Emissions of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans from Various Industrial Sources

Abstract

This study characterized the emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from the stack flue gases of 17 industrial sources, which were classified into 10 categories. The results show that the mean PCDD/PCDF concentration of secondary zinc smelter (Zn-S) and secondary copper smelter (Cu-S) is 2.44 ng international toxic equivalent (I-TEQ)/Nm³ (N represents normal conditions at 0 °C, 760 mmHg), which was found to be significantly greater than that of industrial waste incinerators (mean concentration = 0.15 ng I-TEQ/Nm³). These results imply that the controlling of secondary metallurgical melting processes is more important than industrial waste incineration for the reduction of PCDD/PCDF emissions. The mean emission factors of cement production, Zn-S and Cu-S, are 0.052, 1.99, and 1.73 μg I-TEQ/t product, respectively. For industrial waste incineration, the mean emission factors of waste rubber, waste liquor, waste sludge, industrial waste solid (IWI)-1, IWI-2, IWI-3, and IWI-4 are 0.752, 0.435, 0.760, 6.64, 1.67, 2.38, and 0.094 μg I-TEQ/t feed, respectively. Most of the PCDD/PCDF emission factors established in this study are less than those reported in previous studies, which could be because of the more stringent regulations for PCDD/PCDF emissions in recent years.     

Gaseous Emissions from Unregulated Mobile Sources

The impact of gaseous exhaust emissions is determined for the following categories of mobile sources which are currently not covered by national emission regulations: 1) farm equipment, 2) merchant vessels, 3) locomotives, 4) lawn and garden implements, 5) snowmobiles, 6) outboard motors, 7) transport refrigeration units, and 8) helicopters. Mass emission rates of each category are tabulated and compared to other emissions from both mobile and stationary sources in selected Air Quality Control Regions. Also, projections are made as to the expected increase of emissions from each source category through 1990. The results show that in the near future some categories of mobile sources will be contributing substantial amounts of pollutants, on a mass basis, in regions with critical air pollution problems. As stricter emission standards on regulated sources continue to be implemented, the relative significance of these unregulated sources will increase. The major conclusion is that broad generalizations as to the amounts of air pollution contributed by these unregulated mobile sources nationwide may be grossly misleading. The only effective way to assess their impact is on a region-by-region basis. To this end, generalized computer programs are developed which permit the estimation of each category’s present and future mass emission rates in any Air Quality Control Region in the country     

An Inventory of Particulate Emissions from Open Sources

Open sources are those stationary sources of air pollution too great in extent to be controlled through enclosure or ducting. Open sources of atmospheric particles include: wind erosion, tilling, and prescribed burning of agricultural cropland; surface mining and wind erosion of tailings piles; vehicular travel on both paved and unpaved roads; construction site activity; and forest fires. It is estimated that in 1976 the total open source emissions of particles in the U.S. amounted to over 580 × 10⁶ ton. These estimates indicate that emissions from the two largest open source classes, travel on unpaved roads and agricultural wind erosion, accounted for 86% of this total. The open source emissions in ten states (AZ, CA, KS, MN, MT, NM, ND, OH, SD, TX) contributed 6 2% of the national emissions for 1976.     

Low Emissions from Controlled Combustion for Automotive Rankine Cycle Engines

Rankine cycle engines have a high potential for meeting the emission levels established by the 1970 amendment to the Federal Clean Air Act for the 1975-76 automobile. This paper discusses a Solar research and development program sponsored by EPA/APCO which demonstrates a full scale 2 million Btu per hour working model of a Rankine cycle engine combustor and controls which can surpass the emission goals established.

Special features of the combustor are the unique methods of precisely controlling both the fuel and air to provide optimum flame performance at any engine power level. This paper discusses the special requirements of the Rankine cycle engine and shows why the very wide range of fuel flow required necessitates use. of special techniques in fuel atomization, fuel and air control, and aerodynamics. Sufficient discussion is included to show the design methods that are necessary, in general, to achieve low emissions in continuous flow combustion systems. Emphasis is placed on the importance of interfacing a combustion system with other engine parts if a successful low emission, wide turndown ratio combustor working model is to be achieved. Sufficient discussion on combustion kinetics is included to advise on approaches necessary to minimize NO formation in external combustion systems while maintaining high efficiency and low CO and unburned hydrocarbons.     

Correlating Emissions with Time and Temperature to Predict Worst-Case Emissions from Open Liquid Area Sources

Abstract

The two primary factors influencing ambient air pollutant concentrations are emission rate and dispersion rate. Gaussian dispersion modeling studies for odors, and often other air pollutants, vary dispersion rates using hourly meteorological data. However, emission rates are typically held constant, based on one measured value. Using constant emission rates can be especially inaccurate for open liquid area sources, like wastewater treatment plant units, which have greater emissions during warmer weather, when volatilization and biological activity increase. If emission rates for a wastewater odor study are measured on a cooler day and input directly into a dispersion model as constant values, odor impact will likely be underestimated. Unfortunately, because of project schedules, not all emissions sampling from open liquid area sources can be conducted under worst-case summertime conditions. To address this problem, this paper presents a method of varying emission rates based on temperature and time of the day to predict worst-case emissions. Emissions are varied as a linear function of temperature, according to Henry’s law, and a tenth order polynomial function of time. Equation coefficients are developed for a specific area source using concentration and temperature measurements, captured over a multiday period using a data-logging monitor. As a test case, time/temperature concentration correlation coefficients were estimated from field measurements of hydrogen sulfide (H₂S) at the Rowlett Creek Wastewater Treatment Plant in Garland, TX. The correlations were then used to scale a flux chamber emission rate measurement according to hourly readings of time and temperature, to create an hourly emission rate file for input to the dispersion model ISCST3. ISCST3 was then used to predict hourly atmospheric concentrations of H₂S. With emission rates varying hourly, ISCST3 predicted 384 acres of odor impact, compared with 103 acres for constant emissions. Because field sampling had been conducted on relatively cool days (85–90 °F), the constant emission rate underestimated odor impact significantly (by 73%).     

Carbonyl Emissions from Commercial Cooking Sources in Hong Kong

Abstract

Cooking fumes are an important carbonyl emission source, especially in a highly urbanized city, such as Hong Kong. Cooking exhaust from 15 commercial kitchens of a variety of cooking styles was sampled and analyzed for a suite of 13 carbonyl compounds. Carbonyl compositions were varied among the different cooking styles. Formal dehyde was generally the most abundant carbonyl, and its contribution to the total carbonyl amount on a molar basis ranged from 12 to 60%. Acrolein was also found to be an abundant carbonyl in the cooking exhaust. The highest contribution by acrolein to the total carbonyls was found to be 30% in the exhaust of a western-style steak restaurant. Long-chain saturated carbonyls, that is, heptanal, octanal, and nonanal, accounted for a signifi-cant fraction (>40%) of the total carbonyls in kitchens that always used heated cooking oils. Two dicarbonyls, glyoxal and methylglyoxal, had a various presence in the cooking emissions, ranging from negligible to 10%. The presence of benzaldehyde and tolualdehyde was mostly negligible in the sampled kitchen exhaust. Annual emission rates of both individual carbonyls and total carbon-yls were estimated for various types of commercial kitchens. Local-style fast-food shops contributed the highest total carbonyl emissions per year mainly because of the large number of this kind of restaurant in Hong Kong. The citywide annual emission rates of the three most toxic carbonyls, formaldehyde, acetaldehyde, and acrolein, were estimated assuming that the limited number of sampled restaurants were representative of the average restaurants. Such estimates of carbonyl emission rates were comparable to the estimated carbonyl emissions from vehicular sources, suggesting the importance of commercial cooking as a source for carbonyls in Hong Kong.     

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.     

Automotive Emissions After Hot and Cold Starts in Summer and Winter

Randomly selected passenger automobiles were driven over a 7.5-mile composite route in Cincinnati, Ohio. Samples of the exhaust gases were collected from each car by means of a proportional sampler and analyzed for gross hydrocarbons, carbon monoxide, carbon dioxide, and oxides of nitrogen. In addition, detailed analysis of the hydrocarbons was made. This included parafins, 1 through 8 carbon, olefins, 2 through 6 carbon, and aromatics, 6 through 10 carbon. This paper compares the differences in these emissions immediately after starting with “cold” engines as opposed to emissions from cars started with engines already warmed up or “hot.” This determination was made under both cold and warm weather conditions. A comparison is also made in air pollutants emitted from cars driven under the summer as opposed to the winter conditions normally encountered in Cincinnati, Ohio.     

Toxic Emissions from Mobile Sources: A Total Fuel-Cycle Analysis for Conventional and Alternative Fuel Vehicles

ABSTRACT

Mobile sources are among the largest contributors of four hazardous air pollutants—benzene, 1,3-butadiene, acetal-dehyde, and formaldehyde—in urban areas. At the same time, federal and state governments are promoting the use of alternative fuel vehicles as a means to curb local air pollution. As yet, the impact of this movement toward alternative fuels with respect to toxic emissions has not been well studied. The purpose of this paper is to compare toxic emissions from vehicles operating on a variety of fuels, including reformulated gasoline (RFG), natural gas, ethanol, methanol, liquid petroleum gas (LPG), and electricity. This study uses a version of Argonne National Laboratory's Greenhouse Gas, Regulated Emissions, and Energy Use in Transportation (GREET) model, appropriately modified to estimate toxic emissions. The GREET model conducts a total fuel-cycle analysis that calculates emissions from both downstream (e.g., operation of the vehicle) and upstream (e.g., fuel production and distribution) stages of the fuel cycle. We find that almost all of the fuels studied reduce 1,3-buta-diene emissions compared with conventional gasoline (CG). However, the use of ethanol in E85 (fuel made with 85% ethanol) or RFG leads to increased acetaldehyde emissions, and the use of methanol, ethanol, and compressed natural gas (CNG) may result in increased formaldehyde emissions. When the modeling results for the four air toxics are considered together with their cancer risk factors, all the fuels and vehicle technologies show air toxic emission reduction benefits.     

A Strategy for the Evaluation of Sensory and Pulmonary Irritation Due to Chemical Emissions from Indoor Sources

Abstract

Sensory and pulmonary irritation are physiological responses to chemical exposure which result in characteristic, measurable changes in respiratory activity in mice. A standard method has been applied to the estimation of sensory irritation associated with a specific chemical exposure. This method has been correlated with human responses to these chemicals. Symptoms associated with chemical irritants are consistent with complaints due to problems with indoor air quality, which may include eye and upper respiratory tract irritation, headaches, and nausea. A stepwise strategy for assessing the contribution of indoor products to sensory and pulmonary irritation is discussed in the current paper. The strategy includes product emissions testing using dynamic environmental chambers, the selection of suspected irritants for respiratory irritation testing, respiratory irritation testing of individual compounds and representative mixtures using synthesized atmospheres, and the evaluation of test data to determine those compounds which may contribute to sensory and pulmonary irritation in humans. The current strategy is being applied to evaluate carpet system materials and their constituent chemicals.     

Estimating Gas Emissions from Multiple Sources Using a Backward Lagrangian Stochastic Model

Abstract

Manure storage tanks and animals in barns are important agricultural sources of methane. To examine the possibility of using an inverse dispersion technique based on a backward Lagrangian Stochastic (bLS) model to quantify methane (CH₄) emissions from multiple on-farm sources, a series of tests were carried out with four possible source configurations and three controlled area sources. The simulated configurations were: (C1) three spatially separate ground-level sources, (C2) three spatially separate sources with wind-flow disturbance, (C3) three adjacent ground-level sources to simulate a group of adjacent sources with different emission rates, and (C4) a configuration with a ground level and two elevated sources. For multiple ground-level sources without flow obstructions (C1 and C3), we can use the condition number (k, the ratio of the uncertainty in the calculated emission rate to the uncertainty in the predicted ratio of concentration to emission rate) to evaluate the applicability of this inverse dispersion technique and a preliminary threshold of k < 10 is recommended. For multiple sources with wind disturbance (C2) or an even more complex configuration including ground level and elevated sources (C4), a low k is not sufficient to provide reasonable discrete and total emission rates. The effect of flow obstructions can be neglected as long as the distance between the source and the measurement location is greater than approximately 10 times the height of the flow obstructions. This study shows that the bLS model has the potential to provide accurate discrete emission rates from multiple on-farm emissions of gases provided that certain conditions are met.     

Sources of anthropogenic platinum-group elements (PGE): Automotive catalysts versus pge-processing industries

Soil samples from the area of Hanau (Hessen, Germany) were analyzed for anthropogenic platinum-group elements (PGE). The results confirm the existence of two different sources for anthropogenic PGE: 1. automotive catalysts, and 2. PGE-processing plants. Both sources emit qualitatively and quantitatively different PGE spectra and PGE interelemental ratios (especially the Pt/Rh ratio). Elevated PGE values which are due to automotive catalysts are restricted to a narrow-range along roadside soil, whereas those due to PGE-processing plants display a large-area dispersion. The emitted PGE-containing particles in the case of automotive catalysts are subject to transport by wind and water, whereas those from PGE-processing plants are preferably transported by wind. This points to a different aerodynamic particle size. Pt, Pd, and Rh concentrations along motorways are dependent on the amount of traffic and the driving characteristics.     

中外饮食业油烟控制标准比较

饮食油烟的污染日益受到人们的重视，许多国家已制订了油烟排放的标准。作者从不同角度比较了4个国家或地区的饮食业油烟控制标准的异同，为我国今后饮食业油烟污染控制的技术开发、标准修订、产品推广等提供参考。     

MTBE in California's Drinking Water: A Comparison of Groundwater Versus Surface Water Sources

During the last decade, the fuel oxygenate methyl tertiary butyl ether (MTBE) has received widespread attention as a potential threat to water quality, primarily due to leaking underground gasoline storage tanks and watercraft with two-stroke engines. In this article, we examine the annual detection frequency, number of new source detections, and concentration of MTBE detected in California's public drinking water groundwater and surface water sources from 1995 to 2002. This work builds on our previous evaluations of California's water quality monitoring database. However, it is unique in that it includes separate evaluations for groundwater and surface water sources that are of greatest concern to regulators, and which are likely being used for current public consumption. Our evaluations also include full-year data for 2002 (which have not been published previously) and an analysis of how the sampling and reported detections of MTBE vary by geographic location. We find that MTBE was generally detected (at any level) in approximately 0.5-0.9% and 0.2-0.4% of all groundwater sources assuming a one-detection and two-detection criterion, respectively. The overall detection frequency for MTBE in surface water sources is significantly higher than for groundwater sources, although these surface water detections appear to have substantially declined since 1996 (e.g., 7-9% for all surface water sources during 1996 to 1999 and 4% for all surface water sources during 2000 to 2002, assuming a one-detection criterion). The detection frequency of MTBE concentrations at or above the state drinking water standards in all drinking water sources (both groundwater and surface water sources) and the subset of drinking water sources that are likely to currently be delivered to consumers is markedly lower (and often zero). Despite the significant increase in water sampling over time, the number of new drinking water sources found to contain MTBE in California has not increased at the same rate and appears to have remained relatively stable or to have decreased since 1998. The data also show that nearly all of the 58 counties in California have routinely sampled at least some of their groundwater and surface water sources for MTBE over the last 8 years. Geographical evaluations show that MTBE has been detected (at least once) in groundwater sources in 34 counties and in surface water sources in 18 counties but has only been detected routinely (i.e., for 3 or more years) in 16 and 7 counties, respectively. Detected concentrations of MTBE are also generally below state drinking water standards, particularly for surface water sources. In short: (1) MTBE is rarely found in California groundwater or surface water sources that are of greatest concern to regulators or the public, and (2) drinking water detections of MTBE are expected to decline in the future due to the pending phase-out of MTBE and recent regulatory programs aimed at controlling gasoline releases from underground storage tanks and two-stroke-engine watercraft.     

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).     

Interlaborafory Comparison of Formaldehyde Emissions from Particleboard Underlayment in Small-Scale Environmental Chambers

Formaldehyde (CH₂O) emissions from particleboard underlayment have been measured in 0.17 and 0.2 m³ chambers at separate laboratories to test the comparability of small scale environmental chamber measurements under different ventilation and product loading conditions. Absolute CH₂O calibration was established through intermethod comparison of different monitoring techniques against a CH₂O generation apparatus. Interlaboratory precision was enhanced via co-calibration of each laboratory’s CH₂O colorimetric analyzer against the same blank and bi-level generation source at the beginning and end of the study. The results show excellent intermethod and interlaboratory agreement in both the CH₂O calibration and particleboard emissions testing. The CH₂O emission rates of the test specimens demonstrate a Fick’s Law dependence on CH₂O vapor concentration. Measured CH₂O concentrations are described by a single-compartment, single emitter model, and are inversely proportional to the ratio [N/L (m/h)] of the air exchange rate [N(h^-1)] and product loading [L(m^-1)]. Comparison tests at varying N and L, but uniform N/L were performed; similar CH2O concentrations were measured for N and L levels selected from an indoor compartment model, and for fivefold larger N and L values, which are more convenient for small-scale chamber testing.