low-Z Particle EPMA Research Articles

Single-particle Mineralogy of Asbestos Mineral Particles by the Combined Use of Low-Z Particle EPMA and ATR-FTIR Imaging Techniques

In this work, two single particle analytical techniques such as a quantitative energy-dispersive electron probe X-ray microanalysis (ED-EPMA), called low-Z particle EPMA, and attenuated total reflectance Fourier transform-Infrared (ATR-FTIR) imaging were applied in combination for the characterization and distinction of six standard asbestos and one non-asbestos Mg-silicate minerals of micrometer size. Asbestos fibers have been reported as a natural carcinogen which causes some serious illness like mesothelioma, asbestosis, and lung cancer. Atmospheric aerosols are heterogeneous mixtures and airborne asbestos fibers would be present due to their extensive industrial uses for various purposes. The fibers could also be airborne from natural and anthropogenic sources. As different asbestos fibers have different carcinogenic properties, it is important to determine different types of individual asbestos and non-asbestos Mg-silicate mineral particles and their sources for the public health management. In our previous works, the speciation of individual aerosol particles was performed by the combined use of the two single-particle analytical techniques, which demonstrated that the combined use of the two analytical techniques is powerful for detailed characterization of externally heterogeneous aerosol particle samples and has great potential for characterization of atmospheric aerosols. In this work, it is demonstrated that the identification and differentiation of asbestiform and non-asbestiform Mg-silicate mineral particles is clearly performed using the two single particle analytical techniques in combination than using either technique individually. Especially, anthophyllite and talc can be differentiated using this analytical approach, which has not been easy up until now.

Investigation of aged aerosols in size-resolved Asian dust storm particles transported from Beijing, China, to Incheon, Korea, using low-<i>Z</i> particle EPMA

Abstract. This is the first study of Asian dust storm (ADS) particles collected in Beijing, China, and Incheon, Korea, during a spring ADS event. Using a seven-stage May impactor and a quantitative electron probe X-ray microanalysis (ED-EPMA, also known as low-Z particle EPMA), we examined the composition and morphology of 4200 aerosol particles at stages 1–6 (with a size cut-off of 16, 8, 4, 2, 1, and 0.5 μm in equivalent aerodynamic diameter, respectively) collected during an ADS event on 28–29 April 2005. The results showed that there were large differences in the chemical compositions between particles in sample S1 collected in Beijing immediately after the peak time of the ADS and in samples S2 and S3, which were collected in Incheon approximately 5 h and 24 h later, respectively. In sample S1, mineral dust particles accounted for more than 88% in relative number abundance at stages 1–5; and organic carbon (OC) and reacted NaCl-containing particles accounted for 24% and 32%, respectively, at stage 6. On the other hand, in samples S2 and S3, in addition to approximately 60% mineral dust, many sea spray aerosol (SSA) particles reacted with airborne SO2 and NOx (accounting for 24% and 14% on average in samples S2 and S3, respectively), often mixed with mineral dust, were encountered at stages 1–5, and (C, N, O, S)-rich particles (likely a mixture of water-soluble organic carbon with (NH4)2SO4 and NH4NO3) were abundantly observed at stage 6 (accounting for 68% and 51% in samples S2 and S3, respectively). This suggests that an accumulation of sea-salt components on individual ADS particles larger than 1 μm in diameter occurred and many secondary aerosols smaller than 1 μm in diameter were formed when the ADS particles passed over the Yellow Sea. In the reacted or aged mineral dust and SSA particles, nitrate-containing and both nitrate- and sulfate-containing species vastly outnumbered the sulfate-containing species, implying that ambient NOx had a greater influence on the atmospheric particles than SO2 during this ADS episode. In addition to partially- or totally-reacted CaCO3, reacted or aged Mg-containing aluminosilicates were observed frequently in samples S2 and S3; furthermore, a student's t test showed that both their atomic concentration ratios of [Mg] / [Al] and [Mg] / [Si] were significantly elevated (P < 0.05) compared to those in samples S1 (for [Mg] / [Al], 0.34 ± 0.09 and 0.40 ± 0.03 in samples S2 and S3, respectively, vs. 0.24 ± 0.01 in sample S1; for [Mg] / [Si], 0.21 ± 0.05 and 0.22 ± 0.01 in samples S2 and S3, respectively, vs. 0.12 ± 0.02 in sample S1). The significant increase of [Mg] / [Al] and [Mg] / [Si] ratios in Mg-containing aluminosilicates indicates that a significant evolution or aging must have occurred on the ADS particles in the marine atmosphere during transport from China to Korea.

Combined use of quantitative ED-EPMA, Raman microspectrometry, and ATR-FTIR imaging techniques for the analysis of individual particles.

In this work, quantitative energy-dispersive electron probe X-ray microanalysis (ED-EPMA) (called low-Z particle EPMA), Raman microspectrometry (RMS), and attenuated total reflectance Fourier transform infrared spectroscopic (ATR-FTIR) imaging were applied in combination for the analysis of the same individual airborne particles for the first time. After examining individual particles of micrometer size by low-Z particle EPMA, consecutive examinations by RMS and ATR-FTIR imaging of the same individual particles were then performed. The relocation of the same particles on Al or Ag foils was successfully carried out among the three standalone instruments for several standard samples and an indoor airborne particle sample, resulting in the successful acquisition of quality spectral data from the three single-particle analytical techniques. The combined application of the three techniques to several different standard particles confirmed that those techniques provided consistent and complementary chemical composition information on the same individual particles. Further, it was clearly demonstrated that the three different types of spectral and imaging data from the same individual particles in an indoor aerosol sample provided richer information on physicochemical characteristics of the particle ensemble than that obtainable by the combined use of two single-particle analytical techniques.

Iron Speciation of Airborne Subway Particles by the Combined Use of Energy Dispersive Electron Probe X-ray Microanalysis and Raman Microspectrometry

Quantitative energy-dispersive electron probe X-ray microanalysis (ED-EPMA), known as low-Z particle EPMA, and Raman microspectrometry (RMS) were applied in combination for an analysis of the iron species in airborne PM10 particles collected in underground subway tunnels. Iron species have been reported to be a major chemical species in underground subway particles generated mainly from mechanical wear and friction processes. In particular, iron-containing particles in subway tunnels are expected to be generated with minimal outdoor influence on the particle composition. Because iron-containing particles have different toxicity and magnetic properties depending on their oxidation states, it is important to determine the iron species of underground subway particles in the context of both indoor public health and control measures. A recently developed analytical methodology, i.e., the combined use of low-Z particle EPMA and RMS, was used to identify the chemical species of the same individual subway particles on a single particle basis, and the bulk iron compositions of airborne subway particles were also analyzed by X-ray diffraction. The majority of airborne subway particles collected in the underground tunnels were found to be magnetite, hematite, and iron metal. All the particles collected in the tunnels of underground subway stations were attracted to permanent magnets due mainly to the almost ubiquitous ferrimagnetic magnetite, indicating that airborne subway particles can be removed using magnets as a control measure.

Investigation of aged Asian dust particles by the combined use of quantitative ED-EPMA and ATR-FTIR imaging

Abstract. In our previous works, it was demonstrated that the combined use of quantitative energy-dispersive electron probe X-ray microanalysis (ED-EPMA), which is also known as low-Z particle EPMA, and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) imaging has great potential for a detailed characterization of individual aerosol particles. In this study, extensively chemically modified (aged) individual Asian dust particles collected during an Asian dust storm event on 11 November 2002 in Korea were characterized by the combined use of low-Z particle EPMA and ATR-FTIR imaging. Overall, 109 individual particles were classified into four particle types based on their morphology, elemental concentrations, and molecular species and/or functional groups of individual particles available from the two analytical techniques: Ca-containing (38%), NaNO3-containing (30%), silicate (22%), and miscellaneous particles (10%). Among the 41 Ca-containing particles, 10, 8, and 14 particles contained nitrate, sulfate, and both, respectively, whereas only two particles contained unreacted CaCO3. Airborne amorphous calcium carbonate (ACC) particles were observed in this Asian dust sample for the first time, where their IR peaks for the insufficient symmetric environment of CO32− ions of ACC were clearly differentiated from those of crystalline CaCO3. This paper also reports the first inland field observation of CaCl2 particles probably converted from CaCO3 through the reaction with HCl(g). HCl(g) was likely released from the reaction of sea salt with NOx/HNO3, as all 33 particles of marine origin contained NaNO3 (no genuine sea salt particle was encountered). Some silicate particles with minor amounts of calcium were observed to be mixed with nitrate, sulfate, and water. Among 24 silicate particles, 10 particles are mixed with water, the presence of which could facilitate atmospheric heterogeneous reactions of silicate particles including swelling minerals, such as montmorillonite and vermiculite, and nonswelling ones, such as feldspar and quartz. This paper provides detailed information on the physicochemical characteristics of these aged individual Asia dust particles through the combined use of the two single-particle analytical techniques, and using this analytical methodology it is clearly shown that internal mixing states of the aged particles are highly complicated.

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.

Characterisation of individual aerosol particles collected during a haze episode in Incheon, Korea using the quantitative ED-EPMA technique

Abstract. A quantitative energy-dispersive electron probe X-ray microanalysis (ED-EPMA), called low-Z particle EPMA, was used to analyse individual aerosol particles collected in Incheon, Korea on 13–18 October 2008 (a typical haze episode occurred from 15 to 18 October). Overall 3600 individual particles in PM2.5-10 and PM1.0-2.5 fractions from 12 aerosol samples collected on haze and non-haze days were analysed. The analysed particles were classified, based on their X-ray spectral data together with their secondary electron images. The major particle types included organic carbon (OC), elemental carbon (EC), sea-salt, mineral dust (such as aluminosilicate, SiO2, CaCO3/CaMgCO3, etc.), (NH4)2SO4/NH4HSO4-containing, K-containing, Fe-rich and fly ash particles. Their relative number abundance results showed that OC particles were significantly increased while sea-salts and mineral dust particles were significantly decreased (especially in PM1.0-2.5 fraction) when haze occurred. For the other particle types (except Fe-rich particles in PM2.5-10 fraction), there were no significant differences in their relative abundances between haze and non-haze samples. On non-haze days, the nitrate-containing reacted sea-salt and mineral dust particles in PM1.0-2.5 fraction significantly outnumbered the sulfate-containing ones, whereas it was the reverse on haze days, implying that on haze days there were special sources or formation mechanisms for fine aerosol particles (≤2.5 μm in aerodynamic diameter). The emission of air pollutants from motor vehicles and stagnant meteorological conditions, such as low wind speed and high relative humidity, might be responsible for the elevated level of OC particles on haze days.

Quantitative energy-dispersive electron probe X-ray microanalysis for single-particle analysis and its application for characterizing atmospheric aerosol particles

An energy-dispersive electron probe X-ray microanalysis (ED-EPMA) technique using an energy-dispersive X-ray detector with an ultra-thin window, designated as low-Z particle EPMA, 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 analysed by conventional ED-EPMA. The quantitative determination of low-Z elements (using full Monte Carlo simulations, from the electron impact to the X-ray detection) in individual particles has improved the applicability of single-particle analysis, especially in atmospheric environmental aerosol research; many environmentally important atmospheric particles, e.g. sulphates, nitrates, ammonium and carbonaceous particles, contain low-Z elements. To demonstrate its practical applicability, the application of the low-Z particle EPMA for the characterization of Asian Dust, urban and subway aerosol particles is shown herein. In addition, it is demonstrated that the Monte Carlo calculation can also be applied in a quantitative single-particle analysis using transmission electron microscopy (TEM) coupled with energy-dispersive X-ray spectrometry (EDX), showing that the technique is useful and reliable for the characterization of submicron aerosol particles.

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).

Combined Use of Optical and Electron Microscopic Techniques for the Measurement of Hygroscopic Property, Chemical Composition, and Morphology of Individual Aerosol Particles

In this work, an analytical method for the characterization of the hygroscopic property, chemical composition, and morphology of individual aerosol particles is introduced. The method, which is based on the combined use of optical and electron microscopic techniques, is simple and easy to apply. An optical microscopic technique was used to perform the visual observation of the phase transformation and hygroscopic growth of aerosol particles on a single particle level. A quantitative energy-dispersive electron probe X-ray microanalysis, named low-Z particle EPMA, was used to perform a quantitative chemical speciation of the same individual particles after the measurement of the hygroscopic property. To validate the analytical methodology, the hygroscopic properties of artificially generated NaCl, KCl, (NH(4))(2)SO(4), and Na(2)SO(4) aerosol particles of micrometer size were investigated. The practical applicability of the analytical method for studying the hygroscopic property, chemical composition, and morphology of ambient aerosol particles is demonstrated.

Chemical Speciation of Individual Airborne Particles by the Combined Use of Quantitative Energy-Dispersive Electron Probe X-ray Microanalysis and Attenuated Total Reflection Fourier Transform-Infrared Imaging Techniques

In our previous work, it was demonstrated that the combined use of attenuated total reflectance (ATR) FT-IR imaging and quantitative energy-dispersive electron probe X-ray microanalysis (ED-EPMA), named low-Z particle EPMA, had the potential for characterization of individual aerosol particles. Additionally, the speciation of individual mineral particles was performed on a single particle level by the combined use of the two techniques, demonstrating that simultaneous use of the two single particle analytical techniques is powerful for the detailed characterization of externally heterogeneous mineral particle samples and has great potential for characterization of atmospheric mineral dust aerosols. These single particle analytical techniques provide complementary information on the physicochemical characteristics of the same individual particles, such as low-Z particle EPMA on morphology and elemental concentrations and the ATR-FT-IR imaging on molecular species, crystal structures, functional groups, and physical states. In this work, this analytical methodology was applied to characterize an atmospheric aerosol sample collected in Incheon, Korea. Overall, 118 individual particles were observed to be primarily NaNO(3)-containing, Ca- and/or Mg-containing, silicate, and carbonaceous particles, although internal mixing states of the individual particles proved complicated. This work demonstrates that more detailed physiochemical properties of individual airborne particles can be obtained using this approach than when either the low-Z particle EPMA or ATR-FT-IR imaging technique is used alone.

Speciation of Individual Mineral Particles of Micrometer Size by the Combined Use of Attenuated Total Reflectance-Fourier Transform-Infrared Imaging and Quantitative Energy-Dispersive Electron Probe X-ray Microanalysis Techniques

Our previous work demonstrated for the first time the potential of the combined use of two techniques, attenuated total reflectance FT-IR (ATR-FT-IR) imaging and a quantitative energy-dispersive electron probe X-ray microanalysis, low-Z particle EPMA, for the characterization of individual aerosol particles. In this work, the speciation of mineral particles was performed on a single particle level for 24 mineral samples, including kaolinite, montmorillonite, vermiculite, talc, quartz, feldspar, calcite, gypsum, and apatite, by the combined use of ATR-FT-IR imaging and low-Z particle EPMA techniques. These two single particle analytical techniques provide 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. This work demonstrates that the combined use of the two single particle analytical techniques can powerfully characterize externally heterogeneous mineral particle samples in detail and has great potential for the characterization of airborne mineral dust particles.

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.

F63 Speciation of Nitrogen Compounds in Nanoscopic Fine Aerosol Samples Using TXRF-NEXAFS and Low-Z Particle EPMA

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Single-Particle Characterization of Four “Asian Dust” Samples Collected in Korea, Using Low-Z Particle Electron Probe X-ray Microanalysis

A single-particle analytical technique, named low-Z particle electron probe X-ray microanalysis (low-Z particle EPMA), employing an ultrathin window X-ray detector and enabling the quantitative determination of even low-Z elements such as C, N, and O, is applied to characterize "Asian Dust" samples, collected in ChunCheon, Korea, during four Asian Dust storm events on March 7, 2000, April 7, 2000, March 22, 2001, and May 17, 2001. In this study, it is demonstrated that single-particle analysis using the low-Z particle EPMA provides detailed information on various types of chemical species in the samples. The most abundantly encountered particles, both in coarse and fine fractions, are aluminosilicates. The relative abundances of those particles on the basis of their size are different between the four Asian Dust samples. The sample collected on March 7, 2000 did not experience any chemical modification during its transport because the sample does not contain particles of chemical species that result from atmospheric reactions. The sample collected on April 7, 2000 contains both genuine and reacted sea-salt particles. The genuine sea-salts are in the form of a mixture of NaCl and MgCl2 entrained during their passage over the Yellow Sea. The reacted sea-salts particles are encountered very much in fine fraction. The sample collected on March 22, 2001 shows somewhat significant chemical modification both for CaCO3 and sea-salts particles. For this sample, a significant number of reacted CaCO3 and sea-salt particles, such as those containing nitrate and/or sulfate, are encountered, implying that CaCO3 and sea-salts particles have reacted with sulfur or nitrogen oxide species during their long-range transport. The sample collected on May 17, 2001 experienced the most extensive chemical modification during its transport. In addition to the observation of the extensively reacted CaCO3 and sea-salt particles, reacted K2CO3 particles are also extensively encountered in this sample, which implies that K2CO3 species should be regarded as an additional important chemical species in the study of the chemical modification of Asian Dust particles during long-range transport.