Combustion aerosols: factors governing their size and composition and implications to human health

Particulate matter (PM) emissions from stationary combustion sources burning coal, fuel oil, biomass, and waste, and PM from internal combustion (IC) engines burning gasoline and diesel, are a significant source of primary particles smaller than 2.5 microns (PM2.5) in urban areas. Combustion-generated particles are generally smaller than geologically produced dust and have unique chemical composition and morphology. The fundamental processes affecting formation of combustion PM and the emission characteristics of important applications are reviewed. Particles containing transition metals, ultrafine particles, and soot are emphasized because these types of particles have been studied extensively, and their emissions are controlled by the fuel composition and the oxidant-temperature-mixing history from the flame to the stack. There is a need for better integration of the combustion, air pollution control, atmospheric chemistry, and inhalation health research communities. Epidemiology has demonstrated that susceptible individuals are being harmed by ambient PM. Particle surface area, number of ultrafine particles, bioavailable transition metals, polycyclic aromatic hydrocarbons (PAH), and other particle-bound organic compounds are suspected to be more important than particle mass in determining the effects of air pollution. Time- and size-resolved PM measurements are needed for testing mechanistic toxicological hypotheses, for characterizing the relationship between combustion operating conditions and transient emissions, and for source apportionment studies to develop air quality plans. Citations are provided to more specialized reviews, and the concluding comments make suggestions for further research.     

Combustion Aerosols: Factors Governing Their Size and Composition and Implications to Human Health

ABSTRACT

Particulate matter (PM) emissions from stationary combustion sources burning coal, fuel oil, biomass, and waste, and PM from internal combustion (IC) engines burning gasoline and diesel, are a significant source of primary particles smaller than 2.5 μm (PM_2.5) in urban areas. Combustion-generated particles are generally smaller than geologically produced dust and have unique chemical composition and morphology. The fundamental processes affecting formation of combustion PM and the emission characteristics of important applications are reviewed. Particles containing transition metals, ultrafine particles, and soot are emphasized because these types of particles have been studied extensively, and their emissions are controlled by the fuel composition and the oxidant-tem-perature-mixing history from the flame to the stack. There is a need for better integration of the combustion, air pollution control, atmospheric chemistry, and inhalation health research communities. Epidemiology has demonstrated that susceptible individuals are being harmed by ambient PM. Particle surface area, number of ultrafine particles, bioavailable transition metals, polycyclic aromatic hydrocarbons (PAH), and other particle-bound organic compounds are suspected to be more important than particle mass in determining the effects of air pollution. Time- and size-resolved PM measurements are needed for testing mechanistic toxicological hypotheses, for characterizing the relationship between combustion operating conditions and transient emissions, and for source apportionment studies to develop air quality plans. Citations are provided to more specialized reviews, and the concluding comments make suggestions for further research.     

Relation between particle mass and number for submicrometer airborne particles

The relationship between particle mass and the number of ambient air particles for the submicrometer size range was examined using a tapered element oscillating microbalance (TEOM) to determine the mass concentration, and a scan-ning mobility particle sizer (SMPS) to determine the volume concentration and total number of particles. The techniques were validated through their application to the estimation of submicrometer particle density for two laboratory generated aerosols of known bulk density (sodium chloride and di-2-ethylhexyl-sebacate). Further evaluation was done with the submicrometer fraction of laboratory generated environmental tobacco smoke (ETS), for which the estimated density of 1.18±0.06 g/cm³ was very close to the previously reported literature value of 1.12 g cm³. Finally, ambient air particles were examined and an estimate of the average submicrometer particle densities for these aerosols was found to vary from 1.2 to 1.8 g cm^-3 depending on the time of day. This high variation in the density of the ambient air submicrometer particles, makes it hard to estimate the mass concentration from the SMPS number concentration with better than 60% uncertainty, based on an assumed density value.     

Polybrominated diphenyl ethers in various atmospheric environments of Taiwan: their levels, source identification and influence of combustion sources

In this study, ambient air samples from different atmospheric environments were examined for both PBDE and PCDD/F characteristics to verify that combustion is a significant PBDE emission source. The mean ± SD atmospheric PBDE concentrations were 165 ± 65.0 pg Nm⁻³ in the heavy steel complex area and 93.9 ± 24.5 pg Nm⁻³ in the metals complex areas, 4.7 and 2.7 times higher than that (35.3 ± 15.5 pg Nm⁻³) in the urban areas, respectively. The statistically high correlation (r = 0.871, p < 0.001) found between the atmospheric PBDE and PCDD/F concentrations reveals that the combustion sources are the most likely PBDE emission sources. Correspondence analysis shows the atmospheric PBDEs of the heavy steel and metals complex areas are associated with BDE-209, -203, -207, -208, indicative of combustion source contributions. Furthermore, the PBDEs in urban ambient air experience the influence of the evaporative releases of the commercial penta- and octa-BDE mixtures, as well as combustion source emissions. By comparing the PBDE homologues of indoor air, urban ambient air, and stack flue gases of combustion sources, we found that the lighter brominated PBDEs in urban ambient air were contributed by the indoor air, while their highly brominated ones were from the combustion sources, such as vehicles. The developed source identification measure can be used to clarify possible PBDE sources not only for Taiwanese atmosphere but also for other environmental media in other countries associated with various emission sources in the future.     

南京大气细粒子中重金属污染特征及来源解析简

利用2011年1月、4月、7月和10月在南京市区和北郊采集的气溶胶样品，研究了南京大气细粒子中Zn、Pb、Hg、As和Cd 5种重金属的污染水平，通过元素相关性分析和因子分析方法，对细粒子中这些重金属的污染来源进行了初步解析。结果表明，南京大气细粒子及其重金属污染严重，北郊普遍比市区严重；As严重超标，Cd在南京北郊超标约5倍，Zn在市区与北郊的质量浓度均高于其他重金属元素。每种重金属的浓度均随季节而变化。市区细粒子中，As和Zn可能主要与燃煤、轮胎灰尘和建筑扬尘等有关，Pb、Hg和Cd主要来自交通尘、城市垃圾焚烧等。北郊细粒子中，As、Hg和Zn主要来源于燃煤、钢铁冶炼等工业，Pb和Cd主要与农作物秸秆燃烧、汽车尾气、道路扬尘等影响有关。     

南京大气细粒子中重金属污染特征及来源解析

利用2011年1月、4月、7月和10月在南京市区和北郊采集的气溶胶样品，研究了南京大气细粒子中zn、Ph、Hg、As和cd5种重金属的污染水平，通过元素相关性分析和因子分析方法，对细粒子中这些重金属的污染来源进行了初步解析。结果表明，南京大气细粒子及其重金属污染严重，北郊普遍比市区严重；As严重超标，cd在南京北郊超标约5倍，zn在市区与北郊的质量浓度均高于其他重金属元素。每种重金属的浓度均随季节而变化。市区细粒子中，As和zn可能主要与燃煤、轮胎灰尘和建筑扬尘等有关，Pb、Hg和cd主要来自交通尘、城市垃圾焚烧等。北郊细粒子中，As、Hg和zn主要来源于燃煤、钢铁冶炼等工业，Pb和cd主要与农作物秸秆燃烧、汽车尾气、道路扬尘等影响有关。     

Monitoring of sources and atmospheric processes controlling air quality in an urban Mediterranean environment

Different monitoring parameters (PM mass concentrations, number–size distribution, black carbon, gaseous pollutants, and chemical composition, among others) are currently used in air quality studies. Urban aerosols are the result of several sources and atmospheric processes, which suggests that a single monitoring technique is insufficient to quantitatively evaluate all of them.This study assesses the suitability of a number of monitoring techniques (PM mass concentrations, number and size distribution of ultra-fine particles, levels of gaseous pollutants, and a complete chemical characterization of PM₁₀ and PM_2.5) by examining the response of those techniques to the different emission sources and/or atmospheric processes affecting an urban Mediterranean area (Barcelona, NE Spain).The results of this work reveal that the PM mass, the number concentration and the chemical composition give different, but complementary, information. Whereas the mineral matter, a key atmospheric aerosol component across the Mediterranean, is not properly quantitatively assessed by measuring sub-micrometric particles, the monitoring of the number concentration is indispensable to interpret the origin of specific aerosol episodes. Furthermore, the chemical composition yields very relevant information to deduce the causes of specific pollution episodes.The number concentration of ultra-fine particles in urban areas is strongly dependent upon vehicle exhaust emissions, which may cause adverse health impacts. Moreover, urban Mediterranean environments are favourable to produce nucleation-mode particles (<20 nm) with photochemical origin. In those cases, these particles are expected to be of high solubility and consequently their toxicity may differ from that of traffic-generated ultra-fine particles. Thus, the use of a single monitoring parameter to evaluate the health effects seems to be not enough.     

Dilution-based emissions sampling from stationary sources: Part 2--Gas-fired combustors compared with other fuel-fired systems

With the recent focus on fine particle matter (PM2.5), new, self-consistent data are needed to characterize emissions from combustion sources. Such data are necessary for health assessment and air quality modeling. To address this need, emissions data for gas-fired combustors are presented here, using dilution sampling as the reference. The dilution method allows for collection of emitted particles under conditions simulating cooling and dilution during entry from the stack into the air. The sampling and analysis of the collected particles in the presence of precursor gases, SO2 nitrogen oxide, volatile organic compound, and NH3 is discussed; the results include data from eight gas fired units, including a dual-fuel institutional boiler and a diesel engine powered electricity generator. These data are compared with results in the literature for heavy-duty diesel vehicles and stationary sources using coal or wood as fuels. The results show that the gas-fired combustors have very low PM2.5 mass emission rates in the range of approximately 10(-4) lb/million Btu (MMBTU) compared with the diesel backup generator with particle filter, with approximately 5 x 10(-3) lb/MMBTU. Even higher mass emission rates are found in coal-fired systems, with rates of approximately 0.07 lb/MMBTU for a bag-filter-controlled pilot unit burning eastern bituminous coal. The characterization of PM2.5 chemical composition from the gas-fired units indicates that much of the measured primary particle mass in PM2.5 samples is organic or elemental carbon and, to a much less extent, sulfate. Metal emissions are quite low compared with the diesel engines and the coal- or wood-fueled combustors. The metals found in the gas-fired combustor particles are low in concentration, similar in concentration to ambient particles. The interpretation of the particulate carbon emissions is complicated by the fact that an approximately equal amount of particulate carbon (mainly organic carbon) is found on the particle collector and a backup filter. It is likely that measurement artifacts, mostly adsorption of volatile organic compounds on quartz filters, are positively biasing "true" particulate carbon emission results.     

An inexpensive method to estimate CO and NOx emissions from mobile sources

CO and NO_x measurements from mobile sources at two urban locations in Córdoba City, Argentina, were used to develop a very simple method to estimate emission from these sources. This development was possible because primary urban air pollution in Córdoba comes mostly from mobile sources and because a field measurement campaign was conducted by the city government during 1995–1996 that has allowed us to have a complete and valuable data bank. Air concentrations of CO, NO_x as well as physical, and meteorological variables were measured at two urban sites with two monitoring stations. We compared the measured CO and NO_x air concentration data with the predictions of a method that uses regression analysis to estimate the emission factor from the mobile sources. The agreement is good, considering the simplicity of the approach.     

Analysis of air quality observations with the aid of the source-receptor relationship approach

In this study, an attempt was made to analyze time series of air quality measurements (O3, SO2, SO4(2-), NOx) conducted at a remote place in the eastern Mediterranean (Finokalia at Crete Island in 1999) to obtain concrete information on potential contributions from emission sources. For the definition of a source-receptor relationship, advanced meteorological and dispersion models appropriate to identify "areas of influence" have been used. The model tools used are the Regional Atmospheric Modeling System and the Lagrangian-type particle dispersion model (forward and backward in time), with capabilities to derive influence functions and definition of "areas of influence." When high levels of pollutants have been measured at the remote location of Finokalia, particles are released from this location (receptor) and traced backward in time. The influence function derived from particle distributions characterizes dispersion conditions in the atmosphere and also provides information on potential contributions from emission sources within the modeling domain to this high concentration. As was shown in the simulation results, the experimental site of Finokalia in Crete is influenced during the selected case studies, primarily by pollutants emitted from the urban conglomerate of Athens. Secondarily, it is influenced by polluted air masses arriving from Italy and/or the Black Sea Region. For some specific cases, air pollutants monitored at Finokalia were possibly related to war activities in the West Balkan Region (Kosovo).     

Characterization of atmospheric particulates, particle-bound transition metals and polycyclic aromatic hydrocarbons of urban air in the centre of Athens (Greece)

The concentrations of trace metals and polycyclic aromatic hydrocarbons (PAHs) adsorbed to total suspended particulate (TSP) and finer fractions of airborne particulate matter (PM) were determined from a site in the centre of Athens (Greece), which is characterized by heavy local traffic and is densely populated, during the winter and summer periods in 2003-2004. Also, we collected and analyzed samples of diesel and gasoline exhaust particles from local vehicles (buses, taxis and private cars) and from chimney exhaust of residential central heating appliances. A seasonal effect was observed for the size distribution of aerosol mass, with a shift to larger fine fractions in winter. The most commonly detected trace metals in the TSP and PM fractions were Fe, Pb, Zn, Cu, Cr, V, Ni and Cd and their concentrations were similar to levels observed in heavily polluted urban areas from local traffic and other anthropogenic emissions. Analysis of 16 PAHs bound to PM showed that they are mostly traffic related. In general, the fine particulate PAHs concentrations were higher than coarse particles. The most common PAHs in PM(10.2) and PM(2.1) were pyrene, phenanthrene, acenapthylene and fluoranthene, which are associated with diesel and gasoline exhaust particles. The results of this study underlined the importance of local emission sources, especially vehicular traffic, central heating and other local anthropogenic emissions. Compared with other big cities, Athens has much higher levels of airborne particles, especially of the finer fractions PM(10) and PM(2.5), correlated with traffic-related air pollution.     

Analysis of point source emissions in the Texas-Mexico border region

Pollutant emissions in the Texas-Mexico border were investigated using an emission database that covers 25 Texas counties and the states of Coahuila, Chihuahua, Nuevo Leon and Tamaulipas in Mexico. Major emissions are from energy generation, mainly from two coal-fired facilities in Coahuila, which also generate most of carbon dioxide. Texas exhibits a larger concentration of sources; around Laredo and the Lower Rio Grande Valley and a sugarcane mill is a significant contributor to particles emissions. In Mexico the minerals and metals industries are the second major contributors to emissions, especially particles. Fossil fuel production is the main source of VOCs.     

Estimation of atmospheric trace metal emissions in Vilnius City, Lithuania, using vertical concentration gradient and road tunnel measurement data

A new approach for the estimation of trace metal emissions in Vilnius city was implemented, using vertical concentration profiles in the urban boundary layer and road tunnel measurement data. Heavy metal concentrations were examined in fine and coarse particle fractions using a virtual impactor (cut-off size diameter 2.5 μm). Negative vertical concentration gradients were obtained for all metals (Ba, Pb, V, Sb, Zn) and both fractions. It was estimated that the vertical concentration gradient was formed due to emissions from an area of about 12 km². Road tunnel measurements indicated that trace metal concentrations on fine particles were lower than those on coarse particles, which suggested that re-emitted road dust was highly enriched in trace metal due to historic emissions within the tunnel. Emission rates of different pollutants in the road tunnel were calculated using pollutant concentration differences at the tunnel entrance and exit and traffic flow data. Heavy metal emission rates from the area of Vilnius city were estimated using the vertical gradient of heavy metal concentrations and the coefficient of turbulent mixing, as derived from meteorological measurement data. The emission values calculated by the two different methods coincided reasonably well, which indicated that the main source of airborne trace metals in Vilnius city is traffic. The potential of the vertical concentration gradient method for the direct estimation of urban heavy metal emissions was demonstrated.     

Surface Air Pollutant Concentration Frequency Distributions: Implications for Urban Modeling

With the development of ambient air quality standards (AAQS), the need arises to describe the characteristics of regional surface air-pollutant concentration frequency distributions. In the evaluation of land use plans, numerous agencies will be concerned with evaluating the effectiveness of emission zoning and/or control actions. On a regional basis, one means of performing this assessment lies in determining the changes in the pollutant frequency distributions resulting from control actions.

This study presents new data concerning the surface air-pollutant concentration frequency distributions observed for area sources and continuous point sources, and compares these distributions with those of the pertinent meteorological variables describing the transport and diffusion of the pollutant. The observed surface air pollutant frequency distributions are compared to those corresponding to simple modeling concepts from either an urban area source or a continuous point source. For an urban source and a relatively inert pollutant like CO, we found that the observed frequency distribution for CO surface air concentration parallels the approximately log-normal frequency distribution of the reciprocal of the wind speed. We show that the constant relating these two well-correlated frequency distributions can be determined either experimentally or with a numerical simulation model of air pollution. The usefulness of numerical models in air pollution is discussed.     

Assessment of atmospheric metallic pollution in the metropolitan region of São Paulo, Brazil, employing Tillandsia usneoides L. as biomonitor

Tillandsia usneoides L. is an epiphytic bromeliad plant able to absorb water and nutrients directly from the air. For this reason this species was selected to carry out a monitoring study of air pollution in the metropolitan region of S?o Paulo, Brazil. Five consecutive transplantation experiments (8 weeks each) were performed in 10 sites of the city, submitted to different sources of air pollution (industrial, vehicular), using plants collected from an unpolluted area. After exposure, trace metals were analyzed in the plant by instrumental neutron activation analysis. Traffic-related elements such as Zn and Ba presented high concentrations in exposure sites near to heavy traffic avenues (cars, buses and trucks) and may be associated to vehicular sources. For Zn and Co the highest contents were related to industrial zones and can be associated to the presence of anthropogenic emission sources. The rare earth elements, Fe and Rb, probably have soil particles as main source.     

Analysis of Air Quality Observations with the Aid of the Source-Receptor Relationship Approach

Abstract

In this study, an attempt was made to analyze time series of air quality measurements (O₃, SO₂, SO₄ ^2?NO_x) conducted at a remote place in the eastern Mediterranean (Finokalia at Crete Island in 1999) to obtain concrete information on potential contributions from emission sources. For the definition of a source-receptor relationship, advanced meteorological and dispersion models appropriate to identify “areas of influence” have been used. The model tools used are the Regional Atmospheric Modeling System and the Lagrangian-type particle dispersion model (forward and backward in time), with capabilities to derive influence functions and definition of “areas of influence.” When high levels of pollutants have been measured at the remote location of Finokalia, particles are released from this location (receptor) and traced backward in time. The influence function derived from particle distributions characterizes dispersion conditions in the atmosphere and also provides information on potential contributions from emission sources within the modeling domain to this high concentration. As was shown in the simulation results, the experimental site of Finokalia in Crete is influenced during the selected case studies, primarily by pollutants emitted from the urban conglomerate of Athens. Secondarily, it is influenced by polluted air masses arriving from Italy and/or the Black Sea Region. For some specific cases, air pollutants monitored at Finokalia were possibly related to war activities in the West Balkan Region (Kosovo).     

Estimation of Organic Compound Emissions from Waste Lagoons

Abstract

With the recent focus on fine particle matter (PM_2.5),new, self-consistent data are needed to characterize emissions from combustion sources. Such data are necessary for health assessment and air quality modeling. To address this need, emissions data for gas-fired combustors are presented here, using dilution sampling as the reference.The dilution method allows for collection of emitted particles under conditions simulating cooling and dilution during entry from the stack into the air. The sampling and analysis of the collected particles in the presence of precursor gases, SO₂, nitrogen oxide, volatile organic compound, and NH₃ is discussed; the results include data from eight gas fired units, including a dual-fuel institutional boiler and a diesel engine powered electricity generator. These data are compared with results in the literature for heavy-duty diesel vehicles and stationary sources using coal or wood as fuels. The results show that the gas-fired combustors have very low PM_2.5 mass emission rates in the range of ～10_-4 lb/million Btu (MMBTU) compared with the diesel backup generator with particle filter, with ～5 × 10_-3 lb/MMBTU. Even higher mass emission rates are found in coal-fired systems, with rates of ～0.07 lb/MMBTU for a bag-filter-controlled pilot unit burning eastern bituminous coal. The characterization of PM_2.5 chemical composition from the gas-fired units indicates that much of the measured primary particle mass in PM_2.5 samples is organic or elemental carbon and, to a much less extent, sulfate. Metal emissions are quite low compared with the diesel engines and the coal- or woodfueled combustors. The metals found in the gas-fired combustor particles are low in concentration, similar in concentration to ambient particles. The interpretation of the particulate carbon emissions is complicated by the fact that an approximately equal amount of particulate carbon (mainly organic carbon) is found on the particle collector and a backup filter. It is likely that measurement artifacts, mostly adsorption of volatile organic compounds on quartz filters, are positively biasing “true” particulate carbon emission results.     

Emission factors of air toxics from semiconductor manufacturing in Korea

The development of local, accurate emission factors is very important for the estimation of reliable national emissions and air quality management. For that, this study is performed for pollutants released to the atmosphere with source-specific emission tests from the semiconductor manufacturing industry. The semiconductor manufacturing industry is one of the major sources of air toxics or hazardous air pollutants (HAPs); thus, understanding the emission characteristics of the emission source is a very important factor in the development of a control strategy. However, in Korea, there is a general lack of information available on air emissions from the semiconductor industry. The major emission sources of air toxics examined from the semiconductor manufacturing industry were wet chemical stations, coating applications, gaseous operations, photolithography, and miscellaneous devices in the wafer fabrication and semiconductor packaging processes. In this study, analyses of emission characteristics, and the estimations of emission data and factors for air toxics, such as acids, bases, heavy metals, and volatile organic compounds from the semiconductor manufacturing process have been performed. The concentration of hydrogen chloride from the packaging process was the highest among all of the processes. In addition, the emission factor of total volatile organic compounds (TVOCs) for the packaging process was higher than that of the wafer fabrication process. Emission factors estimated in this study were compared with those of Taiwan for evaluation, and they were found to be of similar level in the case of TVOCs and fluorine compounds.     

Air ion concentrations in various urban outdoor environments

Atmospheric ions are produced by many natural and anthropogenic sources and their concentrations vary widely between different environments. There is very little information on their concentrations in different types of urban environments, how they compare across these environments and their dominant sources. In this study, we measured airborne concentrations of small ions, particles and net particle charge at 32 different outdoor sites in and around a major city in Australia and identified the main ion sources. Sites were classified into seven groups as follows: park, woodland, city centre, residential, freeway, power lines and power substation. Generally, parks were situated away from ion sources and represented the urban background value of about 270 ions cm^?3. Median concentrations at all other groups were significantly higher than in the parks. We show that motor vehicles and power transmission systems are two major ion sources in urban areas. Power lines and substations constituted strong unipolar sources, while motor vehicle exhaust constituted strong bipolar sources. The small ion concentration in urban residential areas was about 960 cm^?3. At sites where ion sources were co-located with particle sources, ion concentrations were inhibited due to the ion-particle attachment process. These results improved our understanding on air ion distribution and its interaction with particles in the urban outdoor environment.     

Concentration, size distribution, and dry deposition rate of particle-associated metals in the Los Angeles region

Daily averaged atmospheric concentrations and dry deposition fluxes of particulate metals were measured seasonally at six urban sites and one non-urban coastal site in the Los Angeles region using a conventional total suspended particulate matter (TSP) filter, surrogate surface deposition plates, and a Noll Rotary Impactor (NRI), which provides information about particle size distribution in four size ranges above 6 μm. With the exception of the non-urban site, particulate metal concentrations and deposition fluxes were remarkably uniform spatially and temporally. At all sites there were significant metal concentrations on particles greater than 10 μm, a commonly used upper limit for many air quality monitoring studies, and these large particles were estimated to be responsible for most of the deposited mass of metals. Annual averaged values of deposition rates measured with a surrogate surface were in good agreement with values estimated using theoretical deposition velocities in conjunction with measured size-segregated particle concentrations. Image analysis of particles deposited on NRI stage A, which collects all particles greater than 6 μm, indicated nighttime metal concentrations and deposition at the non-urban coastal site was higher than in the day time due to offshore advection of urban air associated with the diurnal land breeze. Measured enrichments of crustal elements and metals were correlated, indicating efficient mixing of natural and anthropogenic material from different sources, hypothesized to be the result of cyclical resuspension and deposition of dust by moving vehicles and wind.