Chapter two: methodologies for characterisation of combustion sources and for quantification of their emissions

Emissions from the combustion of biomass and fossil fuels result in generation of a large number of particle and gaseous products in outdoor and/or indoor air, which create health and environmental risks. Of particular importance are the very small particles that are emitted in large quantities from all the combustion sources, and that could be potentially more significant in terms of their impact on health and the environment than larger particles. It is important to quantify particle emissions from combustion sources for regulatory and control purposes in relation to air quality. This paper is a review of particle characteristics that are used as source signatures, their general advantages and limitations, as well as a review of source signatures of the most common combustion pollution sources including road transport, industrial facilities, small household combustion devices, environmental tobacco smoke, and vegetation burning. The current methods for measuring particle physical characteristics (mass and number concentrations) and principles of methodologies for measuring emission factors are discussed in the paper as well. Finally, the paper presents the recommendations for the future techniques for measurements of combustion products.     

Combustion sources of particles: 2. Emission factors and measurement methods

Emissions from the combustion of biomass and fossil fuels are a significant source of particulate matter (PM) in ambient outdoor and/or indoor air. It is important to quantify PM emissions from combustion sources for regulatory and control purposes in relation to air quality. In this paper, we review emission factors for several types of important combustion sources: road transport, industrial facilities, small household combustion devices, environmental tobacco smoke, and vegetation burning. We also review current methods for measuring particle physical characteristics (mass and number concentrations) and principles of methodologies for measuring emission factors. The emission factors can be measured on a fuel-mass basis and/or a task basis. Fuel-mass based emission factors (e.g., g/kg of fuel) can be readily used for the development of emission inventories when the amount of fuels consumed are known. Task-based emission factors (g/mile driven, g/MJ generated) are more appropriate when used to conduct comparisons of air pollution potentials of different combustion devices. Finally, we discuss major shortcomings and limitations of current methods for measuring particle emissions and present recommendations for development of future measurement techniques.     

Is levoglucosan a suitable quantitative tracer for wood burning? Comparison with receptor modeling on trace elements in Lycksele, Sweden

Particle emissions from residential wood combustion in small communities in Northern Sweden can sometimes increase the ambient particle concentrations to levels comparable to densely trafficked streets in the center of large cities. The reason for this is the combination of increased need for domestic heating during periods of low temperatures, leading to higher emission rates, and stable meteorological conditions. In this work, the authors compare two different approaches to quantify the wood combustion contribution to fine particles in Northern Sweden: a multivariate source-receptor analysis on inorganic compounds followed by multiple linear regression (MLR) of fine particle concentrations and levoglucosan used as a tracer. From the receptor model, it can be seen that residential wood combustion corresponds with 70% of modeled particle mass. Smaller contributions are also seen from local nonexhaust traffic particles, road dust, and brake wear (each contributing 14%). Of the mass, 1.5% is explained by long-distance transported particles, and 2% derives from a regional source deriving from either oil combustion or smelter activities. In samples collected in ambient air, a significant linear correlation was found between wood burning particles and levoglucosan. The levoglucosan fraction in the ambient fine particulate matter attributed to wood burning according to the multivariate analysis ranged from < 2% to 50%. This is much higher than the fraction found in the emission from the boilers expected to be responsible for most emissions at this site (between 3% and 6%). A laboratory emission study of wood and pellet boilers gave 0.3% wt to 22% wt levoglucosan to particle mass, indicating that the levoglucosan fraction may be highly dependent on combustion conditions, making it uncertain to use it as a quantitative tracer under real-world burning conditions. Thus, quantitative estimates of wood burning contributions will be very uncertain using solely levoglucosan as a tracer.     

Is Levoglucosan a Suitable Quantitative Tracer for Wood Burning? Comparison with Receptor Modeling on Trace Elements in Lycksele,Sweden

Abstract

Particle emissions from residential wood combustion in small communities in Northern Sweden can sometimes increase the ambient particle concentrations to levels comparable to densely trafficked streets in the center of large cities. The reason for this is the combination of increased need for domestic heating during periods of low temperatures, leading to higher emission rates, and stable meteorological conditions. In this work, the authors compare two different approaches to quantify the wood combustion contribution to fine particles in Northern Sweden: a multivariate source-receptor analysis on inorganic compounds followed by multiple linear regression (MLR) of fine particle concentrations and levoglucosan used as a tracer. From the receptor model, it can be seen that residential wood combustion corresponds with 70% of modeled particle mass. Smaller contributions are also seen from local nonexhaust traffic particles, road dust, and brake wear (each contributing 14%). Of the mass, 1.5% is explained by long-distance transported particles, and 2% derives from a regional source deriving from either oil combustion or smelter activities.

In samples collected in ambient air, a significant linear correlation was found between wood burning particles and levoglucosan. The levoglucosan fraction in the ambient fine particulate matter attributed to wood burning according to the multivariate analysis ranged from <2% to 50%. This is much higher than the fraction found in the emission from the boilers expected to be responsible for most emissions at this site (between 3% and 6%). A laboratory emission study of wood and pellet boilers gave 0.3%_wt to 22%_wt levoglucosan to particle mass, indicating that the levoglucosan fraction may be highly dependent on combustion conditions, making it uncertain to use it as a quantitative tracer under real-world burning conditions. Thus, quantitative estimates of wood burning contributions will be very uncertain using solely levoglucosan as a tracer.     

Comparison of particle emissions from small heavy fuel oil and wood-fired boilers

Flue gas emissions of wood and heavy fuel oil (HFO) fired district heating units of size range 4–15 MW were studied. The emission measurements included analyses of particle mass, number and size distributions, particle chemical compositions and gaseous emissions. Thermodynamic equilibrium calculations were carried out to interpret the experimental findings.In wood combustion, PM1 (fine particle emission) was mainly formed of K, S and Cl, released from the fuel. In addition PM1 contained small amounts of organic material, CO₃, Na and different metals of which Zn was the most abundant. The fine particles from HFO combustion contained varying transient metals and Na that originate from the fuel, sulphuric acid, elemental carbon (soot) and organic material. The majority of particles were formed at high temperature (>800 °C) from V, Ni, Fe and Na. At the flue gas dew point (125 °C in undiluted flue gas) sulphuric acid condensed forming a liquid layer on the particles. This increases the PM1 substantially and may lead to partial dissolution of the metallic cores.Wood-fired grate boilers had 6–21-fold PM1 and 2–23-fold total suspended particle (TSP) concentrations upstream of the particle filters when compared to those of HFO-fired boilers. However, the use of single field electrostatic precipitators (ESP) in wood-fired grate boilers decreased particle emissions to same level or even lower as in HFO combustion. On the other hand, particles released from the HFO boilers were clearly smaller and higher in number concentration than those of wood boilers with ESPs. In addition, in contrast to wood combustion, HFO boilers produce notable SO₂ emissions that contribute to secondary particle formation in the atmosphere. Due to vast differences in concentrations of gaseous and particle emissions and in the physical and chemical properties of the particles, HFO and wood fuel based energy production units are likely to have very different effects on health and climate.     

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.     

Primary sources of selected POPs: regional and global scale emission inventories

During the last decade, a number of studies have been devoted to the sources and emissions of Persistent Organic Pollutants (POPs) at regional and global scales. While significant improvements in knowledge have been achieved for some pesticides, the quantitative understanding of the emission processes and emission patterns for "non-pesticide" POPs are still considered limited. The key issues remaining for the non-pesticide POPs are in part determined by their general source classification. For industrial chemicals, such as the polychlorinated biphenyls (PCBs), there is considerable uncertainty with respect to the relative importance of atmospheric emissions from various source categories. For PCBs, temperature is discussed as a potential key factor influencing atmospheric emission levels and patterns. When it comes to the unintentional by-products of combustion and industrial processes (PCDD/Fs), there is still a large uncertainty with respect to the relative contribution of emissions from unregulated sources such as backyard barrel burning that requires further consideration and characterisation. For hexachlorobenzene (HCB), the relative importance of primary and secondary atmospheric emissions in controlling current atmospheric concentrations remains one of the key uncertainties. While these and other issues may remain unresolved, knowledge concerning the emissions of POPs is a prerequisite for any attempt to understand and predict the distribution and fate of these chemicals on a regional and global scale as well as to efficiently minimise future environmental burdens.     

Updating the conceptual model for fine particle mass emissions from combustion systems

Atmospheric transformations determine the contribution of emissions from combustion systems to fine particulate matter (PM) mass. For example, combustion systems emit vapors that condense onto existing particles or form new particles as the emissions are cooled and diluted. Upon entering the atmosphere, emissions are exposed to atmospheric oxidants and sunlight, which causes them to evolve chemically and physically, generating secondary PM. This review discusses these transformations, focusing on organic PM. Organic PM emissions are semi-volatile at atmospheric conditions and thus their partitioning varies continuously with changing temperature and concentration. Because organics contribute a large portion of the PM mass emitted by most combustion sources, these emissions cannot be represented using a traditional, static emission factor. Instead, knowledge of the volatility distribution of emissions is required to explicitly account for changes in gas-particle partitioning. This requires updating how PM emissions from combustion systems are measured and simulated from combustion systems. Secondary PM production often greatly exceeds the direct or primary PM emissions; therefore, secondary PM must be included in any assessment of the contribution of combustion systems to ambient PM concentrations. Low-volatility organic vapors emitted by combustion systems appear to be very important secondary PM precursors that are poorly accounted for in inventories and models. The review concludes by discussing the implications that the dynamic nature of these PM emissions have on source testing for emission inventory development and regulatory purposes. This discussion highlights important linkages between primary and secondary PM, which could lead to simplified certification test procedures while capturing the emission components that contribute most to atmospheric PM mass.     

Measurement of ultrafine particle size distributions from coal-, oil-, and gas-fired stationary combustion sources

Currently, we have limited knowledge of the physical and chemical properties of emitted primary combustion aerosols and the changes in those properties caused by nucleation, condensation growth of volatile species, and particle coagulations under dilution and cooling in the ambient air. A dilution chamber was deployed to sample exhaust from a pilot-scale furnace burning various fuels at a nominal heat input rate of 160 kW/h(-1) and 3% excess oxygen. The formation mechanisms of particles smaller than 420 nm in electrical mobility diameter were experimentally investigated by measurement with a Scanning Mobility Particle Sizer (SMPS) as a function of aging times, dilution air ratios, combustion exhaust temperatures, and fuel types. Particle formation in the dilution process is a complex mixture of nucleation, coagulation, and condensational growth, depending on the concentrations of available condensable species and solid or liquid particles (such as soot, ash) in combustion exhausts. The measured particle size distributions in number concentrations measured show peaks of particle number concentrations for medium sulfur bituminous coal, No. 6 fuel oil, and natural gas at 40-50 nm, 70-100 nm, and 15-25 nm, respectively. For No. 6 fuel oil and coal, the particle number concentration is constant in the range of a dilution air ratio of 50, but the number decreases as the dilution air ratio decreases to 10. However, for natural gas, the particle number concentration is higher at a dilution air ratio of 10 and decreases at dilution air ratios of 20-50. At a dilution air ratio of 10, severe particle coagulation occurs in a relatively short time. Samples taken at different combustion exhaust temperatures for these fuel types show higher particle number concentrations at 645 K than at 450 K. As the aging time of particles increases, the particles increase in size and the number concentrations decrease. The largest gradient of particle number distribution occurs within the first 10 sec after dilution but shows only minor differences between 10 and 80 sec. The lifetimes of the ultrafine particles are relatively short, with a scale on the order of a few seconds. Results from this study suggest that an aging time of 10 sec and a dilution air ratio of 20 are sufficient to obtain representative primary particle emission samples from stationary combustion sources.     

Trends in hazardous trace metal concentrations in aerosols collected in Beijing, China from 2001 to 2006

Daily observations of hazardous trace metal concentrations in aerosols in Beijing, China were made in the period from 2001 to 2006. We considered coal combustion as a major source of some anthropogenic metals by achieving a correlation analysis and by investigating enrichment factors and relative composition of metals. A possible extra source of some specific metals, such as Cu and Sb, was brake abrasion particles, however, we did not think the transport-related particle was a major source for the hazardous anthropogenic metals even though they could originate from vehicle exhaust and brake/tire abrasion particles. A time-trend model was used to describe temporal variations of chemical constituent concentrations during the five-year period. Several crustal elements, such as Al, Ti, V, Cr, Mn, Fe, and Co, did not show clear increases, with annual rates of change of -15.2% to 3.6%. On the other hand, serious increasing trends were noted from several hazardous trace metals. Cu, Zn, As, Cd, and Pb, which are derived mainly from anthropogenic sources, such as coal combustion, showed higher annual rate of change (4.9-19.8%, p<0.001) according to the regression model. In particular, the Cd and Pb concentrations increased remarkably. We hypothesize that the trend towards increasing concentrations of metals in the air reflects a change that has occurred in the process of burning coal, whereby the use of higher temperatures for coal combustion has resulted in increased emissions of these metals. The increasing use of low-rank coal may also explain the observed trends. In addition, nonferrous metal smelters are considered as a potential, albeit minor, reason for the increasing atmospheric concentrations of anthropogenic hazardous metals in Beijing city.     

Size-resolved trace metal characterization of aerosols emitted by four important source types in Switzerland

In central Switzerland five types of emission sources are mainly responsible for airborne trace metals: traffic, industrial plants burning heavy oil, resuspension of soil particles, residential heatings and refuse incineration plants. The particulate emissions of each of these source types except refuse incineration were sampled using Berner impactors and the mass and elemental size distributions of Cd, Cu, Mn, Pb, Zn, As and Na determined.Cd, Na and Zn are not characteristic for any of these source types. As and Cu, occurring in the fine particle fractions are characteristic for heavy oil combustion, Mn for soil dust and sometimes for heavy and fuel oil combustion and Pb for traffic aerosols. The mass size distributions of aerosols originating from erosion and abrasion processes show a maximum mass fraction in the coarse particle range larger than about 1 μm aerodynamic equivalent diameters (A.E.D.). Aerosols originating from combustion processes show a second maximum mass fraction in the fine particle range below about 0.5μm A.E.D.Scanning electron microscopy combined with an EDS analyzer was used for the morphological characterization of emission and ambient aerosols.     

Particle emission factors during cooking activities

Exposure to particles emitted by cooking activities may be responsible for a variety of respiratory health effects. However, the relationship between these exposures and their subsequent effects on health cannot be evaluated without understanding the properties of the emitted aerosol or the main parameters that influence particle emissions during cooking. Whilst traffic-related emissions, stack emissions and concentrations of ultrafine particles (UFPs, diameter < 100 nm) in urban ambient air have been widely investigated for many years, indoor exposure to UFPs is a relatively new field and in order to evaluate indoor UFP emissions accurately, it is vital to improve scientific understanding of the main parameters that influence particle number, surface area and mass emissions. The main purpose of this study was to characterise the particle emissions produced during grilling and frying as a function of the food, source, cooking temperature and type of oil. Emission factors, along with particle number concentrations and size distributions were determined in the size range 0.006–20 μm using a Scanning Mobility Particle Sizer (SMPS) and an Aerodynamic Particle Sizer (APS). An infrared camera was used to measure the temperature field. Overall, increased emission factors were observed to be a function of increased cooking temperatures. Cooking fatty foods also produced higher particle emission factors than vegetables, mainly in terms of mass concentration, and particle emission factors also varied significantly according to the type of oil used.     

Measurement of Ultrafine Particle Size Distributions from Coal-, Oil-, and Gas-Fired Stationary Combustion Sources

Abstract

Currently, we have limited knowledge of the physical and chemical properties of emitted primary combustion aerosols and the changes in those properties caused by nucleation, condensation growth of volatile species, and particle coagulations under dilution and cooling in the ambient air. A dilution chamber was deployed to sample exhaust from a pilot-scale furnace burning various fuels at a nominal heat input rate of 160 kW/h^?1 and 3% excess oxygen. The formation mechanisms of particles smaller than 420 nm in electrical mobility diameter were experimentally investigated by measurement with a Scanning Mobility Particle Sizer (SMPS) as a function of aging times, dilution air ratios, combustion exhaust temperatures, and fuel types. Particle formation in the dilution process is a complex mixture of nucleation, coagulation, and condensational growth, depending on the concentrations of available condensable species and solid or liquid particles (such as soot, ash) in combustion exhausts. The measured particle size distributions in number concentrations measured show peaks of particle number concentrations for medium sulfur bituminous coal, No. 6 fuel oil, and natural gas at 40-50 nm, 70-100 nm, and 15-25 nm, respectively. For No. 6 fuel oil and coal, the particle number concentration is constant in the range of a dilution air ratio of 50, but the number decreases as the dilution air ratio decreases to 10. However, for natural gas, the particle number concentration is higher at a dilution air ratio of 10 and decreases at dilution air ratios of 20-50. At a dilution air ratio of 10, severe particle coagulation occurs in a relatively short time. Samples taken at different combustion exhaust temperatures for these fuel types show higher particle number concentrations at 645 K than at 450 K. As the aging time of particles increases, the particles increase in size and the number concentrations decrease. The largest gradient of particle number distribution occurs within the first 10 sec after dilution but shows only minor differences between 10 and 80 sec. The lifetimes of the ultrafine particles are relatively short, with a scale on the order of a few seconds. Results from this study suggest that an aging time of 10 sec and a dilution air ratio of 20 are sufficient to obtain representative primary particle emission samples from stationary combustion sources.     

Analysis and discussion on formation and control of primary particulate matter generated from coal-fired power plants

Particulate matter (PM) has been becoming the principal urban pollutant in many major cities in China, and even all over the world. It is reported that the coal combustion process is one of the main sources of PM in the atmosphere. Therefore, an investigation of formation and emission of fine primary PM in coal combustion was conducted. First, the sources and classification of coal-fired primary PM were discussed; then their formation pathways during the coal combustion process were analyzed in detail. Accordingly, the emission control methods for fine particles generated from coal-fired power plants were put forward, and were classified as precombustion control, in-combustion control, and postcombustion control. Precombustion control refers to the processes for improving the coal quality before combustion, such as coal type selection and coal preparation. In-combustion control means to take measures for adjusting the combustion conditions and injection of additives during the combustion process to abate the formation of PM. Postcombustion control is the way that the fine PM are aggregated into larger ones by some agglomeration approaches and subsequently are removed by dust removal devices, or some high-performance modifications of conventional particle emission control devices (PECDs) can be taken for capturing fine particles. Finally, some general management suggestions are given for reducing fine PM emission in coal-fired power plants.

ImplicationsThe analysis and discussions of coal properties and its combustion process are critical to recognizing the formation and emission of the fine primary PM in combustion. The measures of precombustion, in-combustion, and postcombustion control based on the analysis and discussions are favorable for abating the PM emission. Practically, some measures of implementation do need the support of national policies, even needing to sacrifice economy to gain environmental profit, but this is the very time to execute these, and high-performance PECDs, especially novel devices, should be used for removing fine PM in flue gas.     

Analytical solutions to compartmental indoor air quality models with application to environmental tobacco smoke concentrations measured in a house

This paper derives the analytical solutions to multi-compartment indoor air quality models for predicting indoor air pollutant concentrations in the home and evaluates the solutions using experimental measurements in the rooms of a single-story residence. The model uses Laplace transform methods to solve the mass balance equations for two interconnected compartments, obtaining analytical solutions that can be applied without a computer. Environmental tobacco smoke (ETS) sources such as the cigarette typically emit pollutants for relatively short times (7-11 min) and are represented mathematically by a "rectangular" source emission time function, or approximated by a short-duration source called an "impulse" time function. Other time-varying indoor sources also can be represented by Laplace transforms. The two-compartment model is more complicated than the single-compartment model and has more parameters, including the cigarette or combustion source emission rate as a function of time, room volumes, compartmental air change rates, and interzonal air flow factors expressed as dimensionless ratios. This paper provides analytical solutions for the impulse, step (Heaviside), and rectangular source emission time functions. It evaluates the indoor model in an unoccupied two-bedroom home using cigars and cigarettes as sources with continuous measurements of carbon monoxide (CO), respirable suspended particles (RSP), and particulate polycyclic aromatic hydrocarbons (PPAH). Fine particle mass concentrations (RSP or PM3.5) are measured using real-time monitors. In our experiments, simultaneous measurements of concentrations at three heights in a bedroom confirm an important assumption of the model-spatial uniformity of mixing. The parameter values of the two-compartment model were obtained using a "grid search" optimization method, and the predicted solutions agreed well with the measured concentration time series in the rooms of the home. The door and window positions in each room had considerable effect on the pollutant concentrations observed in the home. Because of the small volumes and low air change rates of most homes, indoor pollutant concentrations from smoking activity in a home can be very high and can persist at measurable levels indoors for many hours.     

Formation of fine particles enriched by V and Ni from heavy oil combustion: Anthropogenic sources and drop-tube furnace experiments

The present study attempts to investigate the emission characteristics of fine particles with special emphasis on nickel and vanadium metal elements emitted from the heavy oil combustion in industrial boilers and power plant, which are typical anthropogenic sources in Korea. A series of combustion experiments were performed to investigate the emission characteristics of particles in the size range of submicron by means of drop-tube furnace with three major domestic heavy oils. Cascade impactors were utilized to determine the size distribution of particulates as well as to analyze the partitioning enrichment of vanadium and nickel in various size ranges. Experimental results were compared with field data of particle size distribution and metal partitioning at commercial utility boilers with heavy oil combustion. Such data were interpreted by chemical equilibrium and particle growth mechanism by means of computational models. In general, fine particles were the major portion of PM₁₀ emitted from the heavy oil combustion, with significant fraction of ultra-fine particles. The formation of ultra-fine particles through nucleation/condensation/coagulation from heavy oil combustion was confirmed by field and experimental data. Vanadium and nickel were more enriched in fine particles, particularly in ultra-fine particles. The conventional air pollution devices showed inefficient capability to remove ultra-fine particles enriched with hazardous transition metal elements such as vanadium and nickel.     

Ultrafine particle emission from incinerators: the role of the fabric filter

Incinerators are claimed to be responsible of particle and gaseous emissions: to this purpose Best Available Techniques (BAT) are used in the flue-gas treatment sections leading to pollutant emission lower than established threshold limit values. As regard particle emission, only a mass-based threshold limit is required by the regulatory authorities. However; in the last years the attention of medical experts moved from coarse and fine particles towards ultrafine particles (UFPs; diameter less than 0.1 microm), mainly emitted by combustion processes. According to toxicological and epidemiological studies, ultrafine particles could represent a risk for health and environment. Therefore, it is necessary to quantify particle emissions from incinerators also to perform an exposure assessment for the human populations living in their surrounding areas. A further topic to be stressed in the UFP emission from incinerators is the particle filtration efficiency as function of different flue-gas treatment sections. In fact, it could be somehow important to know which particle filtration method is able to assure high abatement efficiency also in terms of UFPs. To this purpose, in the present work experimental results in terms of ultrafine particle emissions from several incineration plants are reported. Experimental campaigns were carried out in the period 2007-2010 by measuring UFP number distributions and total concentrations at the stack of five plants through condensation particle counters and mobility particle sizer spectrometers. Average total particle number concentrations ranging from 0.4 x 10(3) to 6.0 x 10(3) particles cm(-3) were measured at the stack of the analyzed plants. Further experimental campaigns were performed to characterize particle levels before the fabric filters in two of the analyzed plants in order to deepen their particle reduction effect; particle concentrations higher than 1 x 10(7) particles cm(-3) were measured, leading to filtration efficiency greater than 99.99%.     

Size distribution and anthropogenic sources apportionment of airborne trace metals in Kanazawa, Japan

Aerosol samples were collected from Kanazawa, Japan to examine the size distribution of 12 elements and to identify the major sources of anthropogenic elements. Key emission sources were identified and, concentrations contributed from individual sources were estimated as well. Concentrations of elements V, Ca, Cd, Fe, Ba, Mg, Mn, Pb, Sr, Zn, Co and Cu in aerosols were determined with ICP-MS. The results showed that Ca, Mg, Sr, Mn, Co and Fe were mainly associated with coarse particles (>2.1 μm), primarily from natural sources. In contrast, the elements Zn, Ba, Cd, V, Pb and Cu dominated in fine aerosol particles (<2.1 μm), implying that the anthropogenic origin is the dominant source. Results of the factor analysis on elements with high EF_Crust values (>10) showed that emissions from waste combustion in incinerators, oil combustion (involving waste oil burning and oil combustion in both incinerators and electricity generation plants), as well as coal combustion in electricity generation plants were major contributors of anthropogenic metals in the ambient atmosphere in Kanazawa. Quantitatively estimated sum of mean concentrations of anthropogenic elements from the key sources were in good agreement with the observed values. Results of this study elucidate the need for making pollution control strategy in this area.     

Aerosol laser ablation mass spectrometry of suspended powders from PM sources and its implications to receptor modeling

Primary sources of particulate matter (PM) were analyzed by suspending powdered samples into an aerosol laser ablation mass spectrometer (LAMS). PM sources studied included vehicle exhaust particulates, dust from a non-ferrous smelter, cement powder, incinerator fly ash, two coal fly ash samples, and two soils. Marker peaks signified certain PM source sectors: construction particles could be distinguished by abundant Ca and Ca compounds, fuel combustion was marked by elemental carbon clusters, and nonferrous industrial particles showed inorganic As, Cu, Pb, Zn, and SOx. In addition to the distinction between particles from these different source sectors, mass spectral results also showed that for a single source, different particle types existed, and among different sources within a sector, similar spectra were present. The aerosol LAMS results show the difficulty in differentiating among separate fly ash sources as well as among different soil samples. A particle class balance receptor model that measures the amount of specific particle types rather than the amount of a chemical component is suggested as a means of source apportionment when particle spectra with overlapping source possibilities occur. The assumptions and limitations of receptor modeling aerosol LAMS data are also described. In particular, methods need to be developed to account for the contribution of secondary sources.     

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.