Regional Transport and Urban Contributions to Fine Particle Concentrations in Southeastern Canada

Abstract

The impact of various atmospheric transport directions on ambient fine particle (PM_2.5) concentrations at several sites in southeastern Canada was estimated (for May-September) using back-trajectory analysis. Three-day back trajectories (four per day) were paired with 6-hr average PM_2.5 mass concentrations measured using tapered element oscillating microbalances (TEOM). PM_2.5 concentrations at rural locations in the region were affected by nonlocal sources originating in both Canada and the United States. Comparison of sites revealed that, on average, the local contribution to total PM_2.5 in the greater Toronto area (GTA) is approximately 30–35%. At each location, average PM_2.5 concentrations under south/southwesterly flow conditions were 2–4 times higher than under the corresponding northerly flow conditions. The chemical composition of both urban and rural PM_2.5 was determined during two separate 2-week spring/summer measurement campaigns. Components identified included SO₄ ^2?, NO₃ ^?, NH₄+, black carbon and organic carbon (OC), and trace elements. Higher particle mass at the urban Toronto site was composed of a higher proportion of all components. However, black carbon, NO₃ ^?, NaCl, and trace elements were found to be the most enriched over the rural/regional background levels.     

Characterization of major chemical components of fine particulate matter in North Carolina

This paper presents measurements of daily sampling of fine particulate matter (PM2.5) 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 PM2.5 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 PM2.5 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. PM2.5 mass concentrations display a peak in early morning, and a second peak in late afternoon. Back trajectory analysis shows that air masses with lower PM2.5 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 PM2.5 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.     

Chemical speciation of PM2.5 collected during prescribed fires of the Coconino National Forest near Flagstaff, Arizona

The use of prescribed fire is expected to increase in an effort to reduce the risk of catastrophic fire, particularly at urban/forest interfaces. Fire is a well-known source of particulate matter (PM) with particle sizes < or =2.5 microm (PM2.5), small diameter PM known to affect climate, visibility, and human health. In this work, PM2.5 was collected during seven first-entry burns (flaming and smoldering stages) and one maintenance burn of the Coconino National Forest. Samples were analyzed for organic and elemental carbon, cations (sodium, potassium [K+], and ammonium [NH4+]), anions (nitrate [NO3-] and sulfate), and 48 elements (with atomic weights between sodium and lead). The PM2.5 contained high organic carbon levels (typically >90% by mass), commonly observed ions (K+, NH4+, and NO3-) and elements (K+, chlorine, sulfur, and silicon), as well as titanium and chromium. Flaming produced higher K+ and NH4+ levels than smoldering, and the elemental signature was more complex (20 versus 7 elements). Average organic carbon x 1.4 mass fractions (+/-standard deviation) were lower during flaming (92+/-14%) than during smoldering (124+/-24%). The maintenance (grassland) burn produced lower particle concentrations, lower NH4+ and NO3- levels, and higher K and chlorine levels than did the first-entry fires.     

Semicontinuous PM2.5 sulfate and nitrate measurements at an urban and a rural location in New York: PMTACS-NY summer 2001 and 2002 campaigns

Several collocated semicontinuous instruments measuring particulate matter with particle sizes < or =2.5 microm (PM2.5) sulfate (SO4(2-)) and nitrate (NO3-) were intercompared during two intensive field campaigns as part of the PM2.5 Technology Assessment and Characterization Study. The summer 2001 urban campaign in Queens, NY, and the summer 2002 rural campaign in upstate New York (Whiteface Mountain) hosted an operation of an Aerosol Mass Spectrometer, Ambient Particulate Sulfate and Nitrate Monitors, a Continuous Ambient Sulfate Monitor, and a Particle-Into-Liquid Sampler with Ion Chromatographs (PILS-IC). These instruments provided near real-time particulate SO4(2-) and NO3- mass concentration data, allowing the study of particulate SO4(2-)/NO3- diurnal patterns and detection of short-term events. Typical particulate SO4(2-) concentrations were comparable at both sites (ranging from 0 to 20 microg/m3), while ambient urban particulate NO3- concentrations ranged from 0 to 11 microg/m3 and rural NO3- concentration was typically less than 1 microg/m3. Results of the intercomparisons of the semicontinuous measurements are presented, as are results of the comparisons between the semicontinuous and time-integrated filter-based measurements. The comparisons at both sites, in most cases, indicated similar performance characteristics. In addition, charge balance calculations, based on major soluble ionic components of atmospheric aerosol from the PILS-IC and the filter measurements, indicated slightly acidic aerosol at both locations.     

Comparison of particulate mass, chemical species for urban, suburban and rural areas in central Taiwan, Taichung

Aerosol samples for PM2.5, PM(2.5-10) and TSP were collected from June to September 1998 and from February to March 1999 in central Taiwan. Ion chromatography was used to analyze the acidic anions: sulfate, nitrate and chloride in the Universal samples. The ratios of fine particle concentrations to coarse particle concentrations displayed that the fine particle concentrations are almost greater than that of coarse particle concentrations in Taichung area. The average concentrations of PM2.5, PM(2.5-10) and TSP in urban sites are higher than in suburban and rural sites at both daytime and night-time. Chloride dominated in the coarse mode in daytime and in fine mode in night-time. Nitrate can be found in both the coarse and fine modes. Sulfate dominated in fine mode in both daytime and night-time.     

Characterization of PM2.5 and PM10 in the South Coast Air Basin of southern California: Part 1--Spatial variations

In December 1994, the South Coast Air Quality Management District (SCAQMD) initiated a comprehensive program, the PM10 Technical Enhancement Program (PTEP), to characterize fine PM in the South Coast Air Basin (SCAB). A 1-year special particulate monitoring project was conducted from January 1995 to February 1996 as part of the PTEP. Under this enhanced monitoring, HNO3, NH3, and speciated PM10 and PM2.5 concentrations were measured at five stations (Anaheim, downtown Los Angeles, Diamond Bar, Fontana, and Rubidoux) in the SCAB and at one background station at San Nicolas Island. PM2.5 and PM10 mass and 43 individual species were analyzed for a full chemical speciation of the particle data. The PTEP data indicate that the most abundant chemical components of PM10 and PM2.5 in the SCAB are NH4+ (8-9% of PM10 and 14-17% of PM2.5), NO3- (23-26% of PM10 and 28-41% of PM2.5), SO4- (6-11% of PM10 and 9-18% of PM2.5), organic carbon (OC) (15-19% of PM10 and 18-26% of PM2.5), and elemental carbon (EC) (5-8% of PM10 and 8-13% of PM2.5). On an annual average basis, PM2.5 comprises 52-59% of the SCAB PM10. Annual average PM10 and PM2.5 concentrations showed strong spatial variations, low at coastal sites and high at inland sites. Annual average PM10 concentrations varied from 40.8 micrograms/m3 at Anaheim to 76.8 micrograms/m3 at Rubidoux, while annual average PM2.5 concentrations varied from 21.7 micrograms/m3 at Anaheim to 39.8 micrograms/m3 at Rubidoux. The chemical characterizations of the PM2.5 and PM10 concentrations, as well as their spatial variations, were examined; the important findings are summarized in this paper, and the temporal variations are discussed in the companion paper.     

Observations and Interpretations from the Canadian Fine Particle Monitoring Program

ABSTRACT

Canadian particle monitoring programs examining PM10, PM2.5, and particle composition have been in operation for over 10 years. Until recently, the measurements were manual/filter-based with 24-hr sample collection varying in frequency from daily to every sixth day, using GrasebyAnderson dichotomous samplers. In the past few years, these monitoring activities have been expanded to include hourly measurements using tapered element oscillating microbalances (TEOMs). This continuous monitoring program started operation focusing on PM_10, but now emphasizes PM_2.5 through the addition of more TEOMs and switching of the inlets of some of the existing units. The data from all of these measurement activities show that there are broad geographical differences and also local- to regional-scale spatial differences in mass and composition of PM2.5. Due to variations in sources, significantly different PM2.5 concentrations are not uncommon within the same city. Comparison of nearby urban and rural sites indicates that 30 and 40% of the PM_2.5 is from local urban sources in Montreal and Toronto, respectively. Hourly PM_2.5 measurements in Toronto suggest that vehicular emissions are an important contributor to urban PM_2.5. There has been a decreasing trend in urban PM_2.5, with annual average concentrations between the 1987–1990 and 1993–1995 periods decreasing by 11 to 39%, depending upon the site. The largest declines were in Montreal and Halifax, and the smallest decline was in Toronto. Comparison of 24-hr TEOM and manual dichotomous sampler PM_2.5 measurements from a site in Toronto indicates that the TEOM results in lower concentrations. The magnitude of this difference is relatively small in the warmer months, averaging about 12%. During the colder months the difference averages about 23%, but can be as large as 50%.     

Chemical characterization and factor analysis of PM2.5 in two sites of Monterrey, Mexico

The Monterrey Metropolitan Area (MMA) has shown a high concentration of PM2.5 in its atmosphere since 2003. The contribution of possible sources of primary PM2.5 and its precursors is not known. In this paper we present the results of analyzing the chemical composition of sixty 24-hr samples of PM2.5 to determine possible sources of PM2.5 in the MMA. The samples were collected at the northeast and southeast of the MMA between November 22 and December 12, 2007, using low-volume devices. Teflon and quartz filters were used to collect the samples. The concentrations of 16 airborne trace elements were determined using x-ray fluorescence (XRF). Anions and cations were determined using ion chromatography. Organic carbon (OC) and elemental carbon (EC) were determined by thermal optical analysis. The results show that Ca had the maximum mean concentration of all elements studied, followed by S. Enrichment factors above 50 were calculated for S, Cl, Cu, Zn, Br and Pb. This indicates that these elements may come from anthropogenic sources. Overall, the major average components of PM2.5 were OC (41.7%), SO4(2-) (22.9%), EC (7.4%), crustal material (11.4%), and NO3- (12.6%), which altogether accounted for 96% of the mass. Statistically, we did not find any difference in SO4(2-) concentrations between the two sites. The fraction of secondary organic carbon was between 24% and 34%. The results of the factor analysis performed over 10 metals and OC and EC show that there are three main sources of PM2.5: crustal material and vehicle exhaust; industrial activity; and fuel oil burning. The results show that SO4(2-), OC, and crustal material are important components of PM2.5 in MMA. Further work is necessary to evaluate the proportion of secondary inorganic and organic aerosol in order to have a better understanding of the sources and precursors of aerosols in the MMA.     

The Southeastern Aerosol Research and Characterization Study: Part II. Filter-based measurements of fine and coarse particulate matter mass and composition

The Southeastern Aerosol Research and Characterization Study (SEARCH) was implemented in 1998-1999 to provide data and analyses for the investigation of the sources, chemical speciation, and long-term trends of fine particulate matter (PM2.5) and coarse particulate matter (PM10-2.5) in the Southeastern United States. This work is an initial analysis of 5 years (1999-2003) of filter-based PM2.5 and PM10-2.5 data from SEARCH. We find that annual PM2.5 design values were consistently above the National Ambient Air Quality Standards (NAAQS) 15 microg/m3 annual standard only at monitoring sites in the two largest urban areas (Atlanta, GA, and North Birmingham, AL). Other sites in the network had annual design values below the standard, and no site had daily design values above the NAAQS 65 microg/m3 daily standard. Using a particle composition monitor designed specifically for SEARCH, we found that volatilization losses of nitrate, ammonium, and organic carbon must be accounted for to accurately characterize atmospheric particulate matter. In particular, the federal reference method for PM2.5 underestimates mass by 3-7% as a result of these volatilization losses. Organic matter (OM) and sulfate account for approximately 60% of PM2.5 mass at SEARCH sites, whereas major metal oxides (MMO) and unidentified components ("other") account for > or = 80% of PM10-2.5 mass. Limited data suggest that much of the unidentified mass in PM10-2.5 may be OM. For paired comparisons of urban-rural sites, differences in PM2.5 mass are explained, in large part, by higher OM and black carbon at the urban site. For PM10, higher urban concentrations are explained by higher MMO and "other." Annual means for PM2.5 and PM10-2.5 mass and major components demonstrate substantial declines at all of the SEARCH sites over the 1999-2003 period (10-20% in the case of PM2.5, dominated by 14-20% declines in sulfate and 11-26% declines in OM, and 14-25% in the case of PM10-2.5, dominated by 17-30% declines in MMO and 14-31% declines in "other"). Although declining national emissions of sulfur dioxide and anthropogenic carbon may account for a portion of the observed declines, additional investigation will be necessary to establish a quantitative assessment, especially regarding trends in local and regional emissions, primary carbon emissions, and meteorology.     

Fine and coarse particulate matter chemical characterization in a heavily industrialized city in central Mexico during Winter 2003

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 microm (PM10) and fine PM with aerodynamic diameter of less than 2.5 microm (PM2.5) ranged from 32.2 to 76.6 [g m(-3) and 11.1 to 23.7 microg m(-3), respectively. OC (34%), SO4= (25.1%), EC (12.9%), and geological material (12.5%) were the major components of PM2.5. For PM10 geological material (57.9%), OC (17.3%), and SO4= (9.7%) were the major components. Coarse fraction (PM,, -PM2.5), geological material (81.7%), and OC (8.6%) were the dominant species, which amounted to 90.4%. Correlation analysis showed that sulfate in PM2.5 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 PM2.5 mass concentrations were similar to the submicron fraction concentrations. Furthermore, the correlation between EC in PM2.5 and EC measured from an aethalometer was r(2) = 0.710. Temporal variations of SO2 and nitrogen oxide were observed during a day when the maximum concentration of PM2.5 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 microm.     

The influences of ambient particle composition and size on particle infiltration in Los Angeles, CA, residences

Particle infiltration is a key determinant of the indoor concentrations of ambient particles. Few studies have examined the influence of particle composition on infiltration, particularly in areas with high concentrations of volatile particles, such as ammonium nitrate (NH4NO3). A comprehensive indoor monitoring study was conducted in 17 Los Angeles-area homes. As part of this study, indoor/outdoor concentration ratios during overnight (nonindoor source) periods were used to estimate the fraction of ambient particles remaining airborne indoors, or the particle infiltration factor (FINF), for fine particles (PM2.5), its nonvolatile (i.e., black carbon [BC]) and volatile (i.e., nitrate [NO3-]) components, and particle sizes ranging between 0.02 and 10 microm. FINF was highest for BC (median = 0.84) and lowest for NO3- (median = 0.18). The low FINF for NO3- was likely because of volatilization of NO3- particles once indoors, in addition to depositional losses upon building entry. The FINF for PM2.5 (median = 0.48) fell between those for BC and NO3-, reflecting the contributions of both particle components to PM25. FINF varied with particle size, air-exchange rate, and outdoor NO3- concentrations. The FINF for particles between 0.7 and 2 microm in size was considerably lower during periods of high as compared with low outdoor NO3- concentrations, suggesting that outdoor NO3- particles were of this size. This study demonstrates that infiltration of PM2.5 varies by particle component and is lowest for volatile species, such as NH4NO3. Our results suggest that volatile particle components may influence the ability for outdoor PM concentrations to represent indoor and, thus, personal exposures to particles of ambient origin, because volatilization of these particles causes the composition of PM2.5 to differ indoors and outdoors. Consequently, particle composition likely influences observed epidemiologic relationships based on outdoor PM concentrations, especially in areas with high concentrations of NH4NO3 and other volatile particles.     

Anthropogenic and natural influence on the PM(10) and PM(2.5) aerosol in Madrid (Spain). Analysis of high concentration episodes

Non-mineral carbon is the main component of PM10 and PM2.5 at an urban roadside site in Madrid accounting for more than 50% of the total bulk mass in winter pollution episodes. In these cases a 70-80% of the particle mass is anthropogenic. Particles of crustal/mineral origin contribute significantly to the observed PM10 concentrations, especially in spring and summer. They have also been found in the PM2.5 fraction although secondary particles are the next most important contributor in this size. Long-range transport particle episodes of Saharan dust significantly contribute to exceedence of the new daily limiting PM10 value in the urban network and at nearby rural background stations. This type of long-range transport event also influences PM2.5 concentrations. The crustal contribution can account for up to 67 and 53% of the PM10 and PM2.5 bulk mass in such cases.     

Air quality measurements from the Fresno Supersite

The Fresno Supersite intends to 1) evaluate non-routine monitoring methods, establishing their comparability with existing methods and their applicability to air quality planning, exposure assessment, and health effects studies; 2) provide a better understanding of aerosol characteristics, behavior, and sources to assist regulatory agencies in developing standards and strategies that protect public health; and 3) support studies that evaluate relationships between aerosol properties, co-factors, and observed health end-points. Supersite observables include in-situ, continuous, short-duration measurements of 1) PM2.5, PM10, and coarse (PM10 minus PM2.5) mass; 2) PM2.5 SO4(-2), NO3-, carbon, light absorption, and light extinction; 3) numbers of particles in discrete size bins ranging from 0.01 to approximately 10 microns; 4) criteria pollutant gases (O3, CO, NOx); 5) reactive gases (NO2, NOy, HNO3, peroxyacetyl nitrate [PAN], NH3); and 6) single particle characterization by time-of-flight mass spectrometry. Field sampling and laboratory analysis are applied for gaseous and particulate organic compounds (light hydrocarbons, heavy hydrocarbons, carbonyls, polycyclic aromatic hydrocarbons [PAH], and other semi-volatiles), and PM2.5 mass, elements, ions, and carbon. Observables common to other Supersites are 1) daily PM2.5 24-hr average mass with Federal Reference Method (FRM) samplers; 2) continuous hourly and 5-min average PM2.5 and PM10 mass with beta attenuation monitors (BAM) and tapered element oscillating microbalances (TEOM); 3) PM2.5 chemical speciation with a U.S. Environmental Protection Agency (EPA) speciation monitor and protocol; 4) coarse particle mass by dichotomous sampler and difference between PM10 and PM2.5 BAM and TEOM measurements; 5) coarse particle chemical composition; and 6) high sensitivity and time resolution scalar and vector wind speed, wind direction, temperature, relative humidity, barometric pressure, and solar radiation. The Fresno Supersite is coordinated with health and toxicological studies that will use these data in establishing relationships with asthma, other respiratory disease, and cardiovascular changes in human and animal subjects.     

Wood smoke contribution to winter aerosol in Fresno, CA

In an effort to better quantify wintertime particulate matter (PM) and the contribution of wood smoke to air pollution events in Fresno, CA, a field campaign was conducted in winter 2003-2004. Coarse and fine daily PM samples were collected at five locations in Fresno, including residential, urban, and industrial areas. Measurements of collected samples included gravimetric mass determination, organic and elemental carbon analysis, and trace organic compound analysis by gas chromatograph mass spectrometry (GC/MS). The wood smoke tracer levoglucosan was also measured in aqueous aerosol extracts using high-performance anion exchange chromatography coupled with pulsed amperometric detection. Sample preparation and analysis by this technique is much simpler and less expensive than derivatized levoglucosan analysis by GC/MS, permitting analysis of daily PM samples from all five of the measurement locations. Analyses revealed low spatial variability and similar temporal patterns of PM2.5 mass, organic carbon (OC), and levoglucosan. Daily mass concentrations appear to have been strongly influenced by meteorological conditions, including precipitation, wind, and fog events. Fine PM (PM2.5) concentrations are uncommonly low during the study period, reflecting frequent precipitation events. During the first portion of the study, levoglucosan had a strong relationship to the concentrations of PM2.5 and OC. In the later portion of the study, there was a significant reduction in levoglucosan relative to PM2.5 and OC. This may indicate a change in particle removal processes, perhaps because of fog events, which were more common in the latter period. Combined, the emissions from wood smoke, meat cooking, and motor vehicles appear to contribute approximately 65-80% to measured OC, with wood smoke, on average, accounting for approximately 41% of OC and approximately 18% of PM2.5 mass. Two residential sites exhibit somewhat higher contributions of wood smoke to OC than other locations.     

The Aerosol Research and Inhalation Epidemiology Study (ARIES): PM2.5 mass and aerosol component concentrations and sampler intercomparisons

The Aerosol Research and Inhalation Epidemiology Study (ARIES) was designed to provide high-quality measurements of PM2.5, 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 PM2.5 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 PM2.5 mass and speciation samples and continuous PM2.5 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 PM2.5 components and consider associations and potential mechanistic linkages of PM2.5 mass concentrations with several PM2.5 components. For the 12 months of validated data collected to date (August 1, 1998-July 31, 1999), the monthly average Federal Reference Method (FRM) PM2.5 mass always exceeded the proposed annual average standard (12-month average = 20.3 +/- 9.5 micrograms/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 PM2.5 mass dropped to less than 30% in winter. Particulate NO3- collected on a denuded nylon filter averaged 1.1 +/- 0.9 micrograms/m3. Particle-phase organic compounds (as organic carbon x 1.4) measured on a denuded quartz filter sampler averaged 6.4 +/- 3.1 micrograms/m3 (32% of FRM PM2.5 mass) with less seasonal variability than SO4(2-).     

The Southeastern Aerosol Research and Characterization Study, part 3: continuous measurements of fine particulate matter mass and composition

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 (PM2.5) mass is performed using a dried, 30 degrees 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 PM2.5 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 PM2.5 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 PM2.5 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.     

Determination of source contributions to ambient PM2.5 in Kaohsiung, Taiwan, using a receptor model

Ambient particulates of PM2.5 were sampled at three sites in Kaohsiung, Taiwan, during February and March 1999. In addition, resuspended PM2.5 collected from traffic tunnels, paved roads, fly ash of a municipal solid waste (MSW) incinerator, and seawater was obtained. All the samples were analyzed for twenty constituents, including water-soluble ions, organic carbon (OC), elemental carbon (EC), and metallic elements. In conjunction with local source profiles and the source profiles in the model library SPECIATE EPA, the receptor model based on chemical mass balance (CMB) was then applied to determine the source contributions to ambient PM2.5. The mean concentration of ambient PM2.5 was 42.69-53.68 micrograms/m3 for the sampling period. The abundant species in ambient PM2.5 in the mass fraction for three sites were OC (12.7-14.2%), SO4(2-) (12.8-15.1%), NO3- (8.1-10.3%), NH4+ (6.7-7.5%), and EC (5.3-8.5%). Results of CMB modeling show that major pollution sources for ambient PM2.5 are traffic exhaust (18-54%), secondary aerosols (30-41% from SO4(2-) and NO3-), and outdoor burning of agriculture wastes (13-17%).     

Characterization of particulate matter for three sites in Kuwait

Many studies have shown strong associations between particulate matter (PM) levels and a variety of health outcomes, leading to changes in air quality standards in many regions, especially the United States and Europe. Kuwait, a desert country located on the Persian Gulf, has a large petroleum industry with associated industrial and urban land uses. It was marked by environmental destruction from the 1990 Iraqi invasion and subsequent oil fires. A detailed particle characterization study was conducted over 12 months in 2004-2005 at three sites simultaneously with an additional 6 months at one of the sites. Two sites were in urban areas (central and southern) and one in a remote desert location (northern). This paper reports the concentrations of particles less than 10 microm in diameter (PM10) and fine PM (PM2.5), as well as fine particle nitrate, sulfate, elemental carbon (EC), organic carbon (OC), and elements measured at the three sites. Mean annual concentrations for PM10 ranged from 66 to 93 microg/m3 across the three sites, exceeding the World Health Organization (WHO) air quality guidelines for PM10 of 20 microg/m3. The arithmetic mean PM2.5 concentrations varied from 38 and 37 microg/m3 at the central and southern sites, respectively, to 31 microg/m3 at the northern site. All sites had mean PM2.5 concentrations more than double the U.S. National Ambient Air Quality Standard (NAAQS) for PM2.5. Coarse particles comprised 50-60% of PM10. The high levels of PM10 and large fraction of coarse particles comprising PM10 are partially explained by the resuspension of dust and soil from the desert crust. However, EC, OC, and most of the elements were significantly higher at the urbanized sites, compared with the more remote northern site, indicating significant pollutant contributions from local mobile and stationary sources. The particulate levels in this study are high enough to generate substantial health impacts and present opportunities for improving public health by reducing airborne PM.     

Comparison between urban Toronto PM and selected materials: aerosol characterization using laser ablation/ionization mass spectrometry (LAMS)

Laser ablation/ionization mass spectrometry (LAMS) of particulate matter (PM) was undertaken on-line in order to extend and contrast PM characterization. Qualitative on-line LAMS results for certified materials and Toronto source materials demonstrated the versatility and limitations of the technique. The observation of organic and inorganic components of certified materials verified the proper working condition of the in-house on-line LAMS. Organic and inorganic components of Toronto source materials were also observed with the on-line LAMS. Common components identified from both types of materials were Na, Al, Ca, Fe, and K. Other recognized components were compared with marker elements reported for some common PM emission sources. An in-house off-line LAMS was used to analyze urban Toronto PM deposited on glass substrates, while the on-line LAMS analyzed individual urban Toronto PM particles that were introduced directly into the instrument. Scanning electron microscopy (SEM), X-ray spectrometry and inductively coupled plasma atomic emission spectrometry (ICP-AES) were used for confirmatory purposes. Organic and inorganic components of urban Toronto PM at their typical ng/m3 concentrations were successfully observed in mass spectra using both off-line LAMS and on-line LAMS. Identified ions unique to each analyzed material were compared to identified ions of urban Toronto PM. The ability of LAMS to analyze individual respirable PM particles (viz. < 2 microns), both for inorganic trace elements and for organic components, greatly extended our capability to characterize PM and also to achieve estimates of concentration contributions of each material.     

Comparison of two winter air quality episodes during the California Regional Particulate Air Quality Study

The duration, strength, spatial extent, and chemical makeup of particulate matter (PM) are compared for two winter air quality episodes captured during the California Regional Particulate Air Quality Study (CRPAQS). Each episode, from the beginning of the buildup through dissolution, lasted about 3 weeks. The first episode occurred from December 14, 1999, through January 1, 2000, with peak 24-hr average fine particulate matter (PM2.5) concentrations reaching 129 microg/m3. The second episode occurred a year later, from December 18, 2000, through January 8, 2001, with peak 24-hr average PM2.5 concentrations reaching 179 microg/m3. Although similar in duration, each episode exhibited unique characteristics. One significant difference was the episode buildup rate; rapid in 1999, but slow and steady in 2000. The rapid buildup of the first episode resulted in more days with PM2.5 concentrations above the 24-hr federal standard, whereas the slow and steady increase of the second episode produced higher peaks. Spatial extent and progress also differed between the two episodes. The Northern Valley was impacted more during the December 1999 episode, and the Southern Valley during the December 2000 episode. The differences carried over into chemical composition. Ammonium nitrate dominated the PM2.5 mass during the December 1999 episode. The second episode reflected a dichotomy typical to the San Joaquin Valley, with Fresno concentrations dominated by organic and elemental carbon and the rest of the Valley concentrations dominated by ammonium nitrate. Each episode showed a regional as well as a local component. Ammonium nitrate concentrations, which result from more regional-scale secondary formation and mixing of emissions, were fairly uniform among the urban and rural sites. Carbon concentrations were always higher at urban sites than at rural sites, corresponding to the higher emissions density of primary carbon sources in urban areas.