Quantitative Electron Probe X-ray Microanalysis Research Articles

An ephemeral increase in organic carbon, ion ratios, and heavy metal-containing fine particles was screened in a maritime demarcation zone between North and South Korea

Due to its location in a politically and militarily sensitive area as a maritime demarcation between North and South Korea, increasing attention has been given to the chemical and physical changes in atmospheric aerosols on Baengnyeong Island. To observe modifications in the concentrations and components of basic air pollutants, a Korean State Air Quality Monitoring Superstation was established on the island. The monitoring data obtained from the superstation revealed a significant, short-lived increase in mass concentration of SO2, NO2, and nitrate, organic carbon, and heavy metals (especially Pb) in ambient PM2.5, as well as a gradual decrease in mass concentration of PM10, PM2.5, and sulfate in PM2.5 during September 24–27, 2012. Building upon this data, we conducted source appointment of PM2.5 using the positive matrix factorization receptor model (PMF) and identified six major sources: sea-spray aerosols (29.8%), mobile and biogenic aerosols (24.3%), secondary aerosols (20.0%), gunshot residue (11.1%), mineral dust (8.6%), and oil combustion (6.3%). To examine the physicochemical properties of atmospheric particles, 16 samples collected during that period were investigated using a quantitative energy-dispersive electron probe X-ray microanalysis (ED-EPMA). We analyzed the morphology, mixing state, elemental constituents, and relative elemental atomic concentrations of 2545 individual particles from the aforementioned six sources, with a focus on particles containing Ca, organic carbon, and Pb. The complementary use of PMF and ED-EPMA confirmed that an episode of air pollution, likely resulting from a military exercise or activity, occurred from September 25 to 26 on or near Baengnyeong Island, leading to an increase in aerosols from gunshot residue and oil combustion. The significant increase in the relative number abundance of organic carbon and heavy metal-containing particles precisely matched their mass concentrations from the monitoring data. These findings imply that multiple methods for bulk and single-particle analysis are necessary when addressing important issues related to source appointment of atmospheric particulate matter.

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.

Single-particle characterization of aerosols collected at a remote site in the Amazonian rainforest and an urban site in Manaus, Brazil

Abstract. In this study, aerosol samples collected at a remote site in the Amazonian rainforest and an urban site in Manaus, Brazil, were investigated on a single-particle basis using a quantitative energy-dispersive electron probe X-ray microanalysis (ED-EPMA). A total of 23 aerosol samples were collected in four size ranges (0.25–0.5, 0.5–1.0, 1.0–2.0, and 2.0–4.0 µm) during the wet season in 2012 at two Amazon basin sites: 10 samples in Manaus, an urban area; and 13 samples at an 80 m high tower, located at the Amazon Tall Tower Observatory (ATTO) site in the middle of the rainforest, 150 km northeast of Manaus. The aerosol particles were classified into nine particle types based on the morphology on the secondary electron images (SEIs) together with the elemental concentrations of 3162 individual particles: (i) secondary organic aerosols (SOA); (ii) ammonium sulfate (AS); (iii) SOA and AS mixtures; (iv) aged mineral dust; (v) reacted sea salts; (vi) primary biological aerosol (PBA); (vii) carbon-rich or elemental carbon (EC) particles, such as soot, tarball, and char; (viii) fly ash; and (ix) heavy metal (HM, such as Fe, Zn, Ni, and Ti)-containing particles. In submicron aerosols collected at the ATTO site, SOA and AS mixture particles were predominant (50 %–94 % in relative abundance) with SOA and ammonium sulfate comprising 73 %–100 %. In supermicron aerosols at the ATTO site, aged mineral dust and sea salts (37 %–70 %) as well as SOA and ammonium sulfate (28 %–58 %) were abundant. PBAs were observed abundantly in the PM2−4 fraction (46 %), and EC and fly ash particles were absent in all size fractions. The analysis of a bulk PM0.25−0.5 aerosol sample from the ATTO site using Raman microspectrometry and attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR) showed that ammonium sulfate, organics, and minerals are the major chemical species, which is consistent with the ED-EPMA results. In the submicron aerosols collected in Manaus, either SOA and ammonium sulfate (17 %–80 %) or EC particles (6 %–78 %) were dominant depending on the samples. In contrast, aged mineral dust, reacted sea salt, PBA, SOA, ammonium sulfate, and EC particles comprised most of the supermicron aerosols collected in Manaus. The SOA, ammonium sulfate, and PBAs were mostly of a biogenic origin from the rainforest, whereas the EC and HM-containing particles were of an anthropogenic origin. Based on the different contents of SOA, ammonium sulfate, and EC particles among the samples collected in Manaus, a considerable influence of the rainforest over the city was observed. Aged mineral dust and reacted sea-salt particles, including mineral dust mixed with sea salts probably during long-range transatlantic transport, were abundant in the supermicron fractions at both sites. Among the aged mineral dust and reacted sea-salt particles, sulfate-containing ones outnumbered those containing nitrates and sulfate + nitrate in the ATTO samples. In contrast, particles containing sulfate + nitrate were comparable in number to particles containing sulfate only in the Manaus samples, indicating the different sources and formation mechanisms of secondary aerosols, i.e., the predominant presence of sulfate at the ATTO site from mostly biogenic emissions and the elevated influences of nitrates from anthropogenic activities at the Manaus site.

Characterization of size-resolved urban haze particles collected in summer and winter at Taiyuan City, China using quantitative electron probe X-ray microanalysis

The aim of the study is to characterize the size-resolved urban haze particles and investigate their modification in morphology and composition in summer and winter using the semi-quantitative electron probe X-ray microanalysis (EPMA) based on both scanning and transmission electron microscopies equipped with ultrathin-window energy dispersive X-ray spectrometers (SEM-EDX and TEM-EDX). The haze and non-haze particles were collected through a seven-stage May cascade impactor on Dec. 29–30, 2009 and Jan. 8–9 and July 11–14, 2010 in Taiyuan, a typical inland city in the North China Plain. Approximately 3752 atmospheric particles in the size ranges of 4–2μm, 2–1μm, 1–0.5μm, and 0.5–0.25μm in aerodynamic diameter were measured and identified according to their secondary electron or TEM images and elemental atomic concentrations calculated through a Monte Carlo simulation program. Results show that on the haze days many reacted or aged mineral dust particles were encountered, in which the sulfate-containing ones outnumbered the nitrate-containing ones in the winter samples while it was on the contrary in the summer samples, suggesting different haze formation and evolution mechanisms in summer and winter. Furthermore, in the haze events (especially in summer), many CNOS-rich particles, likely mixtures of water-soluble organic carbon with (NH4)2SO4 or NH4HSO4, were observed not only in the submicron but also in the super-micron fractions. The simultaneous observation of the fresh and aged CNOS-rich particles in the same SEM or TEM images implied that the status and components of secondary particles were complicated and changeable. The significant increase of both elemental concentration ratios of [N]/[S] and [C]/[S] in the aged ones compared to the fresh ones indicated that NH4NO3 and secondary organic matter were likely absorbed onto (NH4)2SO4 or NH4HSO4 particles and mixed with them. K-rich, Fe-rich, and heavy metal-containing particles in TEM-EDX measurement were detected more in the winter haze samples than in the summer ones, suggesting that they tend to be smaller in size and mainly derive from anthropogenic biomass burning and coal combustion. It was concluded that the combined use of SEM-EDX and TEM-EDX can identify both submicron and super-micron urban haze particles in a straightforward way and trace their modifications in size, shape, mixing state, and chemical compositions in different seasons, helping address their evolution processes and hazards on human health.

Cell viability evaluation of transdifferentiated endothelial-like cells by quantitative electron-probe X-ray microanalysis for tissue engineering.

Development of an efficient vascular substitute by tissue engineering is strongly dependent on endothelial cell viability. The aim of this study was to evaluate cell viability of transdifferentiated endothelial-like cells (Tr-ELC) by using for the first time electron probe X-ray microanalysis (EPXMA), not only to accurately analyze cell viability by quantifying the intracellular ionic concentrations, but also to establish their possible use in vascular tissue engineering protocols. Human umbilical cord Wharton's jelly stem cells (HWJSC) and endothelial cells from the human umbilical vein (HUVEC) were isolated and cultured. Transdifferentiation from HWJSC to the endothelial phenotype was induced. EPXMA was carried out to analyze HUVEC, HWJSC and Tr-ELC cells by using a scanning electron microscope equipped with an EDAX DX-4 microanalytical system and a solid-state backscattered electron detector. To determine total ion content, the peak-to-local-background (P/B) ratio method was used with reference to standards composed of dextran containing known amounts of inorganic salts. Our results revealed a high K/Na ratio in Tr-ELC (9.41), in association with the maintenance of the intracellular levels of chlorine, phosphorous and magnesium and an increase of calcium (p=0.031) and sulfur (p=0.022) as compared to HWJSC. Calcium levels were similar for HUVEC and Tr-ELC. These results ensure that transdifferentiated cells are highly viable and resemble the phenotypic and microanalytical profile of endothelial cells. Tr-ELC induced from HWJSC may fulfill the requirements for use in tissue engineering protocols applied to the vascular system at the viability and microanalytical levels.

Investigation of fine chalk dust particles’ chemical compositions and toxicities on alveolar macrophages in vitro

The aim of the study is to investigate chemical compositions of fine chalk dust particles (chalk PM2.5) and examine their adverse effects on alveolar macrophages (AMs) in vitro. Morphologies and element concentrations of individual chalk particles were analyzed by using the quantitative energy-dispersive electron probe X-ray microanalysis (ED-EPMA). The oxidative response of AMs and the potential to generate nitric oxide (NO) by luminol-dependent chemiluminescence (CL) and nitrate reductase method were assessed 4h following the treatment of AMs with differing dosages of fine chalk particles, respectively. Oxidative stress and cytotoxicity elicited by chalk PM2.5 were also examined. The results showed that fine chalk particles were mainly composed of gypsum, calcite, dolomite and a little amount of organic adhesives. Exposure to chalk PM2.5 at 100μgmL−1 or 300μgmL−1 significantly increased intracellular catalase, malondialdehyde, and NO levels and decreased superoxide dismutase level in AMs, leading to leakage of lactate dehydrogenase (LDH) and reduction of the cell viability. Furthermore, luminol-dependent CL from respiratory burst in AMs was enhanced. It was suggested that chalk PM2.5 could make oxidative damages on AMs and result in cytotoxicity, being likely attributed to excessive reactive oxygen species or reactive nitrogen species induced by mixture of fine gypsum and calcite/dolomite particles.

Chemical compositions and effects on chemiluminescence of AMs in vitro of chalk dusts

Abstract The aim of this study was to investigate the chemical compositions of chalk dust and examine the adverse effects of fine chalk particle matters (PM 2.5 ) on rat alveolar macrophages (AMs) in vitro. Morphologies and element concentrations of chalk particles were analyzed using quantitative energy-dispersive electron probe X-ray microanalysis (ED-EPMA). The oxidative response of AMs exposed to chalk PM 2.5 was measured by luminol-dependent chemiluminescence (CL). The results showed that (1) Chalk dust was mainly composed of gypsum (CaSO 4 ), calcite (CaCO 3 )/dolomite (CaMg(CO 3 ) 2 ), and organic adhesives; (2) Fine chalk particles induced the AM production of CL, which was inhibited by about 90% by diphenyleneiodonium chloride (DPI). Based on these results, we showed that cytotoxicity of chalk PM 2.5 may be related to the reactive oxygen species (ROS) generation.

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.

Investigation of the Chemical Mixing State of Individual Asian Dust Particles by the Combined Use of Electron Probe X-ray Microanalysis and Raman Microspectrometry

In this work, quantitative electron probe X-ray microanalysis (EPMA) and Raman microspectrometry (RMS) were applied in combination for the first time to characterize the complex internal structure and physicochemical properties of the same ensemble of Asian dust particles. The analytical methodology to obtain the chemical composition, mixing state, and spatial distribution of chemical species within single particles through the combined use of the two techniques is described. Asian dust aerosol particles collected in Incheon, Korea, during a moderate dust storm event were examined to assess the applicability of the methodology to resolve internal mixtures within single particles. Among 92 individual analyzed particles, EPMA and RMS identified 53% of the particles to be internally mixed with two or more chemical species. Information on the spatial distribution of chemical compounds within internally mixed individual particles can be useful for deciphering the particle aging mechanisms and sources. This study demonstrates that the characterization of individual particles, including chemical speciation and mixing state analysis, can be performed more in detail using EPMA and RMS in combination than with the two single-particle techniques alone.

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 Summertime Antarctic Aerosols Collected at King George Island Using Quantitative Energy-Dispersive Electron Probe X-ray Microanalysis and Attenuated Total Reflection Fourier Transform-Infrared Imaging Techniques

Single-particle characterization of Antarctic aerosols was performed to investigate the impact of marine biogenic sulfur species on the chemical compositions of sea-salt aerosols in the polar atmosphere. Quantitative energy-dispersive electron probe X-ray microanalysis was used to characterize 2900 individual particles in 10 sets of aerosol samples collected between March 12 and 16, 2009 at King Sejong Station, a Korean scientific research station located at King George Island in the Antarctic. Two size modes of particles, i.e., PM(2.5-10) and PM(1.0-2.5), were analyzed, and four types of particles were identified, with sulfur-containing sea-salt particles being the most abundant, followed by genuine sea-salt particles without sulfur species, iron-containing particles, and other species including CaCO(3)/CaMg(CO(3))(2), organic carbon, and aluminosilicates. When a sulfur-containing sea-salt particle showed an atomic concentration ratio of sulfur to sodium of >0.083 (seawater ratio), it is regarded as containing nonsea-salt sulfate (nss-SO(4)(2-)) and/or methanesulfonate (CH(3)SO(3)(-)), which was supported by attenuated total reflection Fourier transform-infrared imaging measurements. These internal mixture particles of sea-salt/CH(3)SO(3)(-)/SO(4)(2-) were very frequently encountered. As nitrate-containing particles were not encountered, and the air-masses for all of the samples originated from the Pacific Ocean (based on 5-day backward trajectories), the oxidation of dimethylsulfide (DMS) emitted from phytoplanktons in the ocean is most likely to be responsible for the formation of the mixed sea-salt/CH(3)SO(3)(-)/SO(4)(2-) 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.

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.