sulfates, nitrates, ammonium, and carbonaceous particles, contain low-Z elements. The low-Z particle EPMA was applied to characterize loess soil particle samples of which the chemical compositions are well defined by the use of various bulk analytical methods. Chemical compositions of the loess samples obtained from the low-Z particle EPMA turn out to be close to those from bulk analyses. In addition, it is demonstrated that the technique can also be used to assess the heterogeneity of individual particles.

Direct observation of nitrate and sulfate formations from mineral dust and sea-salts using low- Z particle electron probe X-ray microanalysis

In the present work, it is demonstrated that a single particle analytical technique, named low- Z particle electron probe X-ray microanalysis, is a practically useful tool for the study of heterogeneous reactions of mineral dust and sea-salts when this analytical technique was applied to a sample collected during an Asian Dust storm event. The technique does not require a special treatment of sample to identify particles reacted in the air. Also, quantitative chemical speciation of reacted particles can provide concrete information on what chemical reaction, if any, occurred for individual particles. Among overall 178 analyzed particles, the number of reacted particles is 81 and heterogeneous chemical reactions mostly occurred on CaCO 3 mineral dust (54 particles) and sea-salts (26 particles). Several observations made for the Asian Dust sample in the present work are: (1) CaCO 3 species almost completely reacted to produce mostly Ca(NO 3) 2 species, and CaSO 4 to a much lesser extent. (2) When reacted particles contain CaSO 4, almost all of them are internally mixed with nitrate. (3) Reacted CaCO 3 particles seem to contain moisture when they were collected. (4) Some reacted CaCO 3 particles have unreacted mineral species, such as aluminosilicates, iron oxide, SiO 2, etc., in the core region. (5) All sea-salt particles are observed to have reacted in the air. Some of them were recrystallized in the air before being collected and they are observed as crystalline NaNO 3 particles. (6) Many sea-salts were collected as water drops, and some of them were fractionally recrystallized on Ag collecting substrate. When sea-salts were not recrystallized on the substrate, they are found as particles internally mixed with NaNO 3 and Mg(NO 3) 2, and in some cases SO 4 and Cl species as additional anions.