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.     

Emission Factors of Air Toxics from Semiconductor Manufacturing in Korea

Abstract

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.     

Anthropogenic mercury emission inventory with emission factors and total emission in Korea

Mercury emissions concentrations, emission factors, and the total national emission from major anthropogenic sources in Korea for the year 2007 were estimated. Uncontrolled and controlled mercury emission factors and the total emission from each source types are presented. The annual national mercury emission from major anthropogenic sources for the year 2007, on average was 12.8 ton which ranged from 6.5 to 20.2 ton. Averaged emissions of elemental, oxidized, and particulate mercury were estimated at 8.25 ton, 3.69 ton, and 0.87 ton, respectively. Due to the removal of a major portion of particulate and oxidized mercury species, elemental mercury was dominant in stack emission. About 54.8% of mercury emission was contributed by industrial sources, 45.0% by stationary combustion sources and 0.02% by mobile sources. Thermal power plants, oil refineries, cement kilns and incinerators (municipal, industrial, medical, sewage sludge) were the major mercury emitters, contributing about 26%, 25%, 21% and 20%, respectively to the total mercury emission. Other sources (crematory, pulp and paper manufacturing, nonferrous metals manufacturing, glass manufacturing) contributed about 8% of the total emission. Priority should be given in controlling mercury emissions from coal-fired power plants, oil refineries, cement kilns and waste incinerators. More measurements including natural and re-emission sources are to be carried out in the future in order to have a clear scenario of mercury emission from the country and to apply effective control measures.     

Source apportionment of polycyclic aromatic hydrocarbons in surface soil in Tianjin, China

Principal component analysis and multiple linear regression were applied to apportion sources of polycyclic aromatic hydrocarbons (PAHs) in surface soils of Tianjin, China based on the measured PAH concentrations of 188 surface soil samples. Four principal components were identified representing coal combustion, petroleum, coke oven plus biomass burning, and chemical industry discharge, respectively. The contributions of major sources were quantified as 41% from coal, 20% from petroleum, and 39% from coking and biomass, which are compatible with PAH emissions estimated based on fuel consumption and emission factors. When the study area was divided into three zones with distinctive differences in soil PAH concentration and profile, different source features were unveiled. For the industrialized Tanggu-Hangu zone, the major contributors were cooking (43%), coal (37%) and vehicle exhaust (20%). In rural area, however, in addition to the three main sources, biomass burning was also important (13%). In urban-suburban zone, incineration accounted for one fourth of the total.     

Improving environmental risk management through historical impact assessments

A historical contaminant impact assessment was conducted at 48 heavy manufacturing facilities located in 20 different states for a U.S.-based company. The facilities evaluated were industrial manufacturing sites that operated for as long as 100 yr and used several types of hazardous substances, including solvents and degreasers, oils and other petroleum products, paints and pigments, and heavy metals. The purpose of conducting the impact assessment was to provide direction and guidance on future environmental objectives and pollution prevention initiatives. The impact assessment involved examining historical investigative and remediation costs since 1985, types of contaminants, subsurface geology, hydrology, and regulatory requirements. The results reveled that 85% of the historical environmental costs were associated with hexavalent chromium and chlorinated solvents. Other contaminants, such as oils and other petroleum products and other heavy metals, were far more commonly detected but only accounted for the remaining 15% of costs. The results also indicated that the costs are also strongly associated with the type of geologic environment to which the chemicals were released. As a result of these findings, an aggressive pollution prevention program has been initiated to eliminate the use of those contaminants that are especially expensive to remediate and to develop stronger and more effective engineering controls at facilities located in sensitive ecological areas.     

我国氮氧化物排放因子的修正和排放量计算:2000年

根据我国城市的发展状况 ,采用城市分类的方法 ,将我国 2 6 1个地级市按照人口数量分为 5个类别。每类城市选取一个典型城市进行实地调查 ,对我国燃烧锅炉和机动车的NOx 的排放因子进行了修正 ,提出了适合我国目前排放水平的各类城市的固定源和移动源的排放因子。并依据 2 0 0 0年中国大陆地区的电站锅炉、工业锅炉和民用炉具的燃料消耗量和机动车保有量 ,以地级市为基本单位 ,估算了 2 0 0 0年我国各地区的NOx 排放量 ,分析了分地区、分行业、分燃料类型的NOx 排放特征。 2 0 0 0年我国NOx 排放总量为 11.12Mt,其中固定源占 6 0 .8% ;移动源占 39.2 %。NOx 排放在地域、行业和燃料类型上分布均不平衡。NOx 的排放主要集中在华东和华北地区 ,其排放量占全国排放量的一半以上。燃煤为最重要的NOx 排放源 ,其排放量占燃料型NOx 排放量的 72 .3%左右。     

Chemical composition of major VOC emission sources in the Seoul atmosphere

This paper describes a chemical analysis of volatile organic compounds (VOCs) for five emission sources in Seoul. The source categories included motor vehicle exhaust, gasoline evaporation, paint solvents, natural gas and liquefied petroleum gas (LPG). These sources were selected because they have been known to emit significant quantities of VOCs in the Seoul area (more than 5% of the total emission inventory). Chemical compositions of the five emission sources are presented for a group of 45 C2-C9 VOCs. Motor vehicle exhaust profiles were developed by conducting an urban tunnel study. These emissions profiles were distinguished from the other emission profiles by a high weight percentage of butanes over seasons and propane in the wintertime. It was found that this is due to the wide use of butane-fueled vehicles. To obtain gasoline vapor profiles, gasoline samples from five major brands for each season were selected. The brands were blended on the basis of the marketshare of these brands in Seoul area. Raoult's law was used to calculate gasoline evaporative compositions based on the liquid gasoline compositions. The measured and estimated gasoline vapor compositions were found to be in good agreement. Vehicle and gasoline evaporation profiles were made over seasons because of the seasonal change in their compositions. Paint solvent emissions profiles were produced based on a product-use survey and sales figures. These profiles are a composite of four major oil-based paints and thinning solvent. The source profile of natural gas was made on a methane-free basis. It was found that Ethane and propane were the most abundant compounds accounting for 95% of the natural gas composition. LPG was largely composed of propane and ethane and the remaining components were minor contributors.     

The European dioxin air emission inventory project--final results

Main results of the second stage of the so-called "European Dioxin Emission Inventory" are presented. They cover emission testing data gained from various facilities in the EU (among these the first emission measurements reported from Portugal and Greece) and some central European countries. Further, updated dioxin emission estimates for the most important emission sources in the 17 western European countries and an evaluation of the emission time trend from 1985 to 2005 are presented. The major conclusions are, that at present, iron ore sintering is likely to be the most important emission source type followed by the former "No. 1", municipal waste incineration; measurement data from a considerable number of installations are still missing, in particular from the metal industries in Spain and Italy; there still exist an unknown number of health care waste incinerators with flue gas PCDD/F concentrations above 100 ng I-TEQ/m3 which must be considered as important local sources; in general, considerable emission reduction has been achieved with respect to the industrial emission sources, whereas emissions from non-industrial sources hardly decreased; hence, in the near future the emissions from non-industrial sources are likely to exceed those from industrial installations; the goal of 90% emission reduction set in the 5th EU Action Programme will be achieved for some source types only.     

Air Levels and Mutagenicity of PM-10 in an Indoor Ice Arena

Abstract

Hazardous waste sites and industrial facilities contain area sources of fugitive emissions. Emission rate measurements or estimates are necessary for air pathway assessments for these sources. Emission rate data can be useful for the design of emission control and remediation strategies as well as for predictive modeling for population exposure assessments. This paper describes the use of a direct emission measurement approach – the enclosure approach using an emission isolation flux chamber – to measure emission rates of various volatile organic compounds (VOCs) from contaminated soil and water. A variety of flux chamber equipment designs and operating procedures have been employed by various researchers. This paper contains a review of the design and operational variables that affect the accuracy and precision of the method. Guidance is given as to the optimum flux chamber design and operating conditions for various types of emission sources. Also presented is a generic quality control program that gives the minimum number of duplicate, blank, background, and repeat samples that should be performed.     

Receptor Model Evaluation of the Southeast Michigan Ozone Study Ambient NMOC Measurements

Abstract

Large-scale studies like the Southeast Michigan Ozone Study (SEMOS) have focused attention on quantifying and spedating inventories for volatile organic compounds (VOCs). One approach for evaluating the accuracy of a VOC emission inventory is the development of a chemical mass balance (CMB) receptor model for ambient non-methane organic compound (NMOC) measurements. CMB evaluations of ambient hydrocarbon data provide a sample-specific allocation of emissions to individual source categories. This study summarizes the results of an application of the CMB model to the NMOC data from the SEMOS study. Comparison of CMB results with emission inventory values for the Detroit area show that vehicle emissions are well represented by the inventory, as are architectural coatings and coke ovens. Estimated emissions from petroleum refineries and graphic arts industries are much lower in the inventory than determined from the receptor allocation. Under-reporting of fugitive VOC emissions from petroleum refineries is an ongoing problem. Emissions from graphic arts industries are underestimated in the inventory partly because of the broad characterization of the emission factor (i.e., mass emitted/capita), which may be less useful when specific locations and days are under consideration. This study also demonstrates the effectiveness of the CMB approach when used prospectively to track the implementation of emission control strategies. While vehicle emission concentrations were unchanged from 1988 to 1993, measurement-based CMB results suggest a decrease in evaporative emissions during this time period resulting from Reid vapor pressure (RVP) reductions (from 11.0 psi in 1988 to 8.6 psi in 1993) and fleet turnover. Changes in emissions from coke plants and petroleum refineries were also seen in the CMB allocations for these sources.     

Polynuclear Hydrocarbon Emissions from Selected Industrial Processes

A number of selected industrial processes considered as potential sources of benzo{a)- pyrene and other polynuclear hydrocarbons were surveyed. Polynuclear hydrocarbon emission levels were measured directly for asphalt hot road mix preparation and asphalt airblowing. Emissions of other pollutants, including particulate matter, carbon monoxide, and total gaseous hydrocarbons were also measured, and are reported together with pertinent data on process design and operation. Results are discussed with reference to the type of process; the type of equipment used, including control devices; and other factors. The significance of some additional processes as contributors of polynuclear hydrocarbons was examined indirectly by collecting atmospheric samples of polynuclear hydrocarbons in residential areas in the vicinity of (1) a carbon black manufacturing area, (2) a steel and coke manufacturing area, (3) an organic chemical industry complex, and (4) a residential and small-industry coal burning area.     

Evaluation of non-enteric sources of non-methane volatile organic compound (NMVOC) emissions from dairies

Dairies are believed to be a major source of volatile organic compounds (VOC) in Central California, but few studies have characterized VOC emissions from these facilities. In this work, samples were collected from six sources of VOCs (Silage, Total Mixed Rations, Lagoons, Flushing Lanes, Open Lots and Bedding) at six dairies in Central California during 2006–2007 using emission isolation flux chambers and polished stainless steel canisters. Samples were analyzed by gas chromatography/mass spectrometry and gas chromatography/flame ionization detection. Forty-eight VOCs were identified and quantified in the samples, including alcohols, carbonyls, alkanes and aromatics. Silage and Total Mixed Rations are the dominant sources of VOCs tested, with ethanol as the major VOC present. Emissions from the remaining sources are two to three orders of magnitude smaller, with carbonyls and aromatics as the main components. The data suggest that animal feed rather than animal waste are the main source of non-enteric VOC emissions from dairies.     

A Comparison of Organic Emissions from Hazardous Waste Incinerators Versus the 1990 Toxics Release Inventory Air Releases

Incineration is often the preferred technology for disposing of hazardous waste and remediating Superfund sites. The effective implementation of this technology is frequently impeded by strong public opposition to hazardous waste incineration (HWI). One of the reasons cited for this opposition is the perception that the emission of organics pose an unreasonable threat to human health. While numerous risk assessments for these facilities have demonstrated that the risks from the inhalation of HWI emissions are very low, this has not totally allayed some of the concerns. In order to put organic emissions in perspective, the mass of these emissions from the incineration of hazardous waste on a national scale has been estimated using “reasonable worst-case” assumptions and compared to the 1990 Toxics Release Inventory (TRI) air releases. Comparisons were made for 15 carcinogenic organic compounds and 17 non-carcinogenic organic compounds. Ratios for all but one of these compound-specific HWI emissions to their corresponding TRI air releases ranged from 0.0003 to 0.678 percent. The total mass emissions (110.5 tons) of all 32 specific organics from HWIs was less than 0.03 percent of the corresponding 1990 TRI air releases (431,586 tons).     

Source apportionment of ambient non-methane hydrocarbons in Hong Kong: application of a principal component analysis/absolute principal component scores (PCA/APCS) receptor model

Receptor-oriented source apportionment models are often used to identify sources of ambient air pollutants and to estimate source contributions to air pollutant concentrations. In this study, a PCA/APCS model was applied to the data on non-methane hydrocarbons (NMHCs) measured from January to December 2001 at two sampling sites: Tsuen Wan (TW) and Central & Western (CW) Toxic Air Pollutants Monitoring Stations in Hong Kong. This multivariate method enables the identification of major air pollution sources along with the quantitative apportionment of each source to pollutant species. The PCA analysis identified four major pollution sources at TW site and five major sources at CW site. The extracted pollution sources included vehicular internal engine combustion with unburned fuel emissions, use of solvent particularly paints, liquefied petroleum gas (LPG) or natural gas leakage, and industrial, commercial and domestic sources such as solvents, decoration, fuel combustion, chemical factories and power plants. The results of APCS receptor model indicated that 39% and 48% of the total NMHCs mass concentrations measured at CW and TW were originated from vehicle emissions, respectively. 32% and 36.4% of the total NMHCs were emitted from the use of solvent and 11% and 19.4% were apportioned to the LPG or natural gas leakage, respectively. 5.2% and 9% of the total NMHCs mass concentrations were attributed to other industrial, commercial and domestic sources, respectively. It was also found that vehicle emissions and LPG or natural gas leakage were the main sources of C(3)-C(5) alkanes and C(3)-C(5) alkenes while aromatics were predominantly released from paints. Comparison of source contributions to ambient NMHCs at the two sites indicated that the contribution of LPG or natural gas at CW site was almost twice that at TW site. High correlation coefficients (R(2) > 0.8) between the measured and predicted values suggested that the PCA/APCS model was applicable for estimation of sources of NMHCs in ambient air.     

Hazardous air pollutant emissions from gas-fired combustion sources: emissions and the effects of design and fuel type

Air emissions from gas-fired combustion devices such as boilers, process heaters, gas turbines and stationary reciprocating engines contain hazardous air pollutants (HAPs) subjected to consideration under the federal clean air act (CAA). This work presents a recently completed major research project to develop an understanding of HAP emissions from gas-fired boilers and process heaters and new HAP emission factors based on field emission tests of gas-fired external combustion devices used in the petroleum industry. The effect of combustion system design and operating parameters on HAP emissions determined by both field and research tests are discussed. Data from field tests of gas-fired petroleum industry boilers and heaters generally show very low emission levels of organic HAPs. A comparison of the emission data for boilers and process heaters, including units with and without various forms of NOx emission controls, showed no significant difference in organic HAP emission characteristics due to process or burner design. This conclusion is also supported by the results of research tests with different burner designs. Based on field tests of units fired with natural gas and various petroleum industry process gases and research tests in which gas composition was intentionally varied, organic HAP emissions were not determined to be significantly affected by the gas composition. Research data indicate that elevated organic HAP emission levels are found only under extreme operating conditions (starved air or high excess air combustion) associated with poor combustion.     

Source Fingerprints for Receptor Modeling of Volatile Organics

The development of receptor models for the determination of the sources of an ambient air pollutant requires that the composition of the pollutant at the point of emission be known. For this study, composition information for 10 sources of volatile organic compounds (VOC) were evaluated and source fingerprints developed. The source categories include motor vehicles, gasoline vapor, petroleum refineries, architectural coatings, graphic arts, waste-water treatment, vapor degreasing, drycleaning, automobile assembly (including body painting), and polyethylene production. The fingerprints are presented for a group of 23 compounds. These compounds were selected for a variety of reasons including ease of measurement in the ambient environment, compound toxicity, reactivity, and usefulness in previous receptor modeling applications. In general, the data for sources of VOC are remarkably consistent from study to study. Because the profiles for many of the sources of VOC are controlled by physical and chemical processes (e.g. combustion) and not raw material composition, the fingerprints have general applicability.     

Seasonal variation and source estimation of organic compounds in urban aerosol of Augsburg, Germany

This study reports a general assessment of the organic composition of the PM_2.5 samples collected in the city of Augsburg, Germany in a summer (August-September 2007) and a winter (February-March 2008) campaign of 36 and 30 days, respectively. The samples were directly submitted to in-situ derivatisation thermal desorption gas chromatography coupled with time of flight mass spectrometry (IDTD-GC-TOFMS) to simultaneously determine the concentrations of many classes of molecular markers, such as n-alkanes, iso- and anteiso-alkanes, polycyclic aromatic hydrocarbons (PAHs), oxidized PAHs, n-alkanoic acids, alcohols, saccharides and others.The PCA analysis of the data identified the contributions of three emission sources, i.e., combustion sources, including fossil fuel emissions and biomass burning, vegetative detritus, and oxidized PAHs. The PM chemical composition shows seasonal trend: winter is characterized by high contribution of petroleum/wood combustion while the vegetative component and atmospheric photochemical reactions are predominant in the hot season.     

Residential proximity to industrial sources of air pollution: interrelationships among race, poverty, and age

This study builds on earlier work investigating statistical relationships between sociodemographic characteristics of populations and their residential proximity to industrial sources of air pollution. The analysis uses demographic data from the 1990 U.S. Census and industrial site data from the U.S. Environmental Protection Agency (EPA)'s 1990 Toxics Release Inventory (TRI). The focus is on examining interactions among race (African Americans and Whites), poverty (above and below household poverty threshold), and age (children from birth to 5 years of age and elderly people 65 years old or older). Results from three different study areas (Kanawha Valley in West Virginia, the Baton Rouge-New Orleans Corridor in Louisiana, and the greater Baltimore metropolitan area in Maryland) suggest there are important interactions among race, poverty, and age that are likely to have consequential ramifications for efforts aimed at investigating issues related to environmental justice. Our results indicate that a substantial proportion of all demographic groups studied live within a mile of the nearest facility, with values ranging from 22% of Whites above poverty in the Baton Rouge-New Orleans Corridor to 60% of African Americans below poverty in Baltimore. Likewise, a substantial proportion of all demographic groups also live within 2 miles of four or more industrial facilities, with values ranging from 16% for Whites above poverty in the Corridor to 70% for African Americans below poverty in Baltimore. In all three study areas, African Americans were more likely than Whites to (1) live in households with incomes below the household poverty line, (2) have children 5 years of age or younger, (3) live closer to the nearest industrial emissions source, and (4) live within 2 miles of multiple industrial emission sources. Findings indicate that, compared with White children, a substantially higher proportion of African-American children 5 years of age or younger lived in poor households that were located in relatively close proximity to one or more industrial sources of air pollution.     

A Strategy and Methodology for Defensibly Correlating Spilled Oil to Source Candidates

The source of crude oils and petroleum products released into navigable waterways and shipping lanes is not always known. Thus, the defensible identification of spilled crude oils and petroleum products and their correlation to suspected sources is a critical part of many oil spill assessments. Quantitative "fingerprinting" analysis, when evaluated using straightforward statistical and numerical analyses, provides a defensible means to differentiate among qualitatively similar oils and provides the best assessment of the source(s) for spilled oils. Polycyclic aromatic hydrocarbon (PAH) and petroleum biomarker concentration data are a particularly useful quantitative measure that can benefit most oil spill investigations. In this paper the strategy and methodology for correlation analysis that relies upon quantitative gas chromatography/mass spectrometry operated in the selected ion monitoring mode (GC/MS-SIM) is demonstrated in a case study involving 66 candidate sources for a heavy fuel oil spill of unknown origin. The strategy includes identification of 19 chemical indices (out of 45 evaluated) based upon PAH's and biomarkers that were (1) independent of weathering; and (2) precisely measured, both of which are determined by statistical analysis of the data. The 19 chemical indices meeting these criteria are subsequently analysed using principal component analysis (PCA), which helps to determine defensibly the "prime suspects" for the oil spill under investigation. The strategy and methodology described, which combines statistical and numerical analysis of quantitative chemical data, can be adapted and applied to other environmental forensic investigations with the objective of correlating any form of contamination to its suspected sources.     

A Strategy and Methodology for Defensibly Correlating Spilled Oil to Source Candidates

The source of crude oils and petroleum products released into navigable waterways and shipping lanes is not always known. Thus, the defensible identification of spilled crude oils and petroleum products and their correlation to suspected sources is a critical part of many oil spill assessments. Quantitative “fingerprinting” analysis, when evaluated using straightforward statistical and numerical analyses, provides a defensible means to differentiate among qualitatively similar oils and provides the best assessment of the source(s) for spilled oils. Polycyclic aromatic hydrocarbon (PAH) and petroleum biomarker concentration data are a particularly useful quantitative measure that can benefit most oil spill investigations. In this paper the strategy and methodology for correlation analysis that relies upon quantitative gas chromatography/mass spectrometry operated in the selected ion monitoring mode (GC/MS-SIM) is demonstrated in a case study involving 66 candidate sources for a heavy fuel oil spill of unknown origin. The strategy includes identification of 19 chemical indices (out of 45 evaluated) based upon PAH's and biomarkers that were (1) independent of weathering; and (2) precisely measured, both of which are determined by statistical analysis of the data. The 19 chemical indices meeting these criteria are subsequently analysed using principal component analysis (PCA), which helps to determine defensibly the “prime suspects” for the oil spill under investigation. The strategy and methodology described, which combines statistical and numerical analysis of quantitative chemical data, can be adapted and applied to other environmental forensic investigations with the objective of correlating any form of contamination to its suspected sources.