Informative Report

Abstract

Chemical composition and particle size data for particulate emissions from stationary sources are required for environmental health effect assessments, air chemistry studies and for air quality modeling investigations such as source apportionment. The Information presented In this paper is directed to those individuals concerned with these environmental Investigations. In this study, particulate emissions from a group of non-ferrous smelters have been physically and chemically characterized. Emission samples were collected at the baghouse outlets from smelter furnaces and at smelter acid plant stacks at three locations; a zinc, a lead, and a copper smelter.

Mass emission rate determinations were made by EPA reference methods. Cascade impactors were used to collect in-stack samples for particle size distribution measurements. Particulate samples for chemical characterization were collected on membrane filters for analysis by X-ray fluorescence spectroscopy. Development of measurement techniques required to determine the elemental composition of the total mass and sized fractions of the emission are discussed. Results of the tests at the three smelters include total mass and elemental emission rates, particle size distribution, and the elemental composition of the total particulate mass and of sized fractions from both the smelter furnaces and acid plants. The results obtained at the copper smelter may not be representative of the emissions at the many copper smelters where reverbatory furnaces have been replaced.     

Lead Contamination of Urban Soils and Vegetation by Emissions from Secondary Lead Industries

The degree and extent of lead contamination of urban soils and vegetation in the vicinity of secondary lead industries are provided. These urban industries, a secondary smelter reprocessing lead from used batteries and scrap metal and a manufacturer of new storage batteries, were located near residential communities. Levels as high as 21,000 ppm of lead in the upper 5 cm of soil (based on air dried weight) and 3500 and 2700 ppm in willow foliage (not washed and washed, respectively, based on dry weight) were found adjacent to the secondary smelter, with the levels decreasing exponentially from the sources. The data on lead contamination of soils and vegetation at various distances and directions from the urban secondary lead industries were compared with levels of lead found in control urban and highway locations. In addition, arsenic levels in soil were examined as a tracer for the source of industrial lead emissions. High levels of lead found In both vegetation and soil in the vicinity of the urban industries reflected both historical and current emissions of lead in those areas. These studies were conducted for industrial abatement purposes; to assist medical related epidemiology studies; to define the areas of severe contamination for soil cleanup purposes; and to formulate guidelines for excessive levels of lead in soil and vegetation. Since lead in soil is persistent, concern arises with respect to pica for small children, contamination of edible vegetables grown in high-lead soil, and reentrainment of leaded particulate matter into the air.     

The Impact of Particulate Emissions Control On the Control of Other MWC Air Emissions

On December 20, 1989, the Environmental Protection Agency (EPA) proposed revised new source performance standards for new municipal waste combustion (MWC) units and guidelines for existing sources. The proposed national regulations require tighter particulate matter control and address pre-combustion, combustion, and post-combustion controls, the latter two depending on capacity and age of the facility.

The air pollutants of concern when municipal solid waste (MSW) is burned will be discussed. Generally, particulate control is an inherent part of the systems used to limit the emissions of these air pollutants. The relationships between MWC air emissions (acid gases, trace organics, and trace heavy metals) control and particulate control will be discussed. Test results to quantify air pollutant emissions from MWC units and their control will be presented and compared with the proposed regulations.     

PM2.5 emissions from aluminum smelters: coefficients and environmental impact

From 2004 to 2009, aiming to better understand implications for its smelters, Rio Tinto Alcan conducted a detailed study of PM2.5 and PM10 (particulate matter [PM] < or = 2.5 and 10 microm in aerodynamic diameter, respectively) in its facilities. This involved a two-level study: part 1, emission quantification; and part 2, assessment of aluminum smelter contribution to the surrounding environment. In the first part, U.S. Environmental Protection Agency Other Test Method (OTM) OTM27 and OTM28 are assessed as relevant and efficient methods for measuring fine particle emissions from aluminum smelter stacks. Rio Tinto Alcan has also developed a safe and robust method called CYCLEX to measure PM2.5 and condensable particulate matter (CPM) at the roof vents of potrooms. This work aims to determine the PM2.5 emission coefficients of 17, 55, and 417 g x t(-1) of aluminum produced (including CPM) in anode baking furnace exhaust (fume treatment center), at potroom scrubber stacks (gas treatment centers), and at potroom roof vents, respectively. Results indicate that roof vents are the primary PM2.5 emitters (85% of all smelter emissions) and that 71% of all smelter PM2.5 comes from CPM. In the second part, preliminary inorganic speciation studies are conducted by scanning electron microscopy-energy-dispersive X-ray analysis and by isotopic ratios to track smelter emissions to their surrounding environment. This paper releases the first speciation results for an aluminum smelter, and the preliminary isotopic ratio study indicates a 3% impact in terms of PM2.5 emissions for a representative smelter in an urban area.     

PM2.5 Emissions from Aluminum Smelters: Coefficients and Environmental Impact

ABSTRACT

From 2004 to 2009, aiming to better understand implications for its smelters, Rio Tinto Alcan conducted a detailed study of PM_2.5 and PM₁₀ (particulate matter [PM] ≤ 2.5 and 10 μm in aerodynamic diameter, respectively) in its facilities. This involved a two-level study: part 1, emission quantification; and part 2, assessment of aluminum smelter contribution to the surrounding environment. In the first part, U.S. Environmental Protection Agency Other Test Method (OTM) OTM27 and OTM28 are assessed as relevant and efficient methods for measuring fine particle emissions from aluminum smelter stacks. Rio Tinto Alcan has also developed a safe and robust method called CYCLEX to measure PM_2.5 and condensable particulate matter (CPM) at the roof vents of potrooms. This work aims to determine the PM_2.5 emission coefficients of 17, 55, and 417 g·t^?1 of aluminum produced (including CPM) in anode baking furnace exhaust (fume treatment center), at potroom scrubber stacks (gas treatment centers), and at potroom roof vents, respectively. Results indicate that roof vents are the primary PM_2.5 emitters (85% of all smelter emissions) and that 71% of all smelter PM_2.5 comes from CPM. In the second part, preliminary inorganic speciation studies are conducted by scanning electron microscopy–energy-dispersive X-ray analysis and by isotopic ratios to track smelter emissions to their surrounding environment. This paper releases the first speciation results for an aluminum smelter, and the preliminary isotopic ratio study indicates a 3% impact in terms of PM_2.5 emissions for a representative smelter in an urban area.

IMPLICATIONS Aluminum smelters tend to continuously improve their competitiveness by incrementally increasing production. In this context, assessing the effect of major contaminants is overriding, and ambient air modeling is often the preferred way to do so. Fine particles fit this category, and the primary aluminum industry needs to accurately know their emission factors to obtain representative modeling. Moreover, not all aluminum smelters have a method to measure PM_2.5 at roof vents, the primary emission outlets. Therefore, this paper describes the first-rate PM_2.5 measurement methods for aluminum smelter roof vents without down-comers. It also provides insight for environmental managers for tracking PM_2.5 emissions in plant surroundings.     

Understorey vegetation along a heavy-metal pollution gradient in SW Finland

Understorey vegetation of Scots pine forests was studied along a 8-km transect running SE from a Cu-Ni smelter at Harjavalta, SW Finland. Long-term accumulation of heavy metals and sulphur in the forest ecosystem has drastically changed plant communities. Vegetation was almost absent up to a distance of 0.5 km from the smelter. The total coverage and the number of plant species increased with increasing distance from the smelter. Ordination by global non-metric multidimensional scaling (GNMDS) indicated that the floristic composition was differentiated in response to the pollution level. The main compositional gradient of GNMDS was correlated with the heavy metal concentrations in the organic soil layer and with the size of the overstorey trees. Vascular plants were more pollution-resistant than ground lichens, whereas mosses were the most sensitive plant group. In addition to heavy metals, nutrient imbalances and the considerably reduced water-holding capacity of the surface soil also restrict plant recolonisation on the degraded sites.     

Characterization of Airborne Dust from Two Nonferrous Foundries by Physico-chemical Methods and Multivariate Statistical Analyses

Abstract

Airborne particulate matter was sampled at a copper smelter and at an aluminum casting plant. Size, shape, quantity, and microlocalization of chemical species in the particulates were measured using closed cassettes, cascade impactors, scanning electron microscopy, X-ray diffraction, infrared and atomic absorption spectrophotometries, secondary ion mass spectrometry, and photoelectron spectroscopy. Cluster and principal components analyses were used in interpreting results. Aerosol chemistry varies as a function of size, and composition becomes more complex as the aerosol size drops into the respirable fraction and lower. Surface chemical properties are evidenced where, generally, volatile species are enriched. A few site-specific elements and characteristics were identified. The formation of particulates may often be related to process and practices, yet the actual distribution of species in the air remains an intricate matter.     

Comparative study of spray booth filter system efficiency

During recent years, greater emphasis has been placed on the control of particulate emissions from painting operations. This has gained more importance as more is learned about the potential release of toxic metals to the atmosphere from painting operations. This has led to queries about the efficiency of various painting arrestor systems to reduce particulate discharges to the atmosphere. Even more important is the capability of the arrestor systems to control PM10 emissions. In 1995, the U.S. Environmental Protection Agency initiated a study to evaluate various dry paint overspray arrestor systems. This study was designed to evaluate not only the total emissions control capability of the arrestor but also the PM10 control capability of the various system designs. Paint overspray arrestor systems using five different filtration concepts or materials were selected. They include systems constructed of fiberglass, paper, Styrofoam, and cardboard materials. These systems used filtration techniques incorporating the following filtration phenomena and designs: cyclone, baffle, bag systems, and mesh systems. The testing used an optical particle counting procedure to determine the concentration of particles of a given size fraction to penetrate a test arrestor system. The results of the testing indicated that there are significant differences in the efficiency of the tested system designs to capture and retain PM10. This paper summarizes the results of the research conducted to determine the capability of the arrestor systems to capture particulate of sizes down to approximately 1 micron in surface diameter.     

Comparative Study of Spray Booth Filter System Efficiency

ABSTRACT

During recent years, greater emphasis has been placed on the control of particulate emissions from painting operations. This has gained more importance as more is learned about the potential release of toxic metals to the atmosphere from painting operations. This has led to queries about the efficiency of various painting arrestor systems to reduce particulate discharges to the atmosphere. Even more important is the capability of the arrestor systems to control PM₁₀ emissions.

In 1995, the U.S. Environmental Protection Agency initiated a study to evaluate various dry paint overspray arrestor systems. This study was designed to evaluate not only the total emissions control capability of the arrestor but also the PM₁₀ control capability of the various system designs. Paint overspray arrestor systems using five different filtration concepts or materials were selected. They include systems constructed of fiberglass, paper, Styrofoam, and cardboard materials. These systems used filtration techniques incorporating the following filtration phenomena and designs: cyclone, baffle, bag systems, and mesh systems.

The testing used an optical particle counting procedure to determine the concentration of particles of a given size fraction to penetrate a test arrestor system. The results of the testing indicated that there are significant differences in the efficiency of the tested system designs to capture and retain PM₁₀.

This paper summarizes the results of the research conducted to determine the capability of the arrestor systems to capture particulate of sizes down to approximately 1 μm in surface diameter.     

Characterization of PM2.5 fugitive metal in the workplaces and the surrounding environment of a secondary aluminum smelter

Fugitive metal in PM_2.5 at the blast furnace (S₁), reverberatory furnace (S₂), and surrounding environment (S₀) of a secondary aluminum smelter (a secondary ALS) was studied. PM_2.5 mass concentration at the blast furnace exceeded that at the reverberatory furnace and this was especially apparent during operation, giving an early indication that the blast furnace is more important as a pollutant source. Further, PM_2.5 mass concentration levels and patterns at S₀ indicated that emissions from the blast furnace and reverberatory furnace were the major source of the observed fine particle pollution in the surrounding environment. Si and K were the main components and hence pollutants by mass in the PM_2.5 at S₁, S₂ and S₀ during both operation and non-operation. Hg was not detected in the PM_2.5 aerosol during smelter operation but was present at all three sampling locations during non-operation. This is due to the falling blast furnace and reverberatory furnace temperatures during non-operation which cause Hg vapor formed during operation to condense to form detectable Hg particles, and hence Hg contributes to the pollutant load during non-operation. Average S₁/S₀ and S₂/S₀ mass concentration ratios of 40.32 and 18.53, respectively, for all measured metals during operation and 7.83 and 5.73 for all measured metals during non-operation indicate that metal particulate pollution at the workplaces of secondary ALSs, particularly at the blast furnace during operation, is a serious issue. S₁/S₀ mass concentration ratios were higher still for Pb (62.22), Ti (113.40) and Ba (248.64), while the S₂/S₀ mass concentration ratio for Mo was 138.20. Principal component analyses produced a PC1 that explained 32.36–48.16% of the total variance during operation of the smelter and 47.86–69.Ten percent during non-operation. Their strong component loadings were mainly related to the fugitive PM_2.5 mass. Compared to atmospheric metal concentrations reported for other regions of the world, the toxic metals that have relatively higher concentrations in the secondary ALS emissions are Cr, Cd, Cu, As, Pb, Se, Al and Zn, especially during smelter operation. Concentrations of these toxic heavy metals are approximately 2–4 orders of magnitude higher than those reported for various industrial regions and metropolises with heavy traffic across the world.     

Simulation of stack plume opacity

The visual impact of primary particles emitted from stacks is regulated according to stack opacity criteria. In-stack monitoring of the flue gas opacity allows plant operators to ensure that the plant meets U.S. Environmental Protection Agency opacity regulations. However, the emission of condensable gases such as SO3 (that hydrolyzes to H2SO4), HCl, and NH3, which may lead to particle formation after their release from the stack, makes the prediction of stack plume opacity more difficult. We present here a computer simulation model that calculates the opacity due to both primary particles emitted from the stack and secondary particles formed in the atmosphere after the release of condensable gases from the stack. A comprehensive treatment of the plume rise due to buoyancy and momentum is used to calculate the location at which the condensed water plume has evaporated (i.e., where opacity regulations apply). Conversion of H2SO4 to particulate sulfate occurs through nucleation and condensation on primary particles. A thermodynamic aerosol equilibrium model is used to calculate the amount of ammonium, chloride, and water present in the particulate phase with the condensed sulfate. The model calculates the stack plume opacity due to both primary and secondary particles. Examples of model simulations are presented for three scenarios that differ by the emission control equipment installed at the power plant: (1) electrostatic precipitators (ESP), (2) ESP and flue gas desulfurization, and (3) ESP and selective catalytic reduction. The calculated opacity is most sensitive to the primary particulate emissions. For the conditions considered here, SO3 emissions showed only a small effect, except if one assumes that most H2SO4 condenses on primary particles. Condensation of NH4Cl occurs only at high NH3 emission rates (about 25 ppm stack concentration).     

Measuring Inorganic and Alkyl Lead Emissions from Stationary Sources

Described are the results from studies done to provide test methods for state and local air pollution control agencies to measure accurately the lead emissions from stationary source stacks as required in the National Ambient Air Quality Standard for Lead. Separate test methods were developed for measuring inorganic lead and alkyl lead compounds. Inorganic lead is collected in a standard particulate sampling train, digested with 50% (V/V) nitric acid and 3% hydrogen peroxide and analyzed by atomic absorption spectrometry. Alkyl lead compounds are collected in iodine monochloride and analyzed by atomic absorption spectrometry without prior solvent extraction. Standard solutions of inorganic lead in dilute nitric acid are used to calibrate the spectrophotometer in both methods. The inorganic lead test method was evaluated using baghouse dust samples from a primary copper and a primary lead smelter and stack samples from a lead recovery furnace, a primary battery manufacturing plant, a gray iron foundry and a secondary lead smelter. The alkyl lead method was evaluated using alkyl lead motor mix fluids and samples from an alkyl lead manufacturing plant vent stack.     

ESP Performance with Atmospheric Fluidized-Bed Combustion

Electric utilities considering atmospheric fluidized-bed combustion (AFBC) as an economic way to reduce SO₂ and NO_x emissions at coal-fired power plants must evaluate the impact AFBC will have on existing or planned plant systems and components. Because fly ash in AFBC units can have characteristics significantly different from that generated in pulverized-coal-fired boilers, a particular concern in this regard is the performance of the plant's particulate control equipment.     

Problems of Meeting Multiple Air Quality Objectives for Coal-Fired Utility Boilers

Gaseous wastes and particulate emissions are produced in the process of burning coal to produce electrical energy. In attempting to control these gaseous wastes, changes in the operation efficiency of boilers and secondary equipment are likely to result, and in addition liquid and solid waste streams are produced. The interrelationships among the various forms of wastes and the effects of air quality control on process efficiency are often overlooked in studies of environmental quality management.

The study was undertaken to evaluate the technical alternatives for handling gaseous and particulate emissions from coal-fired boilers and to determine the feasibility of meeting several standards simultaneously. The gaseous emissions of major importance in the combustion of coal are parti culates, oxides of sulfur, and oxides of nitrogen. Particulates can be controlled by a tradeoff among further preparation at the mine (for additional ash removal), type of boiler, use of dust control equipment and high stacks for dispersion of residual emissions, if ambient air standards are considered. Oxides of sulfur reduction depends currently on fuel substitution, limestone additives in the boiler and some form of contact process such as wet scrubbing, or the use of high stacks. Oxides of nitrogen control in coal fired boilers is restricted to small reductions by either changes in boiler operation, such as lower excess air levels, adsorption during wet scrubbing or by dispersion from high stacks.     

Impact of a smelter closedown on metal contents of wheat cultivated in the neighbourhood

BACKGROUND: The contamination of soils by heavy metals engenders important environmental and sanitary problems in Northern France where a smelter has been located for more than one hundred of years. It has been one of the most important Pb production sites in Europe until its closedown in March 2003. Ore smelting process generated considerable atmospheric emissions of dust. Despite an active environmental strategy, these emissions were still significant in 2002 with up to 17 tonnes of Pb, 32 tonnes of Zn and 1 tonne of Cd. Over the years, the generated deposits have led to an important contamination of the surrounding soils. Previous studies have shown pollutant transfers to plants, which can induce a risk for human and animal health. The objective of this study was to evaluate the consequences of the smelter closedown on the Cd and Pb contents of wheat (grain and straw) cultivated in the area. METHODS: Paired topsoil and vegetable samples were taken at harvest time at various distances to the smelter. The sample sites were chosen in order to represent a large range of soil metal contamination. Sampling was realised on several wheat harvests between 1997 and 2003. 25 samples were collected before the smelter closedown and 15 after. All ears of about 1 m long of two rows were manually picked and threshed in the lab. Similarly, straw was harvested at the same time. Total metal contents in soil and wheat samples were quantified. RESULTS: A negative correlation between metal concentrations in soil and the distance to the smelter was shown. The wheat grain and straw showed significant Cd and Pb contents. The straw had higher metal contents than the grain. During the smelter activity, the grain contents were up to 0.8 mg kg(-1) DM of Cd and 8 mg kg(-1) DM of Pb. For the straw, maximum contents were 5 mg kg(-1) DM of Cd and 114 mg kg(-1) DM of Pb. After the smelter closedown, we observed a very large decrease of Pb in the grain (82%) and in the straw (91%). A smaller decrease was observed for Cd in grain. Despite this improvement, 80% of the studied samples remained non-acceptable for human consumption, according to the European legislation values, due to a high Cd content. DISCUSSION: Results highlighted a difference in metal accumulation in the plant organs as well as a difference in metal uptake. The approach pointed out the importance of atmospheric fallout in the wheat contamination pathways for Pb. The smelter closedown has lead to a decrease of the Pb content in wheat. It is interesting to relate this finding with the lead blood levels in children living close to the smelter. CONCLUSIONS: Those results have confirmed the importance of dust fallout in the plant contamination pathways. Before the closedown, Pb measured in the plant was principally originating from the smelter dust emissions. It raised the question of the sanitary risks for humans and animals living in the surrounding a of the smelter. RECOMMENDATIONS AND PERSPECTIVES: In the literature, very few articles take the dust deposit as contamination pathways for crops into consideration. However, in highly contaminated sites, this pathway can be very important. Thus, it would be worthy studying the uptake of metal contaminants by plants through the foliar system.     

Concentrations of PCDD/PCDF in soil close to a secondary aluminum smelter

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) were analyzed in samples of the emissions from a secondary aluminum smelter (ALS) and soil samples around the plant. The purpose was to estimate the impact of the emissions on the surrounding environment.PCDD/F soil concentrations were higher in the proximity of the plant, exceeding the limit adopted in Italy in soils for green areas and residential uses and the upper limit of several reference concentrations. The most contaminated sites were less than 500 m from the plant and the dioxin concentration with the distance from the ALS.Principal component analysis (PCA) showed that emissions from the ALS were the source of PCDD/F contamination in the soils closest to the plant. Multivariate data analyses such as PCA are therefore useful to identify sources of emission causing contamination.     

Concentrations of PCDD/PCDF in soil close to a secondary aluminum smelter

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) were analyzed in samples of the emissions from a secondary aluminum smelter (ALS) and soil samples around the plant. The purpose was to estimate the impact of the emissions on the surrounding environment.PCDD/F soil concentrations were higher in the proximity of the plant, exceeding the limit adopted in Italy in soils for green areas and residential uses and the upper limit of several reference concentrations. The most contaminated sites were less than 500 m from the plant and the dioxin concentration with the distance from the ALS.Principal component analysis (PCA) showed that emissions from the ALS were the source of PCDD/F contamination in the soils closest to the plant. Multivariate data analyses such as PCA are therefore useful to identify sources of emission causing contamination.     

Simulation of Stack Plume Opacity

ABSTRACT

The visual impact of primary particles emitted from stacks is regulated according to stack opacity criteria. In-stack monitoring of the flue gas opacity allows plant operators to ensure that the plant meets U.S. Environmental Protection Agency opacity regulations. However, the emission of condensable gases such as SO₃ (that hydrolyzes to H₂SO₄), HCl, and NH₃, which may lead to particle formation after their release from the stack, makes the prediction of stack plume opacity more difficult.

We present here a computer simulation model that calculates the opacity due to both primary particles emitted from the stack and secondary particles formed in the atmosphere after the release of condensable gases from the stack. A comprehensive treatment of the plume rise due to buoyancy and momentum is used to calculate the location at which the condensed water plume has evaporated (i.e., where opacity regulations apply).

Conversion of H₂SO₄ to particulate sulfate occurs through nucleation and condensation on primary particles. A thermodynamic aerosol equilibrium model is used to calculate the amount of ammonium, chloride, and water present in the particulate phase with the condensed sulfate. The model calculates the stack plume opacity due to both primary and secondary particles. Examples of model simulations are presented for three scenarios that differ by the emission control equipment installed at the power plant: (1) electrostatic precipitators (ESP), (2) ESP and flue gas desulfurization, and (3) ESP and selective catalytic reduction. The calculated opacity is most sensitive to the primary particulate emissions. For the conditions considered here, SO₃ emissions showed only a small effect, except if one assumes that most H₂SO₄ condenses on primary particles. Condensation of NH₄Cl occurs only at high NH₃ emission rates (about 25 ppm stack concentration).     

Environmental Impact of Residential Wood Combustion Emissions and its Implications

Currently available information suggests a substantial environmental impact from residential wood combustion emissions. Air pollution from this source is widespread and increasing. Current ambient measurements, surveys, and model predictions indicate winter respirable (<2 μm) emissions from residential wood combustion can easily exceed all other sources. Both the chemical potency and deliverability of the emissions from this source are of concern. The emissions are almost entirely in the inhalable size range and contain toxic and priority pollutants, carcinogens, co-carcinogens, cilia toxic, mucus coagulating agents, and other respiratory irritants such as phenols, aldehydes, etc. This source is contributing substantially to the nonattainment of current particulate, carbon monoxide, and hydrocarbon ambient air quality standards and will almost certainly have a significant impact on potential future standards such as inhalable particulates, visibility, and other chemically specific standards. Emission from this growing source is likely to require additional expenditures by industry for air pollution control equipment in nonattainment areas.