Emissions of Trace Products of Incomplete Combustion from a Pilot-Scale Incinerator Secondary Combustion Chamber

Abstract

Experiments were performed on a 73 kW rotary kiln incinerator simulator equipped with a 73 kW secondary combustion chamber (SCC) to examine emissions of products of incomplete combustion (PICs) resulting from incineration of carbon tetrachloride (CC14) and dichloromethane (CH2C12). Species were measured using an on-line gas chromatograph (GC) system capable of measuring concentrations of eight species of volatile organic compounds (VOCs) in a near-realtime fashion. Samples were taken at several points within the SCC, to generate species profiles with respect to system residence time. For the experiments, the afterburner on the SCC was operated at conditions ranging from fuel-rich to fuellean, while the kiln was operated at a constant set of conditions. Results indicate that combustion of CH2C12 produces higher levels of measured PICs than combustion of CC14, particularly 1, 2 dichlorobenzene, and to a lesser extent, monochlorobenzene. Benzene emissions were predominantly affected by the afterburner air/fuel ratio regardless of whether or not a surrogate waste was being fed.     

Prediction of Dioxin/Furan Incinerator Emissions Using Low-Molecular-Weight Volatile Products of Incomplete Combustion

ABSTRACT

Emissions of polychlorinated dibenzo-p-dioxins and poly-chlorinated dibenzofurans (PCDDs/Fs) from incinerators and other stationary combustion sources are of environmental concern because of the toxicity of certain PCDD/F congeners. Measurement of trace levels of PCDDs/Fs in combustor emissions is not a trivial matter. Development of one or more simple, easy-to-measure, reliable indicators of stack PCDD/F concentrations not only would enable incinerator operators to economically optimize system performance with respect to PCDD/F emissions, but could also provide a potential technique for demonstrating compliance status on a more frequent basis. This paper focuses on one approach to empirically estimate PCDD/F emissions using easy-to-measure volatile organic C₂ chlorinated alk-ene precursors coupled with flue gas cleaning parameters. Three data sets from pilot-scale incineration experiments were examined for correlations between C₂ chlorinated alk-enes and PCDDs/Fs. Each data set contained one or more C₂ chloroalkenes that were able to account for a statistically significant fraction of the variance in PCDD/F emissions. Variations in the vinyl chloride concentrations were able to account for the variations in the PCDD/F concentrations strongly in two of the three data sets and weakly in one of the data sets.     

Chemical and Biological Characterization of Products of Incomplete Combustion from the Simulated Field Burning of Agricultural Plastic

Chemical and biological analyses were performed to characterize products of Incomplete combustion emitted during the simulated open field burning of agricultural plastic. A small utility shed equipped with an air delivery system was used to simulate pile burning and forced-air-curtain incineration of a nonhalogenated agricultural plastic that reportedly consisted of polyethylene and carbon black. Emissions were analyzed for combustion gases; volatile, semi-volatile, and particulate organics; and toxic and mutagenlc properties. Emission samples, as well as samples of the used (possibly pesticide-contaminated) plastic, were analyzed for the presence of several pesticides to which the plastic may have been exposed. Although a variety of alkanes, alkenes, and aromatic and polycyclic aromatic hydrocarbon (PAH) compounds were identified in the volatile, seml-volatlle, and particulate fractions of these emissions, a substantial fraction of higher molecular weight organic material was not identified. No pesticides were Identified in either combustion emission samples or dlchloromethane washes of the used plastic. When mutagenlcity was evaluated by exposing Salmonella bacteria (Ames assay) to whole vapor and vapor/partlculate emissions, no toxic or mutagenlc effects were observed. However, organic extracts of the particulate samples were moderately mutagenlc. This mutagenlcity compares approximately to that measured from residential wood heating on a revertant per unit heat release basis. Compared to pile burning, forced air slightly decreased the time necessary to burn a charge of plastic. There was not a substantial difference, however, in the variety or concentrations of organic compounds Identified In samples from these two burn conditions. This study highlights the benefits of a combined chemical/biological approach to the characterization of complex, multi-component combustion emissions. These results may not reflect those of other types of plastic that may be used for agricultural purposes, especially those containing halogens.     

Pilot-Scale Evaluation of an Incinerability Ranking System for Hazardous Organic Compounds

The U.S. Environmental Protection Agency’s (EPA) hazardous waste incinerator performance standards specify a minimum destruction and removal efficiency (DRE) for principal organic hazardous constituents (POHCs) designated in the incinerator waste feed. In the past, selection of appropriate POHCs for incinerator trial burns has been based largely on their heats of combustion. Attempting to improve upon this approach, the University of Dayton Research Institute (UDRI), under contract to the EPA Risk Reduction Engineering Laboratory, has developed a thermal stability-based ranking of compound "incinerability". The subject study was conducted to evaluate the laboratory-developed ranking system in a pilot-scale incinerator.

Mixtures of POHCs, spanning the ranking scale from most- to least-difficult to destroy (Class 1 to Class 7, respectively), were prepared and combined with a clay-based sorbent matrix. These mixtures were then fed into the rotary kiln incineration system at the U.S. EPA Incineration Research Facility (IRF). In a series of five tests, the following conditions were evaluated: baseline/ typical operation; thermal failure (quenching); mixing failure (overcharging); matrix failure (low feed H/CI ratio); and a worst-case combination of the three failure modes.

Under baseline conditions, mixing failure, and matrix failure, kiln-exit DREs for each compound were comparable from test to test. Operating conditions in these 3 modes appeared to be sufficient to effect considerable destruction (greater than 99.99 percent DRE) of all compounds. As a result, separation of the highest-ranked POHCs from the lowest-ranked POHCs according to observed DRE was not possible; a correlation between POHC ranking and DRE could not be confirmed.

A correlation between predicted and observed incinerability was more evident for the thermal failure and worst-case conditions. Kiln-exit DREs for the four POHCs predicted to be most stable (those in Classes 1 and 2) ranged from 99% to 99.99% under these conditions, and were generally lower than DREs for the POHCs predicted to be more easily destroyed. Statistically significant correlations above the 99 percent and 93 percent confidence intervals were identified for the thermal-failure and worst-case tests, respectively.     

Screening Models for Estimating Toxic Air Pollution Near a Hazardous Waste Landfill

This paper is directed to environmental scientists concerned with assessing toxic air pollution downwind of hazardous waste landfills to determine whether potential health threats or exceedances of air quality standards exist. The purpose of this paper is to evaluate the performance of four air quality screening models.

The emission rate of vinyl chloride from the BKK co-disposal landfill in West Covina, California is estimated. Ambient vinyl chloride concentrations are estimated using a ground level point source model, two virtual point source models, arid the simple box model with meteorological and landfill input data representative of periods when ambient monitoring was conducted. The two virtual point source models are most precise and accurate in estimating 24-hour vinyl chloride concentrations. However, the results could include compensating errors in the emission rate and dispersion calculations because the emission rate estimate could not be independently evaluated.     

Research and Evaluation of Organic Hazardous Air Pollutant Source Emission Test Methods

Abstract

Title III of the Clean Air Act Amendments of 1990 has increased the need for well defined and tested stationary source emission sampling and analysis methods. The Methods Branch of the Air Measurements Research Division of U.S. EPA's Office of Research and Development is responsible for a major methods development and evaluation program intended to help fill that need. This paper summarizes recent developments from several of the component projects of that program. Primary emphasis is placed on status and references for methods for organic hazardous air pollutants, such as phosgene, methanol, chloroform, acetonitrile, isocyanates, aldehydes, halogenated organics, non-halogenated organics, and volatile organic material     

Adsorption Characteristics of Activated Carbon and XAD4 Resin for the Removal of Hazardous Organic Solvents

A comparative study has been conducted on adsorption/desorption of six hazardous organic vapors on synthetic resin (XAD4) and activated carbon, using a differential reactor involving the expansion of a quartz spring. While both sorbents can effectively remove the organic vapors, it was observed that at low concentrations activated carbon adsorbed more organic vapor than synthetic resin. At higher, industrial concentrations, the resins adsorbed more vapor as demonstrated by the slopes of the equilibrium isotherms. The resin also showed much higher desorptlon.

The effective Intraparticle diffusion coefficients (D_e) were observed to be strongly dependent on solute concentration. Pore diffusion dominated the adsorption/desorption of the six organic vapors on XAD4 resin. For the carbon system, pore diffusion dominated the adsorption but surface diffusion contributed to the desorptlon process. This is believed to be due to higher Interaction of the adsorbates with activated carbon.     

Characterization of Products from Fluidized-Bed Combustion of Coal

ABSTRACT

The technology of fluidized-bed combustion (FBC) of coal generates byproducts that have a series of unique characteristics and potential uses in technological practice. In this study, the products of fluidized-bed combustion (FBC-P) of coal derived from Moravian heat stations, a.s. Zlin, Cinergy Global Resources, Czech Republic, were characterized. Particular attention was paid to determining the chemical composition of FBC-P, the content of polycyclic aromatic hydrocarbons (PAHs) and toxic metals in the water leachates of these FBC-P, the content of unburned carbon, the capability of FBC-P to solidify with water and form a solid matrix, and the method for discovering optimum mixing water content for FBC-P solidification. The results suggest that one of the qualitatively more important means of utilizing FBC-P could be their application during solidification/stabilization (S/S) of wastes, particularly wastewa-ter treatment sludges.     

Full-Scale Evaluation of the Thermal Stability-Based Hazardous Organic Waste Incinerability Ranking

De nombreuses études épidémiologiques ont observé dans des contextes différents une faible relation à court terme entre les particules et la mortalité cardio-pulmonaire, même quand les normes de qualité de l'air n'étaient pas dépassées. La causalité de cette relation est un enjeu de santé publique en raison de l'importance de la population exposée. Notre objectif est de faire l'inventaire critique des arguments utilisés dans 15 revues de la littérature publiées.

Nous expliquons l'importance de distinguer la validité de la causalité et analysons de façon systématique les différents critères de jugement dans le contexte des études écologiques temporelles. Notre conclusion est que la relation observée est valide et que la plupart des critères de causalité sont respectés. Diminuer le niveau d'exposition des populations aux particules est souhaitable. En Europe, en agissant à la source, notamment sur les émissions Diesel, on diminuera aussi d'autres polluants qui peuvent jouer un rôle sanitaire. Aux États-Unis, la situation est plus complexe car les particules sont surtout secondaires.

Il est également indispensable de poursuivre les recherches pour mieux connaître les déterminants des expositions globales des individus et mieux comprendre le rôle toxique des différents facteurs physico-chimiques des particules.     

Evaluation of Canisters for Measuring Emissions of Volatile Organic Air Pollutants from Hazardous Waste Incineration

Regulation to control air emissions of toxic organic compounds require the collection and analysis of effluent gas from low level sources such as hazardous waste incinerators. The standard SW- 846 Method specifies the use of Tenax and Tenax/charcoal adsorbent traps for collection of volatile organics from incinerators. This study evaluates passivated stainless steel canisters as an alternative to adsorbent traps to eliminate some of the problems associated with adsorbent sampling. Initially the stability of 18 nonpolar, volatile organic compounds was determined in Summa-treated stainless steel canisters with greater than 100 ppmv HCI and saturated with water vapor. All 18 components were stable for a twoweek period; however, an Interference caused a 10-fold increase In the FID response of trlchloroethylene, toluene, and chlorobenzene. No Interference of the ECD response was found for any of the 11 compounds detected with the ECD including trlchloroethylene. A pilot scale incinerator was sampled using canisters, and the destruction efficiency of 1,1,1-trichloroethane was determined at a concentration of less than 0.5 ppbv while determining 1,1-dichloroethylene, the major product of Incomplete combustion, at a concentration of 8000 ppbv from the same sample.     

Chemical Transformations of Nitrogen Oxides While Sampling Combustion Products

The present study reviews the sampling environments and chemical transformations of nitrogen oxides that may occur within probes and sample lines while sampling combustion products. Experimental data are presented for NO_x transformations in silica and 316 stainless steel tubing when sampling simulated combustion products in the presence of oxygen, carbon monoxide, and hydrogen. A temperature range of 25° to 400°C is explored. In the absence of CO and H₂, 316 stainless steel is observed to promote the reduction of nitrogen dioxide to nitric oxide at temperatures in excess of 300°C, and silica is found to be passive to chemical transformation. In the presence of CO, reduction of N0₂ to NO is observed in 316 stainless steel at temperatures in excess of 100°C, and reduction of NO₂ to NO in silica is observed at 400°C. In the presence of H₂, NO₂ is reduced to NO in 316 stainless steel at 200°C and NO_x is removed at temperatures exceeding 200°C. In silica, the presence of H₂ promotes the reduction of NO₂ to NO at 300°C and the removal of NO_x above 300°C.     

Evaluation of Parts-per-billion Organic Cylinder Gases for Use as Audits During Hazardous Waste Trial Burn Tests

A repository of 14 gaseous organic compounds at parts-per-billion levels (7-430 ppb) in compressed gas cylinders has been established by the Environmental Protection Agency. This repository was established to provide audit materials for use in conducting performance audits to assess the accuracy and precision of principal organic hazardous constituent (POHC) measurements, especially those performed during hazardous waste trial burn tests. Five- and nine-component mixtures In a balance gas of nitrogen were prepared in aluminum cylinders for use in the performance audit program. The five-component mixtures contain carbon tetrachloride, chloroform, perchloroethylene, vinyl chloride, and benzene. The ninecomponent mixtures contain trichloroethylene, 1,2-dichloroethane, 1,2-dibromoethane, acetonitrile, trichlorofjuoromethane, dichlorodifluoromethane, bromomethane, methyl ethyl ketone and 1,1,1-trichloroethane.

Studies of all 14 gaseous organic compounds were performed to determine the stability of the compounds and the feasibility of using them in performance audits. Results indicate that ail of the 14 compounds were adequately stable to be used as reliable audit materials. Also, the estimation of specific uncertainties associated with the analysis of these audit materials and how those uncertainties are used to assign a total uncertainty to the final analyte concentration for 14 organics Is described.

Subsequent to completion of the stability studies, several performance audits were conducted using the repository gases to assess the accuracy and precision of the volatile organic sampling train (VOST) and bag measurement methods. The audit results indicate that laboratories can use these methods to analyze POHC with accuracy usually to within ± 50 percent of the audit concentrations.     

Combustion as the Principal Source of Carbonaceous Aerosol in the Ohio River Valley

Organic and elemental carbon and a number of carboxylic acids and n-alkanes were measured in aerosol samples collected at three sites in the Ohio River Valley between October 1980 and August 1981. Approximately 100 filters were analyzed for organic and elemental carbon for each site. For the 11-month period organic and elemental carbon comprised about 19 percent of the total aerosol mass with about two-thirds of the carbon as organic. Regression analysis showed that the principal source of organic carbon was combustion. The measurements of the specific organic compounds indicated a weak biogenic component to the organic aerosol.     

Continuous Infrared Analysis of N2O in Combustion Products

Nitrous oxide (N₂O) levels in the atmosphere are increasing, potentially contributing to the greenhouse effect and depletion of stratospheric ozone. From a limited data base, combustion sources have been identified as a major anthropogenic source of N₂O. However, the existing data base (obtained by traditional grab sampling techniques followed by gas chromatographic analysis) is in question due to the discovery of a sampling artifact. A continuous on-line N₂O analyzer would enable and facilitate the accurate characterization of combustion sources over a range of operating conditions, and also aid in the development of an appropriate sampling technique. This paper addresses the development of a continuous measurement technique, and the evaluation and initial use of a field prototype continuous N₂O analyzer developed at the UCI Combustion Laboratory in cooperation with a major instrument manufacturer. The analyzer is capable of measuring N₂O levels down to a few ppm. The analyzer has been evaluated and used to study the N₂O emissions from a pulverized coal-fired boiler. The N₂O levels found with the analyzer are substantially lower than levels previously attributed to such sources. Initial N₂O measurements made with the analyzer suggest that N₂O levels are not a substantial fraction of the NO_X levels, as previously suggested.     

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).     

A Comparative Analysis of Modeled and Monitored Ambient Hazardous Air Pollutants in Texas: A Novel Approach Using Concordance Correlation

Abstract

Often, in studies evaluating the health effects of hazardous air pollutants (HAPs), researchers rely on ambient air levels to estimate exposure. Two potential data sources are modeled estimates from the U.S. Environmental Protection Agency (EPA) Assessment System for Population Exposure Nationwide (ASPEN) and ambient air pollutant measurements from monitoring networks. The goal was to conduct comparisons of modeled and monitored estimates of HAP levels in the state of Texas using traditional approaches and a previously unexploited method, concordance correlation analysis, to better inform decisions regarding agreement. Census tract-level ASPEN estimates and monitoring data for all HAPs throughout Texas, available from the EPA Air Quality System, were obtained for 1990, 1996, and 1999. Monitoring sites were mapped to census tracts using U.S. Census data. Exclusions were applied to restrict the monitored data to measurements collected using a common sampling strategy with minimal missing values over time. Comparisons were made for 28 HAPs in 38 census tracts located primarily in urban areas throughout Texas. For each pollutant and by year of assessment, modeled and monitored air pollutant annual levels were compared using standard methods (i.e., ratios of model-to-monitor annual levels). Concordance correlation analysis was also used, which assesses linearity and agreement while providing a formal method of statistical inference. Forty-eight percent of the median model-to-monitor values fell between 0.5 and 2, whereas only 17% of concordance correlation coefficients were significant and greater than 0.5. On the basis of concordance correlation analysis, the findings indicate there is poorer agreement when compared with the previously applied ad hoc methods to assess comparability between modeled and monitored levels of ambient HAPs.     

The Use of Electrokinetics for Hazardous Waste Site Remediation

The Superfund Innovative Technology Evaluation (SITE) program was authorized as part of the 1986 amendments to the Superfund legislation. It represents a joint effort between U.S. EPA’s Office of Research and Development and Office of Solid Waste and Emergency Response. The program is designed to assist and encourage the development of waste treatment technologies that would contribute to more solutions to our hazardous waste problems.

Recently, EPA, through the SITE program, issued a work assignment to assess the “stateof- the-art” of electroklnetically enhanced contaminant removal from soils. Prior research efforts, both laboratory and field, have demonstrated that electroosmosis has the potential to be effective In facilitating the removal of certain types of hazardous wastes from soils. Particularly encouraging results have been achieved with inorganics in fine-grained soils where more traditional removal alternatives are less effective.

Although the results of various studies suggest that electrokinetics is a promising technology, further testing Is needed at both the laboratory and field levels to fully develop this technology for site remediation. A conceptual test program Is presented based on best available data which incorporates system design and operating parameters used in previous applications of this technology In the use of electrokinetics treatment as a remediation technique at hazardous waste sites.     

樟脑废水高效优势降解菌的选育及降解效果

针对樟脑废水，从活性污泥中筛选出降解樟脑废水的高效优势菌，通过分离纯化，优选出三株适应能力强、生长旺盛的菌株，分别为ZH-1，ZH-2、TZH-2。经初步鉴定分别为动胶菌属、假单胞菌属、短杆菌属。试验测定了单株菌和混合菌对樟脑废水的降解效果，结果表明，混合菌的降解效果最为明显，降解率为75．23％。     

1987 Market Outlook for Air Pollution Control and Hazardous Waste Management

Change has characterized nearly all aspects of the air pollution control industry during the last year. The supplier companies are changing due to mergers and increased activity from foreign suppliers. Both the products and the markets are changing due to developing technologies and a changing regulatory picture. Waste-to energy and VOC control are seen as growth industries in the U.S., and a resurgence is expected in the FGD and utility particulate control arenas over the next ten years. Expansion of air pollution control companies into hazardous