Differential pulmonary inflammation and in vitro cytotoxicity of size-fractionated fly ash particles from pulverized coal combustion

Exposure to airborne particulate matter (PM) has been associated with adverse health effects in humans. Pulmonary inflammatory responses were examined in CD1 mice after intratracheal instillation of 25 or 100 microg of ultrafine (< 0.2 microm), fine (< 2.5 microm), and coarse (> 2.5 microm) coal fly ash from a combusted Montana subbituminous coal, and of fine and coarse fractions from a combusted western Kentucky bituminous coal. After 18 hr, the lungs were lavaged and the bronchoalveolar fluid was assessed for cellular influx, biochemical markers, and pro-inflammatory cytokines. The responses were compared with saline and endotoxin as negative and positive controls, respectively. On an equal-mass basis, the ultrafine particles from combusted Montana coal induced a higher degree of neutrophil inflammation and cytokine levels than did the fine or coarse PM. The western Kentucky fine PM caused a moderate degree of inflammation and protein levels in bronchoalveolar fluid that were higher than the Montana fine PM. Coarse PM did not produce any significant effects. In vitro experiments with rat alveolar macrophages showed that of the particles tested, only the Montana ultrafine displayed significant cytotoxicity. It is concluded that fly ash toxicity is inversely related with particle size and is associated with increased sulfur and trace element content.     

Size and composition distributions of particulate matter emissions: part 1--light-duty gasoline vehicles

Size-resolved particulate matter (PM) emitted from light-duty gasoline vehicles (LDGVs) was characterized using filter-based samplers, cascade impactors, and scanning mobility particle size measurements in the summer 2002. Thirty LDGVs, with different engine and emissions control technologies (model years 1965-2003; odometer readings 1264-207,104 mi), were tested on a chassis dynamometer using the federal test procedure (FTP), the unified cycle (UC), and the correction cycle (CC). LDGV PM emissions were strongly correlated with vehicle age and emissions control technology. The oldest models had average ultrafine PM0.1 (0.056- to 0.1-microm aerodynamic diameter) and fine PM1.8 (< or =1.8-microm aerodynamic diameter) emission rates of 9.6 mg/km and 213 mg/km, respectively. The newest vehicles had PM0.1 and PM1.8 emissions of 51 microg/km and 371 microg/km, respectively. Light duty trucks and sport utility vehicles had PM0.1 and PM1.8 emissions nearly double the corresponding emission rates from passenger cars. Higher PM emissions were associated with cold starts and hard accelerations. The FTP driving cycle produced the lowest emissions, followed by the UC and the CC. PM mass distributions peaked between 0.1- and 0.18-microm particle diameter for all vehicles except those emitting visible smoke, which peaked between 0.18 and 0.32 microm. The majority of the PM was composed of carbonaceous material, with only trace amounts of water-soluble ions. Elemental carbon (EC) and organic matter (OM) had similar size distributions, but the EC/OM ratio in LDGV exhaust particles was a strong function of the adopted emissions control technology and of vehicle maintenance. Exhaust from LDGV classes with lower PM emissions generally had higher EC/OM ratios. LDGVs adopting newer technologies were characterized by the highest EC/OM ratios, whereas OM dominated PM emissions from older vehicles. Driving cycles with cold starts and hard accelerations produced higher EC/OM ratios in ultrafine particles.     

Size and composition distributions of particulate matter emissions: part 2--heavy-duty diesel vehicles

Particulate matter (PM) emissions from heavy-duty diesel vehicles (HDDVs) were collected using a chassis dynamometer/dilution sampling system that employed filter-based samplers, cascade impactors, and scanning mobility particle size (SMPS) measurements. Four diesel vehicles with different engine and emission control technologies were tested using the California Air Resources Board Heavy Heavy-Duty Diesel Truck (HHDDT) 5 mode driving cycle. Vehicles were tested using a simulated inertial weight of either 56,000 or 66,000 lb. Exhaust particles were then analyzed for total carbon, elemental carbon (EC), organic matter (OM), and water-soluble ions. HDDV fine (< or =1.8 microm aerodynamic diameter; PM1.8) and ultrafine (0.056-0.1 microm aerodynamic diameter; PM0.1) PM emission rates ranged from 181-581 mg/km and 25-72 mg/km, respectively, with the highest emission rates in both size fractions associated with the oldest vehicle tested. Older diesel vehicles produced fine and ultrafine exhaust particles with higher EC/OM ratios than newer vehicles. Transient modes produced very high EC/OM ratios whereas idle and creep modes produced very low EC/OM ratios. Calcium was the most abundant water-soluble ion with smaller amounts of magnesium, sodium, ammonium ion, and sulfate also detected. Particle mass distributions emitted during the full 5-mode HDDV tests peaked between 100-180 nm and their shapes were not a function of vehicle age. In contrast, particle mass distributions emitted during the idle and creep driving modes from the newest diesel vehicle had a peak diameter of approximately 70 nm, whereas mass distributions emitted from older vehicles had a peak diameter larger than 100 nm for both the idle and creep modes. Increasing inertial loads reduced the OM emissions, causing the residual EC emissions to shift to smaller sizes. The same HDDV tested at 56,000 and 66,000 lb had higher PM0.1 EC emissions (+22%) and lower PM0.1 OM emissions (-38%) at the higher load condition.     

Size and composition distribution of airborne particulate matter in northern California: I--particulate mass, carbon, and water-soluble ions

The San Joaquin Valley (SJV) in California has one of the most severe particulate air quality problems in the United States during the winter season. In the current study, measurements of particulate matter (PM) smaller than 10 microm in aerodynamic diameter (PM10), fine particles (PM18), and ultrafine particles (PM0.1) made during the period December 16, 2000-February 3, 2001, at six locations near or within the SJV are discussed: Bodega Bay, Davis, Sacramento, Modesto, Bakersfield, and Sequoia National Park. Airborne PM1.8 concentrations at the most heavily polluted site (Bakersfield) increased from 20 to 172 microg/m3 during the period December 16, 2000-January 7, 2001. The majority of the fine particle mass was ammonium nitrate driven by an excess of gas-phase ammonia. Peak PM0.1 concentrations (8-12 hr average) were approximately 2.4 microg/m3 measured at night in Sacramento and Bakersfield. Ultrafine particle concentrations were distinctly diurnal, with daytime concentrations approximately 50% lower than nighttime concentrations. PMO.1 concentrations did not accumulate during the multiweek stagnation period; rather, PMO.1 mass decreased at Bakersfield as PM1.8 mass was increasing. The majority of the ultrafine particle mass was associated with carbonaceous material. The high concentrations of ultrafine particles in the SJV pose a potential serious public health threat that should be addressed.     

Aerosol ion characteristics during the Big Bend Regional Aerosol and Visibility Observational study

The ionic compositions of particulate matter with aerodynamic diameter < or = 2.5 microm (PM2.5) and size-resolved aerosol particles were measured in Big Bend National Park, Texas, during the 1999 Big Bend Regional Aerosol and Visibility Observational study. The ionic composition of PM2.5 aerosol was dominated by sulfate (SO4(2-)) and ammonium (NH4+). Daily average SO4(2-) and NH4+ concentrations were strongly correlated (R2 = 0.94). The molar ratio of NH4+ to SO4(2-) averaged 1.54, consistent with concurrent measurements of aerosol acidity. The aerosol was observed to be comprised of a submicron fine mode consisting primarily of ammoniated SO4(2-) and a coarse particle mode containing nitrate (NO3-). The NO3- appears to be primarily associated with sea salt particles where chloride has been replaced by NO3-, although formation of calcium nitrate (Ca(NO3)2) is important, too, on several days. Size-resolved aerosol composition results reveal that a size cut in particulate matter with aerodynamic diameter < or = 1 microm would have provided a much better separation of fine and coarse aerosol modes than the standard PM2.5 size cut utilized for the study. Although considerable nitric acid exists in the gas phase at Big Bend, the aerosol is sufficiently acidic and temperatures sufficiently high that even significant future reductions in PM2.5 SO4(2-) are unlikely to be offset by formation of particulate ammonium nitrate in summer or fall.     

Synopsis of the temporal variation of particulate matter composition and size

A synopsis of the detailed temporal variation of the size and number distribution of particulate matter (PM) and its chemical composition on the basis of measurements performed by several regional research consortia funded by the U.S. Environmental Protection Agency (EPA) PM Supersite Program is presented. This program deployed and evaluated a variety of research and emerging commercial measurement technologies to investigate the physical and chemical properties of atmospheric aerosols at a level of detail never before achieved. Most notably these studies demonstrated that systematic size-segregated measurements of mass, number, and associated chemical composition of the fine (PM2.5) and ultrafine (PM0.1) fraction of ambient aerosol with a time resolution down to minutes and less is achievable. A wealth of new information on the temporal variation of aerosol has been added to the existing knowledge pool that can be mined to resolve outstanding research and policy-related questions. This paper explores the nature of temporal variations (on time scales from several minutes to hours) in the chemical and physical properties of PM and its implications in the identification of PM formation processes, and source attribution (primary versus secondary), the contribution of local versus transported PM and the development of effective PM control strategies. The PM Supersite results summarized indicate that location, time of day, and season significantly influence not only the mass and chemical composition but also the size-resolved chemical/elemental composition of PM. Ambient measurements also show that ultrafine particles have different compositions and make up only a small portion of the PM mass concentration compared with inhalable coarse and fine particles, but their number concentration is significantly larger than their coarse or fine counterparts. PM size classes show differences in the relative amounts of nitrates, sulfates, crustal materials, and most especially carbon as well as variations in seasonal and diurnal patterns.     

Size and Composition Distributions of Particulate Matter Emissions: Part 1—Light-Duty Gasoline Vehicles

Abstract

Size-resolved particulate matter (PM) emitted from light-duty gasoline vehicles (LDGVs) was characterized using filter-based samplers, cascade impactors, and scanning mobility particle size measurements in the summer 2002. Thirty LDGVs, with different engine and emissions control technologies (model years 1965–2003; odometer readings 1264–207,104 mi), were tested on a chassis dynamometer using the federal test procedure (FTP), the unified cycle (UC), and the correction cycle (CC). LDGV PM emissions were strongly correlated with vehicle age and emissions control technology. The oldest models had average ultrafine PM_0.1 (0.056- to 0.1-μm aerodynamic diameter) and fine PM_1.8 (≤1.8-μm aerodynamic diame ter) emission rates of 9.6 mg/km and 213 mg/km, respectively. The newest vehicles had PM_0.1 and PM_1.8 emis sions of 51 μg/km and 371 μg/km, respectively. Light duty trucks and sport utility vehicles had PM_0.1 and PM_1.8 emissions nearly double the corresponding emission rates from passenger cars. Higher PM emissions were associated with cold starts and hard accelerations. The FTP driving cycle produced the lowest emissions, followed by the UC and the CC. PM mass distributions peaked between 0.1-and 0.18-μm particle diameter for all vehicles except those emitting visible smoke, which peaked between 0.18 and 0.32 μm. The majority of the PM was composed of carbonaceous material, with only trace amounts of water-soluble ions. Elemental carbon (EC) and organic matter (OM) had similar size distributions, but the EC/OM ratio in LDGV exhaust particles was a strong function of the adopted emissions control technology and of vehicle maintenance. Exhaust from LDGV classes with lower PM emissions generally had higher EC/OM ratios. LDGVs adopting newer technologies were characterized by the highest EC/OM ratios, whereas OM dominated PM emissions from older vehicles. Driving cycles with cold starts and hard accelerations produced higher EC/OM ratios in ultrafine particles.     

Relationship between indoor and outdoor carbonaceous particulates in roadside households

Concentrations of particulate matter (PM) and carbonaceous particulates in indoor and outdoor air at roadside private households were measured in Osaka, Japan. The particulate samples were collected on filters using a portable AND sampler capable of separating particles into three different size ranges: over 10 microm, 2-10 microm (coarse) and below 2 microm (fine) in aerodynamic diameter. The filters were weighed and then analyzed for elemental carbon (EC) and organic carbon (OC) by thermal oxidation using a CHN CORDER. The results showed that indoor fine PM concentration is considerably affected by fine EC and the fine EC in indoor air is significantly correlated to that in outdoor air, r=0.86 (n=30, p<0.001). A simple estimation from EC content ratio in diesel exhaust particles indicated that about 30% of indoor particulates of less than 10 microm (PM10) were contributed from diesel exhaust. Additionally, the size characteristics of outdoor PM at roadside and background sites were examined using Andersen Cascade Impactors.     

Characteristics of inhalable particulate matter concentration and size distribution from power plants in China

In this investigation, the collection efficiency of particulate emission control devices (PECDs), particulate matter (PM) emissions, and PM size distribution were determined experimentally at the inlet and outlet of PECDs at five coal-fired power plants. Different boilers, coals, and PECDs are used in these power plants. Measurement in situ was performed by an electrical low-pressure impactor with a sampling system, which consisted of an isokinetic sampler probe, precut cyclone, and two-stage dilution system with a sample line to the instruments. The size distribution was measured over a range from 0.03 to 10 microm. Before and after all of the PECDs, the particle number size distributions display a bimodal distribution. The PM2.5 fraction emitted to atmosphere includes a significant amount of the mass from the coarse particle mode. The controlled and uncontrolled emission factors of total PM, inhalable PM (PM10), and fine PM P(M2.5) were obtained. Electrostatic precipitator (ESP) and baghouse total collection efficiencies are 96.38-99.89% and 99.94%, respectively. The minimum collection efficiency of the ESP and the baghouse both appear in the particle size range of 0.1-1 microm. In this size range, ESP and baghouse collection efficiencies are 85.79-98.6% and 99.54%. Real-time measurement shows that the mass and number concentration of PM10 will be greatly affected by the operating conditions of the PECDs. The number of emitted particles increases with increasing boiler load level because of higher combustion temperature. During test run periods, the data reproducibility is satisfactory.     

Measurements of ultrafine particles and other vehicular pollutants inside a mobile exposure system on Los Angeles freeways

A mobile exposure and air pollution measurement system was developed and used for on-freeway ultrafine particle health effects studies. A nine-passenger van was modified with a high-efficiency particulate air (HEPA) filtration system that can deliver filtered or unfiltered air to an exposure chamber inside the van. State-of-the-art instruments were used to measure concentration and size distribution of fine and ultrafine particles and the concentration of carbon monoxide (CO), black carbon (BC), particle-bound polycyclic aromatic hydrocarbons (PAHs), fine particulate matter (PM2.5) mass, and oxides of nitrogen (NOx) inside the exposure chamber. This paper presents the construction and technical details of the van and air pollutant concentrations collected in 32 2-hr runs on two major Los Angeles freeways, Interstate 405 (1-405; mostly gasoline traffic) and Interstate 710 (1-710; large proportion of heavy-duty diesel traffic). More than 97% of particles were removed when the flow through the filter box was switched from bypass mode to filter mode while the vehicle was driving on both freeways. The filtration system thus provides a great particulate matter exposure contrast while keeping gas-phase pollutant concentrations the same. Under bypass mode, average total particle number concentration observed inside the exposure chamber was around 8.4 x 10(4) and 1.3 x 10(5) particles cm(-3) on the I-405 and the I-710 freeways, respectively. Bimodal size distributions were consistent and similar for both freeways with the first mode around 16-20 nm and the second mode around 50-55 nm. BC and particle-bound PAH concentrations were more than two times greater on the I-710 than on the I-405 freeway. Very weak correlations were observed between total particle number concentrations and other vehicular pollutants on the freeways.     

Source identification of atlanta aerosol by positive matrix factorization

Data characterizing daily integrated particulate matter (PM) samples collected at the Jefferson Street monitoring site in Atlanta, GA, were analyzed through the application of a bilinear positive matrix factorization (PMF) model. A total of 662 samples and 26 variables were used for fine particle (particles < or = 2.5 microm in aerodynamic diameter) samples (PM2.5), and 685 samples and 15 variables were used for coarse particle (particles between 2.5 and 10 microm in aerodynamic diameter) samples (PM10-2.5). Measured PM mass concentrations and compositional data were used as independent variables. To obtain the quantitative contributions for each source, the factors were normalized using PMF-apportioned mass concentrations. For fine particle data, eight sources were identified: SO4(2-) -rich secondary aerosol (56%), motor vehicle (22%), wood smoke (11%), NO(3-) -rich secondary aerosol (7%), mixed source of cement kiln and organic carbon (OC) (2%), airborne soil (1%), metal recycling facility (0.5%), and mixed source of bus station and metal processing (0.3%). The SO4(2-) -rich and NO(3-) -rich secondary aerosols were associated with NH(4+). The SO4(2-) -rich secondary aerosols also included OC. For the coarse particle data, five sources contributed to the observed mass: airborne soil (60%), NO(3-)-rich secondary aerosol (16%), SO4(2-) -rich secondary aerosol (12%), cement kiln (11%), and metal recycling facility (1%). Conditional probability functions were computed using surface wind data and identified mass contributions from each source. The results of this analysis agreed well with the locations of known local point sources.     

Chemical coupling between ammonia, acid gases, and fine particles

The concentrations of inorganic aerosol components in the fine particulate matter (PM(fine)< or =2.5 microm) consisted of primarily ammonium, sodium, sulfate, nitrate, and chloride are related to the transfer time scale between gas to particle phase, which is a function of the ambient temperature, relative humidity, and their gas phase constituent concentrations in the atmosphere. This study involved understanding the magnitude of major ammonia sources; and an up-wind and down-wind (receptor) ammonia, acid gases, and fine particulate measurements; with a view to accretion gas-to-particle conversion (GTPS) process in an agricultural/rural environment. The observational based analysis of ammonia, acid gases, and fine particles by annular denuder system (ADS) coupled with a Gaussian dispersion model provided the mean pseudo-first-order k(S-1) between NH(3) and H(2)SO(4) aerosol approximately 5.00 (+/-3.77)x10(-3) s(-1). The rate constant was found to increase as ambient temperature, wind speed, and solar radiation increases, and decreases with increasing relative humidity. The observed [NH(3)][HNO(3)] products exceeded values predicted by theoretical equilibrium constants, due to a local excess of ammonia concentration.     

A review of the impact of fireworks on particulate matter in ambient air

To determine the impact of fireworks (FW) and firecrackers (FC) on particulate matter (PM) in ambient air, we reviewed evidence related to ambient PM during FW/FC periods; specifically, PM concentration, size, morphology, chemical components, including water-soluble ions and trace metals, and associated human health risks caused by exposure to FW/FC PM were reviewed. A large body of research suggests that outdoor ambient PM levels increase significantly during FW/FC displays. Furthermore, FW/FC PM remains suspended in the air, contributing to high PM concentrations for a long period. Increased PM from burning FW and FC mainly comprises fine and ultrafine spherical particles. Elevated levels of various trace metals, ions, elemental carbon (EC), organic carbon (OC), and organics in PM are present during FW/FC periods.Implications: Unique physical and chemical properties of ambient PM during short-term FW/FC burning can lead to a substantial increase in adverse health effects compared with during non-FW/FC periods. Further epidemiological and toxicological research into the potential health effects resulting from exposure to various pollutants from FW/FC is vital. Geographical distributions of PM concentrations during FW displays highlight the importance of implementing PM controls at the regional level and formulating stricter protective environmental legislation, particularly in Asian (e.g., India, China, or Taiwan) where festivals are not the only periods celebrated with FW/FC.     

Loading effect correction for real-time aethalometer measurements of fresh diesel soot

In this study, a correction was developed for the aethalometer to measure real-time black carbon (BC) concentrations in an environment dominated by fresh diesel soot. The relationship between the actual mass-specific absorption coefficient for BC and the BC-dependent attenuation coefficients was determined from experiments conducted in a diesel exposure chamber that provided constant concentrations of fine particulate matter (PM; PM(2.5); PM < 2.5 microm in aerodynamic diameter) from diesel exhaust. The aethalometer reported BC concentrations decreasing with time from 48.1 to 31.5 microg m(-3) when exposed to constant PM(2.5) concentrations of 55 +/- 1 microg m(-3) and b(scat) = 95 +/- 3 Mm(-1) from diesel exhaust. This apparent decrease in reported light-absorbing PM concentration was used to derive a correction K(ATN) for loading of strong light-absorbing particles onto or into the aethalometer filter tape, which was a function of attenuation of light at 880 nm by the embedded particles.     

Determination of levoglucosan in atmospheric fine particulate matter

A microanalytical method suitable for the quantitative determination of the sugar anhydride levoglucosan in low-volume samples of atmospheric fine particulate matter (PM) has been developed and validated. The method incorporates two sugar anhydrides as quality control standards. The recovery standard sedoheptulosan (2,7-anhydro-beta-D-altro-heptulopyranose) in 20 microL solvent is added onto samples of the atmospheric fine PM and aged for 1 hr before ultrasonic extraction with ethylacetate/ triethylamine. The extract is reduced in volume, an internal standard is added (1,5-anhydro-D-mannitol), and a portion of the extract is derivatized with 10% by volume N-trimethylsilylimidazole. The derivatized extract is analyzed by gas chromatography/mass spectrometry (GC/MS). The recovery of levoglucosan using this procedure was 69 +/- 6% from five filters amended with 2 microg levoglucosan, and the reproducibility of the assay is 9%. The limit of detection is approximately 0.1 microg/mL, which is equivalent to approximately 3.5 ng/m3 for a 10 L/min sampler or approximately 8.7 ng/m3 for a 4 L/min personal sampler (assuming 24-hr integrated samples). We demonstrated that levoglucosan concentrations in collocated samples (expressed as ng/m3) were identical irrespective of whether samples were collected by PM with aerodynamic diameter < or = 2.5 microm or PM with aerodynamic diameter < or = 10 microm impactors. It was also demonstrated that X-ray fluorescence analysis of samples of atmospheric PM, before levoglucosan determinations, did not alter the levels of levoglucosan.     

Transport of atmospheric fine particulate matter: part 1--findings from recent field programs on the extent of regional transport within North America

Air quality field data, collected as part of the fine particulate matter Supersites program and other field measurements programs, have been used to assess the role of aerosol transport, over length scales of approximately 100-1000 km, on fine particulate matter concentrations. Assessment of data from New York, NY; Baltimore, MD; Pittsburgh, PA; Atlanta, GA; Houston, TX; St. Louis, MO; and Fresno, CA, indicates that in virtually all of the regions, transport of aerosol over distances of 100-1000 km has a significant impact on urban particulate matter concentrations and a dominant role in determining rural particulate matter concentrations, though the nature of the regional contributions differs from region to region. This assessment is generally consistent with previous conceptual models of fine particulate matter formation and accumulation in these regions. The nature of the transported aerosol is largely sulfate in Eastern and Midwestern cities and nitrate in the Central Valley of California. In addition to physical transport of aerosol over distances of 100-1000 km, regional transport of aerosol precursors may lead to conditions conducive to large-scale nucleation events. Regional nucleation events have been reported in the East, Midwest, and in California. The events occurred in the morning soon after surface layers coupled with layers aloft, and the events generate ultrafine particles. In some cases, these nucleation events have been correlated with availability of sulfur dioxide and, therefore, may be sulfate formation events.     

Size distribution and source identification of total suspended particulate matter and associated heavy metals in the urban atmosphere of Delhi

A study of the atmospheric particulate size distribution of total suspended particulate matter (TSPM) and associated heavy metal concentrations has been carried out for the city of Delhi. Urban particles were collected using a five-stage impactor at six sites in three different seasons, viz. winter, summer and monsoon in the year 2001. Five samples from each site in each season were collected. Each sample (filter paper) was extracted with a mixture of nitric acid, hydrochloric acid and hydrofluoric acid. The acid solutions of the samples were analysed in five-particle fractions by atomic absorption spectrometry (AAS). The impactor stage fractionation of particles shows that a major portion of TSPM concentration is in the form of PM0.7 (i.e. <0.7microm). Similarly, the most of the metal mass viz. Mn, Cr, Cd, Pb, Ni, and Fe are also concentrated in the PM0.7 mode. The only exceptions are size distributions pertaining to Cu and Ca. Though, Cu is more in PM0.7 mode, its presence in size intervals 5.4-1.6microm and 1.6-0.7microm is also significant, whilst in case of Ca there is no definite pattern in its distribution with size of particles. The average PM10.9 (i.e. <10.9microm) concentrations are approximately 90.2%+/-4.5%, 81.4%+/-1.4% and 86.4%+/-9.6% of TSPM for winter, summer and monsoon seasons, respectively. Source apportionment reveals that there are two sources of TSPM and PM10.9, while three and four sources were observed for PM1.6 (i.e. <1.6microm) and PM0.7, respectively. Results of regression analyses show definite correlations between PM10.9 and other fine size fractions, suggesting PM10.9 may adequately act as a surrogate for both PM1.6 and PM0.7, while PM1.6 may adequately act as a surrogate for PM0.7.     

Improved identification of transition metals in airborne aerosols by SEM–EDX combined backscattered and secondary electron microanalysis

The SEM EDX backscattered electron (BSE) atomic number contrast has been largely used in this work, in combination with conventional secondary electron microanalysis, to investigate the presence of metal particles in airborne particulate collected at three sites (industrial, residential, and rural background) in the Po Valley (Italy). Individual particle x-ray microanalysis was used for this aim. In many cases, the presence of metal particles was not evident by secondary electron imaging and it was instead revealed by BSE detection. Metal particles were observed either as isolated (not clustered to other particles), or gathered together (homogeneous clusters). In addition, the BSE microanalysis put on evidence two main types of association of metals to other particulate components: heterogeneous clusters and metals embedded or enclosed in other materials. In this study, the first association (heterogeneous clusters) was observed mostly between Fe-bearing metallic particles and soot aggregates (or other carbonaceous particles) and it was found in the particulate matter (PM) of all studied sites. The second association, conversely, seems to be characterized by more selective relationships between composition/size of metal particles and type of other particulate components. These associations could be evidenced only when using the BSE Z-contrast and mainly concern three cases: (1) unusual silicate–carbonate mixed aggregates were observed at the industrial site only. In these aggregates, embedded Mn, Cr, Co, Bi, W, and Zr fine particles were selectively observed. (2) Ni and V rich ultrafine particles were only observed as embedded particles in the surface structure of carbon cenospheres. (3) Pb or Pb–Zn bearing fine and ultrafine particles were largely detected only in oxygenated organic aerosols in the ultrafine PM.     

Chemical composition of PM10 and PM2.5 collected at ground level and 100 meters during a strong winter-time pollution episode in Xi'an, China

An intensive sampling of aerosol particles from ground level and 100 m was conducted during a strong pollution episode during the winter in Xi'an, China. Concentrations of water-soluble inorganic ions, carbonaceous compounds, and trace elements were determined to compare the composition of particulate matter (PM) at the two heights. PM mass concentrations were high at both stations: PM10 (PM with aerodynamic diameter < or =10 microm) exceeded the China National Air Quality Standard Class II value on three occasions, and PM2.5 (PM with aerodynamic diameter < or =2.5 microm) exceeded the daily U.S. National Ambient Air Quality Standard more than 10 times. The PM10 organic carbon (OC) and elemental carbon (EC) were slightly lower at the ground than at 100 m, both in terms of concentration and percentage of total mass, but OC and EC in PM2.5 exhibited the opposite pattern. Major ionic species, such as sulfate and nitrate, showed vertical variations similar to the carbonaceous aerosols. High sulfate concentrations indicated that coal combustion dominated the PM mass both at the ground and 100 m. Correlations between K+ and OC and EC at 100 m imply a strong influence from suburban biomass burning, whereas coal combustion and motor vehicle exhaust had a greater influence on the ground PM. Stable atmospheric conditions apparently led to the accumulation of PM, especially at 100 m, and these conditions contributed to the similarities in PM at the two elevations. Low coefficient of divergence (CD) values reflect the similarities in the composition of the aerosol between sites, but higher CDs for fine particles compared with coarse ones were consistent with the differences in emission sources between the ground and 100 m.     

Carbonaceous aerosol characteristics in outdoor and indoor environments of Nanchang, China, during summer 2009

A study of carbonaceous aerosol was initiated in Nanchang, a city in eastern China, for the first time. Daily and diurnal (daytime and nighttime) PM2.5 (particulate matter with aerodynamic diameter < or =2.5 microm) samples were collected at an outdoor site and in three different indoor environments (common office, special printing and copying office, and student dormitory) in a campus of Nanchang University during summer 2009 (5-20 June). Daily PM10 (particulate matter with aerodynamic diameter < or =10 microm) samples were collected only at the outdoor site, whereas PM2.5 samples were collected at both indoor and outdoor sites. Loaded PM2.5 and PM10 samples were analyzed for organic and elemental carbon (OC, EC) by thermal/optical reflectance following the Interagency Monitoring of Protected Visual Environments-Advanced (IMPROVE-A) protocol. Ambient mass concentrations of PM10 and PM2.5 in Nanchang were compared with the air quality standards in China and the United States, and revealed high air pollution levels in Nanchang. PM2.5 accounted for about 70% of PM10, but the ratio of OC and EC in PM2.5 to that in PM10 was higher than 80%, which indicated that OC and EC were mainly distributed in the fine particles. The variations of carbonaceous aerosol between daytime and nighttime indicated that OC was released and formed more rapidly in daytime than in nighttime. OC/EC ratios were used to quantify secondary organic carbon (SOC). The differences in SOC and SOC/OC between daytime and nighttime were useful in interpreting the secondary formation mechanism. The results of (1) OC and EC contributions to PM2.5 at indoor sites and the outdoor site; (2) indoor-outdoor correlation of OC and EC; (3) OC-EC correlation; and (4) relative contributions of indoor and outdoor sources to indoor carbonaceous aerosol indicated that OC indoor sources existed in indoor sites, with the highest OC emissions in I2 (the special printing and copying office), and that indoor EC originated from outdoor sources. The distributions of eight carbon fractions in emissions from the printer and copier showed obviously high OC1 (>20%) and OC2 (approximately 30%), and obviously low EC1-OP (a pyrolyzed carbon fraction) (<10%), when compared with other sources.