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.     

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.     

Simulation of aerosols and gas-phase species over Europe with the Polyphemus system. Part II: Model sensitivity analysis for 2001

This paper presents a multi-pollutant sensitivity study of an air quality model over Europe with a focus on aerosols. Following the evaluation presented in the companion paper, the aim here is to study the sensitivity of the model to input data, mathematical parameterizations and numerical approximations. To that end, 30 configurations are derived from a reference configuration of the model by changing one input data set, one parameterization or one numerical approximation at a time. Each of these configurations is compared to the same reference simulation over two time periods of the year 2001, one in summer and one in winter. The sensitivity of the model to the different configurations is evaluated through a statistical comparison between the simulation results and through comparisons to available measurements. The species studied are ozone (O₃), nitrogen dioxide (NO₂), sulfur dioxide (SO₂), ammonia (NH₃), coarse and fine aerosol particles (PM_c and PM_2.5), sulfate, nitrate, ammonium, chloride and sodium.For all species, the modeled concentrations are very sensitive to the parameterization used for vertical turbulent diffusion and to the number of vertical levels. For the other configurations considered in this work, the sensitivity of the modeled concentration to configuration choice varies with the species and the period of the year. O₃ is impacted by options related to boundary conditions. PM_c is sensitive to sea-salt related options, to options influencing deposition and to options related to mass transfer between gas and particulate phases. PM_2.5 is sensitive to a larger number of options than PM_c: sea-salt, boundary conditions, heterogeneous reactions, aqueous chemistry and gas/particle mass transfer. NO₂ is strongly influenced by heterogeneous reactions. Nitrate shows the highest variability of all species studied. As with NO₂, nitrate is strongly sensitive to heterogeneous reactions but also to mass transfer, thermodynamic related options, aqueous chemistry and computation of the wet particle diameter. While SO₂ is mostly sensitive to aqueous chemistry, sulfate is also sensitive to boundary conditions and, to a lesser extent, to heterogeneous reactions. As with nitrate, ammonium is largely impacted by the different configuration choices, although the sensitivity is slightly lower than for nitrate. NH₃ is sensitive to aqueous chemistry, mass transfer and heterogeneous reactions. Chloride and sodium are impacted by sea-salt related options, by options influencing deposition and by options concerning the aqueous-phase module.     

Response of Fine Particulate Matter to Emission Changes of Oxides of Nitrogen and Anthropogenic Volatile Organic Compounds in the Eastern United States

Abstract

A three-dimensional chemical transport model (Particulate Matter Comprehensive Air Quality Model with Extensions [PMCAMx]) is used to investigate changes in fine particle (PM_2.5) concentrations in response to 50% emissions changes of oxides of nitrogen (NO_x) and anthropogenic volatile organic compounds (VOCs) during July 2001 and January 2002 in the eastern United States. The reduction of NO_x emissions by 50% during the summer results in lower average oxidant levels and lowers PM_2.5 (8% on average), mainly because of reductions of sulfate (9–11%), nitrate (45–58%), and ammonium (7–11%). The organic particulate matter (PM) slightly decreases in rural areas, whereas it increases in cities by a few percent when NO_x is reduced. Reduction of NO_x during winter causes an increase of the oxidant levels and a rather complicated response of the PM components, leading to small net changes. Sulfate increases (8–17%), nitrate decreases (18– 42%), organic PM slightly increases, and ammonium either increases or decreases a little. The reduction of VOC emissions during the summer causes on average a small increase of the oxidant levels and a marginal increase in PM_2.5. This small net change is due to increases in the inorganic components and decreases of the organic ones. Reduction of VOC emissions during winter results in a decrease of the oxidant levels and a 5–10% reduction of PM_2.5 because of reductions in nitrate (4–19%), ammonium (4–10%), organic PM (12–14%), and small reductions in sulfate. Although sulfur dioxide (SO₂) reduction is the single most effective approach for sulfate control, the coupled decrease of SO₂ and NO_x emissions in both seasons is more effective in reducing total PM_2.5 mass than the SO₂ reduction alone.     

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.     

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.     

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%.     

The Southeastern Aerosol Research and Characterization Study,Part 3: Continuous Measurements of Fine Particulate Matter Mass and Composition

Abstract

Deployment of continuous analyzers in the Southeastern Aerosol Research and Characterization Study (SEARCH) network began in 1998 and continues today as new technologies are developed. Measurement of fine particulate matter (PM_2.5) mass is performed using a dried, 30 °C tapered element oscillating microbalance (TEOM). TEOM measurements are complemented by observations of light scattering by nephelometry. Measurements of major constituents include: (1) SO₄ ^2? via reduction to SO₂; (2) NH₄ ⁺ and NO₃ ^? via respective catalytic oxidation and reduction to NO, (3) black carbon (BC) by optical absorption, (4) total carbon by combustion to CO₂, and (5) organic carbon by difference between the latter two measurements. Several illustrative examples of continuous data from the SEARCH network are presented. A distinctive composite annual average diurnal pattern is observed for PM_2.5 mass, nitrate, and BC, likely indicating the influence of traffic-related emissions, growth, and break up of the boundary layer and formation of ammonium nitrate. Examination of PM_2.5 components indicates the need to better understand the continuous composition of the unmeasured “other” category, because it contributes a significant fraction to total mass during periods of high PM_2.5 loading. Selected episodes are presented to illustrate applications of SEARCH data. An SO₂ conversion rate of 0.2%/hr is derived from an observation of a plume from a coal-fired power plant during early spring, and the importance of local, rural sources of NH₃ to the formation of ammonium nitrate in particulate matter (PM) is demonstrated.     

Effect of PM2.5 chemical constituents on atmospheric visibility impairment

PM_2.5 sampling was conducted at a curbside location in Delhi city for summer and winter seasons, to evaluate the effect of PM_2.5 and its chemical components on the visibility impairment. The PM_2.5 concentrations were observed to be higher than the National Ambient Air Quality Standards (NAAQS), indicating poor air quality. The chemical constituents of PM_2.5 (the water-soluble ionic species SO₄^2-, NO₃^?, Cl^?, and NH₄⁺, and carbonaceous species: organic carbon, elemental carbon) were analyzed to study their impact on visibility impairment by reconstructing the light extinction coefficient, b_ext. The visibility was found to be negatively correlated with PM_2.5 and its components. The reconstructed b_ext showed that organic matter was the largest contributor to b_ext in both the seasons which may be attributed to combustion sources. In summer season, it was followed by elemental carbon and ammonium sulfate; however, in winter, major contributions were from ammonium nitrate and elemental carbon. Higher elemental carbon in both seasons may be attributed to traffic sources, while lower concentrations of nitrate during summer, may be attributed to volatility because of higher atmospheric temperatures.

Implications: The chemical constituents of PM_2.5 that majorly effect the visibility impairment are organic matter and elemental carbon, both of which are products of combustion processes. Secondary formations that lead to ammonium sulfate and ammonium nitrate production also impair the visibility.     

Determination of sources of fine particles in different ambient atmospheres in South Korea using a chemical mass balance model

Abstract

To determine the sources of particulate matter less than 2.5?μm (PM_2.5 in different ambient atmospheres (urban, roadside, industrial, and rural sites), the chemical components of PM_2.5 such as ions (Cl^-, NO₃^-, SO₄^2-, NH₄⁺, Na⁺, K⁺, Ca²⁺, and Mg²⁺), carbonaceous species, and elements (Al, As, Ba, Cd, Cu, Fe, Mn, Ni, Pb, Se, V, and Zn) were measured. The average mass concentrations of PM_2.5 at the urban, roadside, industrial, and rural sites were 31.5?±?14.8, 31.6?±?22.3, 31.4?±?16.0, and 25.8?±?12.4?μg/m³, respectively. Except for secondary ammonium sulfate and ammonium nitrate, the model results showed that the traffic source (i.e., the sum of gasoline and diesel vehicle sources) was the most dominant source of PM_2.5 (17.1%) followed by biomass burning (13.8%) at the urban site. The major primary sources of PM_2.5 were consistent with the site characteristics (diesel vehicle source at the roadside site, coal-fired plants at the industrial site, and biomass burning at the rural site). Seasonal data from the urban site suggested that ammonium sulfate and ammonium nitrate were the most dominant sources of PM_2.5 during all seasons. Further, the contribution of road dust source to PM_2.5 increased during spring and fall seasons. We conclude that the determination of the major PM_2.5 sources is useful for establishing efficient control strategies for PM_2.5 in different regions and seasons.     

Source apportionment of PM2.5 for supporting control strategies in the Monterrey Metropolitan Area,Mexico

The Monterrey Metropolitan Area (MMA) in Northeast Mexico has shown high PM_2.5 concentrations since 2003. The data shows that the annual average concentration exceeds from 2 to 3 times the Mexican PM_2.5 annual air quality standard of 12 µg/m³. In a previous work we studied the chemical characterization of PM_2.5 in two sites of the MMA during the winter season. Among the most important components we found ammonium sulfate and nitrate, elemental and organic carbon, and crustal matter. In this work we present the results of a second chemical characterization study performed during the summer time and the application of the chemical mass balance (CMB) model to determine the source apportionment of air pollutants in the region. The chemical analysis results show that the chemical composition of PM_2.5 is similar in both sites and periods of the year. The results of the chemical analysis and the CMB model show that industrial, traffic, and combustion activities in the area are the major sources of primary PM_2.5 and precursor gases of secondary inorganic and organic aerosol (SO₂, NOx, NH₃, and volatile organic compounds [VOCs]). We also found that black carbon and organic carbon are important components of PM_2.5 in the MMA. These results are consistent with the MMA emission inventory that reports as major sources of particles and SO₂ a refinery and fuel combustion, as well as nitrogen oxides and ammonium from transportation and industrial activities in the MMA and ammonium form agricultural activities in the state. The results of this work are important to identify and support effective actions to reduce direct emissions of PM_2.5 and its precursor gases to improve air quality in the MMA. Implications: The Monterrey Metropolitan Area (MMA) has been classified as the most air-polluted area in Mexico by the World Health Organization (WHO). Effective actions need to be taken to control primary sources of PM_2.5 and its precursors, reducing health risks on the population exposed and their associated costs. The results of this study identify the main sources and their estimated contribution to PM_2.5 mass concentration, providing valuable information to the local environmental authorities to take decisions on PM_2.5 control strategies in the MMA.     

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.     

Photochemical model performance for PM2.5 sulfate,nitrate, ammonium,and precursor species SO2, HNO3, and NH3 at background monitor locations in the central and eastern United States

Health studies have shown premature death is statistically associated with exposure to particulate matter <2.5 μm in diameter (PM2.5). The United States Environmental Protection Agency requires all States with PM2.5 non-attainment counties or with sources contributing to visibility impairment at Class I areas to submit an emissions control plan. These emission control plans will likely focus on reducing emissions of sulfur oxides and nitrogen oxides, which form two of the largest chemical components of PM2.5 in the eastern United States: ammonium sulfate and ammonium nitrate. Emission control strategies are simulated using three-dimensional Eulerian photochemical transport models.A monitor study was established using one urban (Detroit) and nine rural locations in the central and eastern United States to simultaneously measure PM2.5 sulfate ion (SO₄²⁻), nitrate ion (NO₃⁻), ammonium ion (NH₄⁺), and precursor species sulfur dioxide (SO₂), nitric acid (HNO₃), and ammonia (NH₃). This monitor study provides a unique opportunity to assess how well the modeling system predicts the spatial and temporal variability of important precursor species and co-located PM2.5 ions, which is not well characterized in the central and eastern United States.The modeling system performs well at estimating the PM2.5 species, but does not perform quite as well for the precursor species. Ammonia is under-predicted in the coldest months, nitric acid tends to be over-predicted in the summer months, and sulfur dioxide appears to be systematically over-predicted. Several indicators of PM2.5 ammonium sulfate and ammonium nitrate formation and chemical composition are estimated with the ambient data and photochemical model output. PM2.5 sulfate ion is usually not fully neutralized to ammonium sulfate in ambient measurements and is usually fully neutralized in model estimates. The model and ambient estimates agree that the ammonia study monitors tend to be nitric acid limited for PM2.5 nitrate formation. Regulatory strategies in this part of the country should focus on reductions in NO_X rather than ammonia to control PM2.5 ammonium nitrate.     

Fine particle measurements at two background sites in Korea between 1996 and 1997

Five intensive field measurements were carried out at two background sites in Korea; Kosan and Kangwha during spring, fall, and winters of 1996 and 1997 to investigate the characteristics of long-range transport of air pollutants in northeastern Asia. Fine particles (PM_2.5) were collected by low-volume samplers and the concentrations of major ions, organic and elemental carbons, and nitric acid were quantified. The concentrations of anthropogenic species in PM_2.5 measured at both sites were generally higher than those at other background areas, Nagano, Japan and San Nicolas Is., USA due to continental outflow of air pollutants, but lower than those at an urban background site, Qingdao, China. The major components of PM_2.5 were sulfate, organic carbon (OC), and ammonium for Kosan and sulfate, OC, ammonium, and nitrate for Kangwha. The major fractions of sulfate at both sites are non-sea-salts (nss) sulfate. Based on the relationship among major anthropogenic species, analysis of the nss sulfate to total nitrate molar ratios, and backward air parcel trajectories, it was found that fine particles measured at both sites during the measurement periods are mainly coming from China. At Kosan, the concentrations of anthropogenic species were higher when air parcels were coming from southern China than when air parcels were from northern China. At Kangwha, however, the differences of the concentrations were not statistically significant since most air parcels were from northern China and local effects are prominent.     

The air pollution caused by the burning of fireworks during the lantern festival in Beijing

The effects of the burning of fireworks on air quality in Beijing was firstly assessed from the ambient concentrations of various air pollutants (SO₂, NO₂, PM_2.5, PM₁₀ and chemical components in the particles) during the lantern festival in 2006. Eighteen ions, 20 elements, and black carbon were measured in PM_2.5 and PM₁₀, and the levels of organic carbon could be well estimated from the concentrations of dicarboxylic acids. Primary components of Ba, K, Sr, Cl⁻, Pb, Mg and secondary components of C₅H₆O₄²⁻, C₃H₂O₄²⁻, C₂O₄²⁻, C₄H₄O₄²⁻, SO₄²⁻, NO₃⁻ were over five times higher in the lantern days than in the normal days. The firework particles were acidic and of inorganic matter mostly with less amounts of secondary components. Primary aerosols from the burning of fireworks were mainly in the fine mode, while secondary formation of acidic anions mainly took place on the coarse particles. Nitrate was mainly formed through homogeneous gas-phase reactions of NO₂, while sulfate was largely from heterogeneous catalytic transformations of SO₂. Fe could catalyze the formation of nitrate through the reaction of α-Fe₂O₃ with HNO₃, while in the formation of sulfate, Fe is not only the catalyst, but also the oxidant. A simple method using the concentration of potassium and a modified method using the ratio of Mg/Al have been developed to quantify the source contribution of fireworks. It was found that over 90% of the total mineral aerosol and 98% of Pb, 43% of total carbon, 28% of Zn, 8% of NO₃⁻, and 3% of SO₄²⁻ in PM_2.5 were from the emissions of fireworks on the lantern night.     

Loss of PM2.5 Nitrate from Filter Samples in Central California

Abstract

Evaporative loss of particulate matter (with aerodynamic diameter <2.5 μm, [PM_2.5]) ammonium nitrate from quartz-fiber filters during aerosol sampling was evaluated from December 3, 1999, through February 3, 2001, at two urban (Fresno and Bakersfield) and three nonurban (Bethel Island, Sierra Nevada Foothills, and Angiola) sites in central California. Compared with total particulate nitrate, evaporative nitrate losses ranged from <10% during cold months to >80% during warm months. In agreement with theory, evaporative loss from quartz-fiber filters in nitric acid denuded samplers is controlled by the ambient nitric acid-to-particulate nitrate ratio, which is determined mainly by ambient temperature. Accurate estimation of nitrate volatilization requires a detailed thermodynamic model and comprehensive chemical measurements. For the 14-month average of PM_2.5 acquired on Teflon-membrane filters, measured PM_2.5 mass was 8–16% lower than actual PM_2.5 mass owing to nitrate volatilization. For 24-hr samples, measured PM_2.5 was as much as 32–44% lower than actual PM_2.5 at three California Central Valley locations.     

Composition and secondary formation of fine particulate matter in the Salt Lake Valley: Winter 2009

Under the National Ambient Air Quality Standards (NAAQS), put in place as a result of the Clean Air Amendments of 1990, three regions in the state of Utah are in violation of the NAAQS for PM₁₀ and PM_2.5 (Salt Lake County, Ogden City, and Utah County). These regions are susceptible to strong inversions that can persist for days to weeks. This meteorology, coupled with the metropolitan nature of these regions, contributes to its violation of the NAAQS for PM during the winter. During January–February 2009, 1-hr averaged concentrations of PM_10-2.5, PM_2.5, NO_x, NO₂, NO, O₃, CO, and NH₃ were measured. Particulate-phase nitrate, nitrite, and sulfate and gas-phase HONO, HNO₃, and SO₂ were also measured on a 1-hr average basis. The results indicate that ammonium nitrate averages 40% of the total PM_2.5 mass in the absence of inversions and up to 69% during strong inversions. Also, the formation of ammonium nitrate is nitric acid limited. Overall, the lower boundary layer in the Salt Lake Valley appears to be oxidant and volatile organic carbon (VOC) limited with respect to ozone formation. The most effective way to reduce ammonium nitrate secondary particle formation during the inversions period is to reduce NO_x emissions. However, a decrease in NO_x will increase ozone concentrations. A better definition of the complete ozone isopleths would better inform this decision.

Implications: Monitoring of air pollution constituents in Salt Lake City, UT, during periods in which PM_2.5 concentrations exceeded the NAAQS, reveals that secondary aerosol formation for this region is NO_x limited. Therefore, NO_x emissions should be targeted in order to reduce secondary particle formation and PM_2.5. Data also indicate that the highest concentrations of sulfur dioxide are associated with winds from the north-northwest, the location of several small refineries.     

Analysis of a Summertime PM2.5 and Haze Episode in the Mid-Atlantic Region

Abstract

Observations of the mass and chemical composition of particles less than 2.5 μm in aerodynamic diameter (PM_2.5), light extinction, and meteorology in the urban Baltimore-Washington corridor during July 1999 and July 2000 are presented and analyzed to study summertime haze formation in the mid-Atlantic region. The mass fraction of ammoniated sulfate (SO₄ ^2-) and carbonaceous material in PM_2.5 were each ～50% for cleaner air (PM_2.5 < 10 μg/m³) but changed to ～60% and ～20%, respectively, for more polluted air (PM_2.5 > 30 μg/m³). This signifies the role of SO₄ ^2- in haze formation. Comparisons of data from this study with the Interagency Monitoring of Protected Visual Environments network suggest that SO₄ ^2? is more regional than carbonaceous material and originates in part from upwind source regions. The light extinction coefficient is well correlated to PM_2.5 mass plus water associated with inorganic salt, leading to a mass extinction efficiency of 7.6 ± 1.7 m²/g for hydrated aerosol. The most serious haze episode occurring between July 15 and 19, 1999, was characterized by westerly transport and recirculation slowing removal of pollutants. At the peak of this episode, 1-hr PM_2.5 concentration reached ～45 μg/m³, visual range dropped to ～5 km, and aerosol water likely contributed to ～40% of the light extinction coefficient.     

Attainment Flip-Flops and the Achievability of the Ozone Air Quality Standard

Abstract

This paper presents the results of the first reported study on fine particulate matter (PM) chemical composition at Salamanca, a highly industrialized urban area of Central Mexico. Samples were collected at six sites within the urban area during February and March 2003. Several trace elements, organic carbon (OC), elemental carbon (EC), and six ions were analyzed to characterize aerosols. Average concentrations of PM with aerodynamic diameter of less than 10 μm (PM₁₀) and fine PM with aerodynamic diameter of less than 2.5 μm (PM_2.5) ranged from 32.2 to 76.6 μg m^-3 and 11.1 to 23.7 μg m^-3, respectively. OC (34%), SO₄ ⁼ (25.1%), EC (12.9%), and geological material (12.5%) were the major components of PM_2.5. For PM₁₀, geological material (57.9%), OC (17.3%), and SO₄ ⁼ (9.7%) were the major components. Coarse fraction (PM₁₀ –PM_2.5), geological material (81.7%), and OC (8.6%) were the dominant species, which amounted to 90.4%. Correlation analysis showed that sulfate in PM_2.5 was present as ammonium sulfate. Sulfate showed a significant spatial variation with higher concentrations to the north resulting from predominantly southwesterly winds above the surface layer and by major SO₂ sources that include a power plant and refinery. At the urban site of Cruz Roja it was observed that PM_2.5 mass concentrations were similar to the submicron fraction concentrations. Furthermore, the correlation between EC in PM_2.5 and EC measured from an aethalometer was r² = 0.710. Temporal variations of SO₂ and nitrogen oxide were observed during a day when the maximum concentration of PM_2.5 was measured, which was associated with emissions from the nearby refinery and power plant. From cascade impactor measurements, the three measured modes of airborne particles corresponded with diameters of 0.32, 1.8, and 5.6 μm.     

Chemical composition of the fine and coarse fraction of aerosols in the northeastern Mediterranean

Two-stage aerosol samples (PM_10–2.5 and PM_2.5) were collected at a coastal rural site located in the northeastern Mediterranean, between April 2001 and 2002. A total of 562 aerosol samples were analyzed for trace elements (Fe, Ti, Mn, Ca, V, Ni, Zn, Cr) and water-soluble ions (Na⁺, NH₄⁺, K⁺, Mg²⁺, Ca²⁺, Cl⁻, Br⁻, NO₃⁻, SO₄²⁻, C₂O₄²⁻ and MS⁻:methane sulfonate). PM₁₀, crustal elements, sea salt aerosols and NO₃⁻ were mainly associated with the coarse mode whereas non-sea salt (nss)SO₄²⁻, C₂O₄²⁻; MS⁻, NH₄⁺, Cr and Ni were found predominantly in the fine fraction. Concentrations of aerosol species exhibited orders of magnitude change from day to day and the aerosol chemical composition is heavily affected by dust events under the influence of airflow from North Africa. During the sampling period, 11 specific mineral dust events of duration varying from 1 day to a week have been identified and their influence on the chemical composition of aerosols has been studied in detail. Ionic balance analysis performed in the coarse and fine aerosol fractions indicated anion and cation deficiency due to CO₃²⁻ and H⁺, respectively. A relationship between nssSO₄²⁻ and NH₄⁺ denoted that sulfate particles were partially neutralized (70%) by ammonium. Excess-K/BC presented two distinct ratios for winter and summer, indicating two different sources: fossil fuel burning in winter and biomass burning in summer.