Seasonal variations of acidic air pollutants in Seoul,South Korea

The annular denuder system (ADS) was used to characterize seasonal variations of acidic air pollutants in Seoul, South Korea. Fifty- four 24 h samples were collected over four seasons from October 1996 to September 1997. The annual mean concentrations of HNO₃, HNO₂, SO₂ and NH₃ in the gas phase were 1.09, 4.51, 17.3 and 4.34 μg m^-3, respectively. The annual mean concentrations of PM_2.5(d_p≤2.5 μm in aerodynamic diameter, 50% cutoff), SO^2-₄, NO^-₃ and NH⁺₄ in the particulate phase were 56.9, 8.70, 5.97 and 4.19 μg m^-3, respectively. All chemical species monitored from this study showed statistical seasonal variations. Nitric acid (HNO₃) and ammonia (NH₃) exhibited substantially higher concentrations during the summer, while nitrous acid (HNO₂) and sulfur dioxide(SO₂) were higher during the winter. Concentrations of PM_2.5, SO^2-₄, NO^-₃ and NH⁺₄ in the particulate phase were higher during the winter months. SO^2-₄, NO^-₃ and NH⁺₄ accounted for 26–38% of PM_2.5. High correlations were found among PM_2.5, SO^2-₄, NO^-₃ and NH⁺₄. The mean H⁺ concentration measured only in the fall was 5.19 nmole m^-3.     

PM2.5–10, PM2.5 and associated water-soluble inorganic species at a coastal urban site in the metropolitan region of Rio de Janeiro

The concentrations of PM_2.5−10, PM_2.5 and associated water-soluble inorganic species (WSIS) were determined in a coastal site of the metropolitan region of Rio de Janeiro, Southeastern Brazil, from October 1998 to September 1999 (n=50). Samples were dissolved in water and analyzed for major inorganic ions. The mean (± standard deviation; median) concentrations of PM_2.5−10 and PM_2.5 were, respectively, 26 (± 16; 21) μg m⁻³ and 17 (± 13; 14) μg m⁻³. Their mean concentrations were 1.7–1.8 times higher in dry season (May–October) than in rainy season (November–April). The WSIS comprised, respectively, 34% and 28% of the PM_2.5−10 and PM_2.5 masses. Chloride, Na⁺ and Mg²⁺ were the predominant ions in PM_2.5−10, indicating a significant influence of sea-salt aerosols. In PM_2.5, SO₄²⁻ (∼97% nss-SO₄²⁻) and NH₄⁺ were the most abundant ions and their equivalent concentration ratio (SO₄²⁻/NH₄⁺ ∼1.0) suggests that they were present as (NH₄)₂SO₄ particles. The mean concentration of (NH₄)₂SO₄ was 3.4 μg m⁻³. The mean equivalent PM_2.5 NO₃⁻ concentration was eight times smaller than those of SO₄²⁻ and NH₄⁺. The PM_2.5 NO₃⁻ concentration in dry season was three times higher than in rainy season, probably due to reaction of NaCl (sea salt) with HNO₃ as a result of higher levels of NO_y during the dry season and/or reduced volatilization of NH₄NO₃ due to lower wintertime temperature. Chloride depletion was observed in both size ranges, although more pronouncely in PM_2.5.     

Major ionic compositions of fine particulate matter in an animal feeding operation facility and its vicinity

Animal feeding operations (AFOs) produce particulate matter (PM) and gaseous pollutants. Investigation of the chemical composition of PM_2.5 inside and in the local vicinity of AFOs can help to understand the impact of the AFO emissions on ambient secondary PM formation. This study was conducted on a commercial egg production farm in North Carolina. Samples of PM_2.5 were collected from five stations, with one located in an egg production house and the other four located in the vicinity of the farm along four wind directions. The major ions of NH₄⁺, Na⁺, K⁺, SO₄^2?, Cl^?, and NO₃^? were analyzed using ion chromatography (IC). In the house, the mostly abundant ions were SO₄^2?, Cl^?, and K⁺. At ambient stations, SO₄^2?, and NH₄⁺ were the two most abundant ions. In the house, NH₄⁺, SO₄^2?, and NO₃^? accounted for only 10% of the PM_2.5 mass; at ambient locations, NH₄⁺, SO₄^2?, and NO₃^? accounted for 36–41% of the PM_2.5 mass. In the house, NH₄⁺ had small seasonal variations indicating that gas-phase NH₃ was not the only major force driving its gas–particle partitioning. At the ambient stations, NH₄⁺ had the highest concentrations in summer. In the house, K⁺, Na⁺, and Cl^? were highly correlated with each other. In ambient locations, SO₄^2? and NH₄⁺ had a strong correlation, whereas in the house, SO₄^2? and NH₄⁺ had a very weak correlation. Ambient temperature and solar radiation were positively correlated with NH₄⁺ and SO₄^2?. This study suggests that secondary PM formation inside the animal house was not an important source of PM_2.5. In the vicinity, NH₃ emissions had greater impact on PM_2.5 formation.

ImplicationsThe chemical composition of PM_2.5 inside and in the local vicinity of AFOs showed the impact of the AFO emissions on ambient secondary PM_2.5 formation, and the fate and transport of air pollutants associated with AFOs. The results may help to manage in-house animal facility air quality, and to develop regional air quality control strategies and policies, especially in animal agriculture-concentrated areas.     

Chemical characterization of particles in winter-night smog in Tokyo

Continuous measurement of PM₁₀, PM_2.5 and carbon (organic, elemental composition) concentrations, and samples of PM₁₀ and PM_2.5 collected on a polycarbonate membrane filter (Nuclepore^®, pore size: 0.8 μm), were carried out during a period from December 1998 to January 1999 at Shinjuku in Tokyo in order to investigate the chemical characterization of particles in winter-night smog within a large area of the Japan Kanto Plain including the Tokyo Metropolitan area. These were measured using an ambient particulate monitor (tapered element oscillating microbalance—TEOM) and a carbon particulate monitor. Elemental compositions in the filter samples of PM₁₀ and PM_2.5 were determined by means of particle-induced X-ray emission (PIXE) analysis. Ionic species (anion: F⁻, Cl⁻, NO₃⁻, SO₄²⁻ and C₂O₄²⁻; cation: Na⁺, NH₄⁺, K⁺, Ca²⁺ and Mg²⁺) in the filter samples were analyzed by ion chromatography. The temporal variation patterns of PM_2.5 were similar to those of PM₁₀ and carbon. PM_2.5 made up 90% of the PM₁₀ at a high concentration, and 70% at a low concentration. Concentrations of 22 elements in both the PM₁₀ and PM_2.5 samples were consistently determined by PIXE, and Na, Mg, Al, Si, S, Cl, K, Ca, Fe, Zn and Pb were found to be the major components. Among these S and Cl were the most dominant elements of the PM_2.5 and PM₁₀ at high concentrations. Ionic species were mainly composed of Cl⁻, NO₃⁻, SO₄²⁻ and NH₄⁺. The component proportion of carbon, the other elements (total amount of measured elements other than S and Cl) and secondary-formed particles of PM_2.5 was similar to that of PM₁₀. The major component was carbon particles at a low concentration and secondary-formed particles at a high concentration. The proportion of NH₄NO₃ and NH₄Cl plus HCl in secondary-formed particles at a high concentration, in particular, was as high as 90%.     

Seasonal variation of ionic species in fine particles at Qingdao,China

Totally nine measurement campaigns for ambient particles and SO₂ have been conducted during the period of 1997–2000 in Qingdao in order to understand the characteristics of the particulate matter in coastal areas of China. The mass fractions of PM_2.5, PM_2.5−10 and PM_>10 in TSP are 49%, 25% and 26%, respectively. The size distribution of particles mass concentrations in Qingdao shows bi-modal distribution. Mass fraction percentages of water-soluble ions in PM_2.5, PM_2.5−10 and PM_>10 decreased from 62% to 35% and 21%. In fine particles, sulfate, nitrate and ammonium, secondary formed compounds, are major components, totally accounting for 50% of PM_2.5 mass concentration.The ratios of sulfate, chloride, ammonium and potassium in PM_2.5 for heating versus non-heating periods are 1.34, 1.80, 1.56 and 1.44, respectively. The ratio of nitrate is 3.02 and this high ratio could be caused by reduced volatilization at lower temperature. Sulfate concentrations are higher than nitrate in PM_2.5. The chemical forms of sulfate and nitrate are probably (NH₄)₂SO₄ and NH₄NO₃ and chloride depletion was observed.Backward trajectory analysis reflected possible influence of air pollutant transport to Qingdao local aerosol pollution.     

Sensitivity analyses of factors influencing CMAQ performance for fine particulate nitrate

Improvement of air quality models is required so that they can be utilized to design effective control strategies for fine particulate matter (PM_2.5). The Community Multiscale Air Quality modeling system was applied to the Greater Tokyo Area of Japan in winter 2010 and summer 2011. The model results were compared with observed concentrations of PM_2.5 sulfate (SO₄^2-), nitrate (NO₃^?) and ammonium, and gaseous nitric acid (HNO₃) and ammonia (NH₃). The model approximately reproduced PM_2.5 SO₄^2? concentration, but clearly overestimated PM_2.5 NO₃^? concentration, which was attributed to overestimation of production of ammonium nitrate (NH₄NO₃). This study conducted sensitivity analyses of factors associated with the model performance for PM_2.5 NO₃^? concentration, including temperature and relative humidity, emission of nitrogen oxides, seasonal variation of NH₃ emission, HNO₃ and NH₃ dry deposition velocities, and heterogeneous reaction probability of dinitrogen pentoxide. Change in NH₃ emission directly affected NH₃ concentration, and substantially affected NH₄NO₃ concentration. Higher dry deposition velocities of HNO₃ and NH₃ led to substantial reductions of concentrations of the gaseous species and NH₄NO₃. Because uncertainties in NH₃ emission and dry deposition processes are probably large, these processes may be key factors for improvement of the model performance for PM_2.5 NO₃^?.

Implications: The Community Multiscale Air Quality modeling system clearly overestimated the concentration of fine particulate nitrate in the Greater Tokyo Area of Japan, which was attributed to overestimation of production of ammonium nitrate. Sensitivity analyses were conducted for factors associated with the model performance for nitrate. Ammonia emission and dry deposition of nitric acid and ammonia may be key factors for improvement of the model performance.     

The characterization of water-soluble inorganic ions in PM2.5 during a winter period in Xi'an,China

The characteristics of water-soluble inorganic ions (WSIIs) during a winter period in a suburb of Xi'an, China, were investigated. Our results show that the total mass concentration of the dominant WSIIs (8) was 91.27 µg m^–3, accounting for 50.1% of the total mass concentration of PM_2.5 (particulates with a size of 2.5 µm or less). Secondary inorganic aerosols (SO₄^2?, NO₃^? and NH₄⁺) were the most abundant ions, accounting for up to 95.12% of the total ions. By using the anion and cation equivalence ratio method, PM_2.5 was shown to have weak alkalinity, and the chemical forms of WSIIs were mainly (NH₄)₂SO₄ and NH₄NO₃. The sulfur oxidation ratio (SOR) and nitrogen oxidation ratio (NOR) suggested that larger proportions of SO₄^2? and NO₃^? were formed by gas-phase SO₂ and NO₂ in the sampling site. Ratio analysis also indicated that anthropogenic sources significantly contributed to WSII pollution. Among the anthropogenic sources, fixed pollution sources were found to be dominant over mobile sources.     

Characterization of Major Chemical Components of Fine Particulate Matter in North Carolina

Abstract

This paper presents measurements of daily sampling of fine particulate matter (PM_2.5) and its major chemical components at three urban and one rural locations in North Carolina during 2002. At both urban and rural sites, the major insoluble component of PM_2.5 is organic matter, and the major soluble components are sulfate (SO₄ ^2?), ammonium (NH₄ ⁺), and nitrate (NO₃ ^?). NH₄ ⁺ is neutralized mainly by SO₄ ^2? rather than by NO₃ ^?, except in winter when SO₄ ^2? concentration is relatively low, whereas NO₃ ^? concentration is high. The equivalent ratio of NH₄ ⁺ to the sum of SO₄ ^2? and NO₃ ^? is <1, suggesting that SO₄ ^2?and NO₃ ^?are not completely neutralized by NH₄ ⁺. At both rural and urban sites, SO₄ ^2?concentration displays a maximum in summer and a minimum in winter, whereas NO₃ ^?displays an opposite seasonal trend. Mass ratio of NO₃ ^? to SO₄ ^2?is consistently <1 at all sites, suggesting that stationary source emissions may play an important role in PM_2.5 formation in those areas. Organic carbon and elemental carbon are well correlated at three urban sites although they are poorly correlated at the agriculture site. Other than the daily samples, hourly samples were measured at one urban site. PM_2.5 mass concen trations display a peak in early morning, and a second peak in late afternoon. Back trajectory analysis shows that air masses with lower PM_2.5 mass content mainly originate from the marine environment or from a continental environment but with a strong subsidence from the upper troposphere. Air masses with high PM_2.5 mass concentrations are largely from continental sources. Our study of fine particulate matter and its chemical composition in North Carolina provides crucial information that may be used to determine the efficacy of the new National Ambient Air Quality Standard (NAAQS) for PM fine. Moreover, the gas-to-particle conversion processes provide improved prediction of long-range transport of pollutants and air quality.     

Characterization of PM10 atmospheric aerosol at urban and urban background sites in Fuzhou city, China

Background

PM₁₀ aerosol samples were simultaneously collected at two urban and one urban background sites in Fuzhou city during two sampling campaigns in summer and winter. PM₁₀ mass concentrations and chemical compositions were determined.

Methods

Water-soluble inorganic ions (Cl^?, NO ₃ ^? , SO ₄ ^2? , NH ₄ ⁺ , K⁺, Na⁺, Ca²⁺, and Mg²⁺), carbonaceous species (elemental carbon and organic carbon), and elements (Al, Si, Mg, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Br, and Pb) were detected using ion chromatography, thermal/optical reflectance, and proton-induced X-ray emission methods, respectively.

Results

PM₁₀ mass concentrations, as well as most of the chemical components, were significantly increased from urban background to urban sites, which were due to enhanced anthropogenic activities in urban areas. Elements, carbonaceous species, and most of the ions were more uniformly distributed at different types of sites in winter, whereas secondary ion SO ₄ ^2? , NO ₃ ^? , and NH ₄ ⁺ showed more evident urban-background contrast in this season. The chemical mass closure indicated that mineral dust, organic matters, and sulfate were the most abundant components in PM₁₀. The sum of individually measured components accounted for 86.9?C97.7% of the total measured PM₁₀ concentration, and the discrepancy was larger in urban area than in urban background area.

Conclusion

According to the principal component analysis?Cmultivariate linear regression model, mineral dust, secondary inorganic ions, sea salt, and motor vehicle were mainly responsible for the PM₁₀ particles in Fuzhou atmosphere, and contributed 19.9%, 53.3%, 21.3%, and 5.5% of PM₁₀, respectively.     

Assessing the Relationship between Personal Particulate and Gaseous Exposures of Senior Citizens Living in Baltimore,MD

ABSTRACT

We conducted a multi-pollutant exposure study in Baltimore, MD, in which 15 non-smoking older adult subjects (>64 years old) wore a multi-pollutant sampler for 12 days during the summer of 1998 and the winter of 1999. The sampler measured simultaneous 24-hr integrated personal exposures to PM₂₅, PM₁₀, SO₄ ^2-, O₃, NO₂, SO₂, and exhaust-related VOCs.

Results of this study showed that longitudinal associations between ambient PM_2.5 concentrations and corresponding personal exposures tended to be high in the summer (median Spearman's r = 0.74) and low in the winter (median Spearman's r = 0.25). Indoor ventilation was an important determinant of personal PM_2.5 exposures and resulting personal-ambient associations. Associations between personal PM₂₅ exposures and corresponding ambient concentrations were strongest for well-ventilated indoor environments and decreased with ventilation. This decrease was attributed to the increasing influence of indoor PM_{2 5} sources. Evidence for this was provided by SO₄ ^2-measurements, which can be thought of as a tracer for ambient PM₂₅. For SO₄ ^2-, personal-ambient associations were strong even in poorly ventilated indoor environments, suggesting that personal exposures to PM_2.5 of ambient origin are strongly associated with corresponding ambient concentrations. The results also indicated that the contribution of indoor PM_2.5 sources to personal PM_2.5 exposures was lowest when individuals spent the majority of their time in well-ventilated indoor environments.

Results also indicate that the potential for confounding by PM_2.5 co-pollutants is limited, despite significant correlations among ambient pollutant concentrations. In contrast to ambient concentrations, PM_2.5 exposures were not significantly correlated with personal exposures to PM_2.5-10, PM_2.5 of non-ambient origin, O₃, NO₂, and SO₂. Since a confounder must be associated with the exposure of interest, these results provide evidence that the effects observed in the PM_2.5 epidemiologic studies are unlikely to be due to confounding by the PM_2.5 co-pollutants measured in this study.     

Ambient suspended particulate matters and related chemical species study in central Taiwan,Taichung during 1998–2001

Ambient suspended particulate (PM_2.5, PM_2.5–10, TSP) was collected from June 1998 to February 2001 in Taichung, central Taiwan. In addition, the related water-soluble ionic species (Cl⁻, NO₃⁻, SO₄²⁻, Na⁺, NH₄⁺, K⁺, Mg²⁺, Ca²⁺) and metallic species (Fe, Zn, Pb, Ni) were also analyzed in this study. The results showed that the concentrations of particulate mass are higher in the traffic site (CCRT) than the other sampling sites in this study. Also, the fine particle (PM_2.5) concentration is the dominant species of the total suspended particles in Taichung, central Taiwan. The dominant species for PM_2.5 are sulfate and ammonium at all sampling sites during the period of 1998–2001. The results of diurnal variation at THUC sampling site are also discussed in this study. Overall, acidic and secondary aerosol (Cl⁻, NO₃⁻, SO₄²⁻ and NH₄⁺) is a more serious air pollutant issue in southern and central Taiwan than at several sites around the world. Therefore, ambient suspended particulate monitoring in Taichung, central Taiwan will be continuing in our following study to provide more information for the government to formulate environmental strategy.     

The Aerosol Research and Inhalation Epidemiology Study (ARIES): PM25 Mass and Aerosol Component Concentrations and Sampler Intercomparisons

ABSTRACT

The Aerosol Research and Inhalation Epidemiology Study (ARIES) was designed to provide high-quality measurements of PM₂₅, its components, and co-varying pollutants for an air pollution epidemiology study in Atlanta, GA.

Air pollution epidemiology studies have typically relied on available data on particle mass often collected using filter-based methods. Filter-based PM_2.5 sampling is susceptible to both positive and negative errors in the measurement of aerosol mass and particle-phase component concentrations in the undisturbed atmosphere. These biases are introduced by collection of gas-phase aerosol components on the filter media or by volatilization of particle phase components from collected particles. As part of the ARIES, we collected daily 24-hr PM_2.5 mass and speciation samples and continuous PM_2.5 data at a mixed residential-light industrial site in Atlanta. These data facilitate analysis of the effects of a wide variety of factors on sampler performance. We assess the relative importance of PM_2.5 components and consider associations and potential mechanistic linkages of PM_2.5 mass concentrations with several PM_2.5 components.

For the 12 months of validated data collected to date (August 1, 1998-July 31, 1999), the monthly average Federal Reference Method (FRM) PM_{2 5} mass always exceeded the proposed annual average standard (12-month average = 20.3 ± 9.5 ug/m³). The particulate SO₄ ^2- fraction (as (NH₄)₂SO₄) was largest in the summer and exceeded 50% of the FRM mass. The contribution of (NH₄)₂SO₄ to FRM PM_2.5 mass dropped to less than 30% in winter. Particu-late NO₃ ^- collected on a denuded nylon filter averaged 1.1 ± 0.9 ug/m³. Particle-phase organic compounds (as organic carbon × 1.4) measured on a denuded quartz filter sampler averaged 6.4 ± 3.1 ug/m³ (32% of FRM PM_{2 5} mass) with less seasonal variability than SO₄ ^2-.     

Source Identification and Trends in Concentrations of Gaseous and Fine Particulate Principal Species in Seoul,South Korea

Abstract

Ambient measurements were made using two sets of annular denuder system during the four seasons (April 2001 to February 2002) and were then compared with the results during the period of 1996–1997 to estimate the trends and seasonal variations in concentrations of gaseous and fine particulate matter (PM_2.5) principal species. Annual averages of gaseous HNO₃ and NH₃ increased by 11% and 6%, respectively, compared with those of the previous study, whereas HONO and SO₂ decreased by 11% and 136%, respectively. The PM_2.5 concentration decreased by ～17%, 35% for SO₄ ^2?, and 29% for NH₄ ⁺, whereas NO₃ ^? increased by 21%. Organic carbon (OC) and elemental carbon (EC) were 12.8 and 5.98 μg/m^-3, accounting for ～26 and 12% of PM_2.5 concentration, respectively. The species studied accounted for 84% of PM_2.5 concentration, ranging from 76% in winter to 97% in summer.

Potential source contribution function (PSCF) analysis was used to identify possible source areas affecting air pollution levels at a receptor site in Seoul. High possible source areas in concentrations of PM_2.5, NO₃ ^?, SO₄ ^2?, NH₄ ⁺, and K⁺ were coastal cities of Liaoning province (possibly emissions from oil-fired boilers on ocean liners and fishing vessels and industrial emissions), inland areas of Heibei/Shandong provinces (the highest density areas of agricultural production and population) in China, and typical port cities (Mokpo, Yeosu, and Busan) of South Korea. In the PSCF map for OC, high possible source areas were also coastal cities of Liaoning province and inland areas of Heibei/Shandong provinces in China. In contrast, high possible source areas of EC were highlighted in the south of the Yellow Sea, indicating possible emissions from oil-fired boilers on large ships between South Korea and Southeast Asia. In summary, the PSCF results may suggest that air pollution levels in Seoul are affected considerably by long-range transport from external areas, such as the coastal zone in China and other cities in South Korea, as well as Seoul itself.     

Influence of sulfur dioxide-related interactions on PM2.5 formation in iron ore sintering

The formation of PM_2.5 (aerosol particulate matter less than 2.5 µm in aerodynamic diameter) in association with SO₂ emission during sintering process has been studied by dividing the whole sintering process into six typical sampling stages. A low-pressure cascade impactor was used to collect PM_2.5 by automatically segregating particulates into six sizes. It was found that strong correlation existed between the emission properties of PM_2.5 and SO₂. Wet mixture layer (overwetted layer and raw mixture layer) had the function to simultaneously capture SO₂ and PM_2.5 during the early sintering stages, and released them back into flue gas mainly in the flue gas temperature-rising period. CaSO₄ crystals constituted the main SO₂-related PM_2.5 during the disappearing process of overwetted layer, which was able to form perfect individual crystals or to form particles with complex chemical compositions. Besides the existence of individual CaSO₄ crystals, mixed crystals of K₂SO₄-CaSO₄ in PM_2.5 were also found during the first half of the temperature-rising period of flue gas. The interaction between fine-grained Ca-based fluxes, potassium vapors, and SO₂ was the potential source of SO₂-related PM_2.5.

Implications: The emission property of PM_2.5 and SO₂ throughout the sintering process exhibited well similarity. This phenomenon tightened the relationship between the formation of PM_2.5 and the emission of SO₂. Through revealing the properties of SO₂-related PM_2.5 during sintering process, the potential interaction between fine-grained Ca-based fluxes, potassium vapors, and SO₂ was found to be the source of SO₂-related PM_2.5. This information can serve as the guidance to develop efficient techniques to control the formation and emission of PM_2.5 in practical sintering plants.     

Particulate matter emissions from on-road vehicles in a freeway tunnel study

Particulate matter, including coarse particles (PM_2.5–10, aerodynamic diameter of particle between 2.5 and 10 μm) and fine particles (PM_2.5, aerodynamic diameter of particle lower than 2.5 μm) and their compositions, including elemental carbon, organic carbon, and 11 water-soluble ionic species, and elements, were measured in a tunnel study. A comparison of the six-hour average of light-duty vehicle (LDV) flow of the two sampling periods showed that the peak hours over the weekend were higher than those on weekdays. However, the flow of heavy-duty vehicles (HDVs) on the weekdays was significant higher than that during the weekend in this study. EC and OC content were 49% for PM_2.5–10 and 47% for PM_2.5 in the tunnel center. EC content was higher than OC content in PM_2.5–10, but EC was about 2.3 times OC for PM_2.5. Sulfate, nitrate, ammonium were the main species for PM_2.5–10 and PM_2.5. The element contents of Na, Al, Ca, Fe and K were over 0.8 μg m^?3 in PM_2.5–10 and PM_2.5. In addition, the concentrations of S, Ba, Pb, and Zn were higher than 0.1 μg m^?3 for PM_2.5–10 and PM_2.5. The emission factors of PM_2.5–10 and PM_2.5 were 18 ± 6.5 and 39 ± 11 mg km^?1-vehicle, respectively. The emission factors of EC/OC were 3.6/2.7 mg km^?1-vehicle for PM_2.5–10 and 15/4.7 mg km^?1-vehicle for PM_2.5 Furthermore, the emission factors of water-soluble ions were 0.028(Mg²⁺)–0.81(SO₄^2?) and 0.027(NO₂^?)–0.97(SO₄^2?) mg km^?1-vehicle for PM_2.5–10 and PM_2.5, respectively. Elemental emission factors were 0.003(V)–1.6(Fe) and 0.001(Cd)–1.05(Na) mg km^?1-vehicle for PM_2.5–10 and PM_2.5, respectively.     

PM2.5 particles and size-segregated ionic species measured during fall season in three urban sites in Korea

Twelve hours integrated fine particles (PM_2.5) and 24-h average size-segregated particles were collected to investigate the chemical characteristics and to determine the size distribution of ionic species during October–December 1999 in three cities of different urban scale; Chongju, Kwangju, and Seoul, Korea. Concentrations of 5-min PM_2.5 black carbon (BC) and hourly criteria air pollutants (PM₁₀, CO, NO_x, SO₂, and O₃) were also measured using the Aethalometer and ambient air monitoring system, respectively.Highest PM_2.5 mass concentrations at Chongju, Kwangju, and Seoul sites were 63.0, 77.9, and 143.7 μg m⁻³, respectively. For the time period when highest PM_2.5 mass occurred, BC level out of PM_2.5 chemical species was highest at both Chongju and Kwangju, and highest NO₃⁻ (23.6 μg m⁻³) followed by BC (23.1 μg m⁻³) were observed at Seoul site, indicating that highest PM_2.5 pollution is closely associated with the traffic emissions. Strong relationships of Fe with BC and Zn at both Kwangju and Seoul sites support that the Fe and Zn measured there are originated partly from same source as BC, i.e. diesel traffics. However, it is suggested that the Fe measured at Chongju is most likely derived from dispersion of soil dust.The size distributions of SO₄²⁻, NO₃⁻, and NH₄⁺ ionic species indicated similar unimodal distributions at all sampling sites. However, different unimodal patterns in the accumulation mode size range with a peak in the smaller size (0.28–0.53 μm, condensation mode) in both Kwangju and Seoul, and in the relatively larger size (0.53–1.0 μm, droplet mode) in Chongju, were found. The potassium ion under the study sites dominates in the fine mode, and its size distribution showed unimodal character with a maximum in the size range 0.56–1.0 μm.     

NH4+, NO3−, and SO42− in roadside and rural size-resolved particles and transformation of NO2/SO2 to nanoparticle-bound NO3−/SO42−

This study investigates ammonium, nitrate, and sulfate (NH₄⁺, NO₃^?, and SO₄^2?) in size-resolved particles (particularly nano (PM_0.01–0.056)/ultrafine (PM_0.01–0.1)) and NO_x/SO₂ collected near a busy road and at a rural site. The average (mass) cumulative fraction of secondary inorganic aerosols (SO₄^2?+NO₃^?+NH₄⁺) in nano or ultrafine particles at the roadside was found to be three to four times that at the rural site. The above three secondary inorganic aerosol species were present in similar cumulative fractions in particles of size 1–18 μm at both sites; however, dissimilar fractions were observed for Cl^?, Na⁺, and K⁺. The nitrogen ratios (NRs: NR = NO₃^??N/(NO₃^??N + NO₂–N)), sulfur ratios (SRs: SR = SO₄^2??S/(SO₄^2??S + SO₂–S)), dNR/D_P (derivative of NR with respect to D_P (particle diameter)), and dSR/D_P (derivative of SR with respect to D_P) at the roadside were higher than those at the rural site for nano/ultrafine particles. At both sites (particularly the roadside), the nanoparticles had significantly higher dNR/D_P and dSR/D_P values than differently sized particles, implying that NO₃^?/SO₄^2? (from NO₂/SO₂ transformation or NO₃^?/SO₄^2? deposition) were present on these particles.     

Characterization of the major chemical species in PM2.5 in the Kaohsiung City,Taiwan

The concentrations and characteristics of the major components in ambient fine particles in the urban city of Kaohsiung, Taiwan were measured and evaluated. PM_2.5 samples were collected using a dichotomous sampler from November 1998 to April 1999 and analyzed for water-soluble ion species using ion chromatography and for carbonaceous species using an elemental analyzer. It was found that SO₄²⁻, NO₃⁻, and NH₄⁺ dominated the identifiable components, and occupied 42.2% and 90.0% of PM_2.5 mass and total dissolved ionic concentrations. Carbonaceous species (organic and elemental carbon) accounted for 20.8% of PM_2.5. The secondary aerosol formed through the NO₂/SO₂ gas-to-particle conversion was estimated based on the sulfur/nitrogen oxidation ratio (SOR/NOR), i.e., sulfate sulfur/nitrate nitrogen to total sulfur/total nitrogen. The average SOR and NOR values were 0.25 and 0.07 for PM_2.5. The high SOR and NOR values obtained in this study suggested that there existed a secondary formation of SO₄²⁻ from SO₂ along with NO₃⁻ from NO₂ in the atmosphere. The secondary organic carbon formed through the volatile organic compound gas-to-particle conversion was estimated from the minimum ratio between organic and elemental carbon obtained in this study, and was found to constitute 40.0% of the total organic carbon for PM_2.5 (6.6% of the particle mass). The results obtained in this study suggest that the formation of secondary aerosols due to conversion from gaseous precursors is significant and important in urban locations.     

The use of real-time monitoring data to evaluate major sources of airborne particulate matter

Real-time chemical measurements have been made as part of a field study of air quality in the city and harbour of Cork, Ireland. The data relate to the year 2008, with particular attention paid to the period between May and August. Eight air quality parameters were measured: NO, O₃, NO₂, SO₂, EC, OC, particulate SO₄^2? and PM_2.5. The data have been used in a novel way involving wind and temporal averaging, along with Principal Component Analysis (PCA) and Positive Matrix Factorisation (PMF) methodologies to extrapolate major source contributions for PM_2.5. It is demonstrated that continuous monitoring of standard air quality parameters, such as NO, NO₂, SO₂, along with EC, OC and particulate SO₄^2?, can be used to provide relevant, cost-effective initial estimates of source contributions to ambient PM_2.5 levels. It is also shown that the benefit of including OC and particulate SO₄^2? in the monitoring protocol is considerable. Three major source groups of ambient PM_2.5 mass in Cork were identified and quantified using this combined monitoring and modelling approach; road transport (19%), domestic solid fuel burning (14%) and oil-fired domestic and industrial boilers, including power generation plants (31%).     

Evaluation of the community multiscale air quality (CMAQ) model version 4.5: Sensitivities impacting model performance; Part II—particulate matter

This paper is Part II in a pair of papers that examines the results of the Community Multiscale Air Quality (CMAQ) model version 4.5 (v4.5) and discusses the potential explanations for the model performance characteristics seen. The focus of this paper is on fine particulate matter (PM_2.5) and its chemical composition. Improvements made to the dry deposition velocity and cloud treatment in CMAQ v4.5 addressing compensating errors in 36-km simulations improved particulate sulfate (SO₄²⁻) predictions. Large overpredictions of particulate nitrate (NO₃⁻) and ammonium (NH₄⁺) in the fall are likely due to a gross overestimation of seasonal ammonia (NH₃) emissions. Carbonaceous aerosol concentrations are substantially underpredicted during the late spring and summer months, most likely due, in part, to a lack of some secondary organic aerosol (SOA) formation pathways in the model. Comparisons of CMAQ PM_2.5 predictions with observed PM_2.5 mass show mixed seasonal performance. Spring and summer show the best overall performance, while performance in the winter and fall is relatively poor, with significant overpredictions of total PM_2.5 mass in those seasons. The model biases in PM_2.5 mass cannot be explained by summing the model biases for the major inorganic ions plus carbon. Errors in the prediction of other unspeciated PM_2.5 (PM_Other) are largely to blame for the errors in total PM_2.5 mass predictions, and efforts are underway to identify the cause of these errors.