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.     

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     

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.     

Pilot-Scale Demonstration of an Innovative Treatment for Vapor Emissions

ABSTRACT

Researchers from the National Renewable Energy Laboratory recently conducted a pilot-scale study at McClellan Air Force Base (AFB) in Sacramento, CA. The objective of the test was to determine the effectiveness of an ambient-temperature, solar-powered photocatalytic oxidation treatment unit for destroying emissions of chlorinated organic compounds from an air stripper. This paper reports test results and discusses applications and limitations of the technology.

A 10-standard-cubic-foot-per-minute (SCFM) (28.3 L/min) slip stream of air from an air stripper at Operative Unit 29-31 at McClellan AFB was passed through a reactor that contained a lightweight, perforated, inert support coated with photoactive titanium dioxide. The reactor faced south and was tilted at a 45° angle from vertical so that the light-activated catalyst received most of the available sunlight. An online portable gas chro-matograph with two identical columns simultaneously analyzed the volatile organic compounds contained in the reactor inlet and outlet air streams. Summa canister grab samples of the inlet and outlet were also collected and sent to a certified laboratory for U.S. Environmental

Protection Agency Method TO-14 analysis and verification of our field analyses. Three weeks of testing demonstrated that the treatment system's destruction and removal efficiencies (DREs) are greater than 95% at 10 SCFM with UV intensities at or greater than 1.5 milliwatts/square centimeter (mW/cm²). DREs greater than 95% at 20 SCFM were obtained under conditions where UV irradiation measured at or greater than 2 mW/cm². In Sacramento, this provided 6 hours of operation per clear or nearly clear day in April. A solar tracking system could extend operating time. The air stream also contained trace amounts of benzene. We observed no loss of system performance during testing.     

Long-path FTIR Measurements of Volatile Organic Compounds in an Industrial Setting

A long-path Fourier transform spectrometer was used to make measurements of volatile organic compounds in an industrial complex in New Castle, Delaware as part of the Superfund Innovative Technology Evaluation (SITE) program. These data are compared to data taken with a whole-air canister technique. To provide an effective comparison the canisters were transported along the path for a 32-min period. For each FTIR spectrum, 256 interferograms were co-added over a 4-mln period. Eight individual spectra were then co-added to obtain the comparison data.     

Screening Approach for Principal Organic Hazardous Constituents and Products of Incomplete Combustion

The body of information presented in this paper is directed to those individuals concerned with developing or implementing screening strategies for characterizing organic emissions from incinerators and other combustion sources. The need to characterize hazardous waste incinerator emissions for multiple organic compounds has been steadily increasing for several years. The regulatory approach makes use of a type of indicator compound procedure that concentrates on principal organic hazardous constituents (POHCs). In addition to continuing interest in POHCs, interest has been growing in the types and concentrations of products of incomplete combustion (PICs). Sampling and analysis methods have been developed previously for approximately 225 of the more important POHCs and PICs. These methods may be used as components of a cost-effective screening protocol aimed at maximum characterization of emissions, whether the project budget is large or small. This paper contains a discussion of fundamental principles of several kinds of screening strategies and recommends an approach suitable for incinerators and other combustion sources. The concept of a risk-driven analysis strategy is introduced and illustrated with a simplified example.     

Development and Demonstration of a Pilot-Scale Debris Washing System

Metallic, masonry, and other solid debris that may be contaminated with hazardous chemicals litter numerous hazardous waste sites in the United States. Polychlorinated biphenyls (PCBs), pesticides, lead or other metals are some of the contaminants of concern. In some cases, cleanup standards have been established (e.g., 10 μg PCBs/100 cm² for surfaces to which humans may be frequently exposed). Decontaminated debris could be either returned to the site as “clean” fill or, in the case of metallic debris, sold to a metal smelter.

This project involves the development and demonstration of a technology specifically for per forming on-site decontamination of debris. Both bench-scale and pilot-scale versions of a debris washing system (DWS) have been designed, constructed, and demonstrated. The DWS entails the application of an aqueous solution during a high-pressure spray cycle, followed by turbulent wash and rinse cycles. The aqueous cleaning solution is recovered and reconditioned for reuse concurrently with the debris-cleaning process, which minimizes the quantity of process water required to clean the debris.     

Evaluation of Continuous Performance Monitoring Techniques for Hazardous Waste Incinerators

This paper discusses monitoring the waste destruction efficiency of hazardous waste incinerators. The particular problem is to ensure that incinerators do not release, without detection, significant quantities of waste as a result of operating fluctuations or equipment degradation. To detect these conditions, continuous, automated, and real-time source monitoring is required. Detection of degraded performance by monitoring and measuring waste compounds directly is not presently possible on a continuous basis. An alternative is to use commercially available continuous monitors to measure combustion intermediates (e.g., CO or hydrocarbons) and thereby infer waste destruction efficiency. Required, however, is a correlation between the emission of intermediates and the emission of waste. In this paper, the response of a number of these continuous monitors is compared with waste destruction efficiency measurements from a laboratory scale, liquid-spray incinerator operated on fuel oil doped with model waste compounds: benzene, chlorobenzene, acrylonitrile, and chloroform. Total hydrocarbon and CH₄ measurements are found to vary with waste emission in a nearly linear manner; however, a substantial increase in CO emission occurs before a significant amount of waste is released. These results suggest that CO may serve as an indicator of the approach of waste release, while total hydrocarbons may provide an indicator of immediate waste release.     

Microwave Plasma Conversion of Volatile Organic Compounds

Abstract

A microwave-induced, steam/Ar/O₂ , plasma “torch” was operated at atmospheric pressure to determine the feasibility of destroying volatile organic compounds (VOCs) of concern. The plasma process can be coupled with adsorbent technology by providing steam as the fluid carrier for desorbing the VOCs from an adsorbent. Hence, N₂ can be excluded by using a relatively inexpensive carrier gas, and thermal formation of oxides of nitrogen (NO_x ) is avoided in the plasma.

The objectives of the study were to evaluate the technical feasibility of destroying VOCs from gas streams by using a commercially available microwave plasma torch and to examine whether significant byproducts were produced. Trichloroethene (TCE) and toluene (TOL) were added as representative VOCs of interest to a flow that contained Ar as a carrier gas in addition to O₂ and steam.The O₂ was necessary to ensure that undesirable byproducts were not formed in the process. Microwave power applied at 500–600 W was found to be sufficient to achieve the destruction of the test compounds, down to the detection limits of the gas chromatograph that was used in the analysis. Samples of the postmicrowave gases were collected on sorbent tubes for the analysis of dioxins and other byproducts. No hazardous byproducts were detected when sufficient O₂ was added to the flow. The destruction efficiency at a fixed microwave power improved with the addition of steam to the flow that passed through the torch.     

Thermal Oxidation Kinetics of Selected Organic Compounds

A thermal oxidizer destroys organic pollutants by oxidation to CO₂ and water. Time, temperature, and turbulence, govern the performance of a thermal oxidizer just as they do all other combustion devices. To achieve a desired degree of destruction, a higher temperature allows the use of a shorter residence time and vice versa. For most organics, a thermal oxidizer designed at 1400°-1500°F with 0.1 to 0.3 seconds residence time is normally enough to obtain nearly complete destruction.¹ However, some chemicals require more extreme conditions. These time-temperature requirements can be determined from kinetic rate studies.     

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.     

生活垃圾填埋场填埋气中挥发性有机物释放规律分析

于2007年2月在上海老港垃圾填埋场选取10个不同填满年限的填埋单元进行填埋气的采样分析,用色谱-质谱技术检测了填埋气中的挥发性有机物(VOCs).检测到脂肪烃、卤代脂肪烃、单环芳烃、醚和酮等5类22种化合物,其中11种为美国环境保护署优先控制污染物,甲苯、乙苯和间,对二甲苯的浓度较高.填满时间距采样时间较近(1～2年)的填埋单元检出的VOCs种类较多,脂肪烃和单环芳烃的浓度随填满时间的增加呈现较明显的衰减特征,而卤代脂肪烃、醚和酮的浓度与填满时间的相关性不显著.检出的5种化合物中,1,1,1三氯乙烷、甲苯和间,对-二甲苯的浓度均低于美国加利福尼亚州环保局推荐的健康阈值,氯乙烯和苯则超过该阈值.     

An Evaluation of Commercial Hazardous Waste Thermal Destruction Capacity

Thermal destruction capacity for commercial hazardous waste in the United States is examined to determine current and future capacity requirements. This study focuses on commercial incinerators and cement kilns burning conventional hazardous wastes. Aggregate maximum and available capacity estimates are derived using the most recent information. On a national basis, available capacity far exceeds present demand. On a regional basis, capacity appears sufficient with the exception of the California area. However, this shortfall appears insignificant given the overall capacity situation. While incineration demand may increase for solids and sludges as a consequence of Land Ban disposal restrictions and other reasons, capacity for these wastes again appears sufficient to meet current and projected demands. Thus, arguments that additional commercial incineration capacity will be needed to accommodate an expected increase in incinerable hazardous waste cannot be supported by the available information. The analysis raises concerns about the determination of realistic capacity estimates, and the lack of interaction between the capacity assurance process that documents the need for capacity and state siting processes for new waste management facilities. The excess incineration capacity shown in this paper will contribute to the successful implementation of EPA’s goal to reduce national capacity.     

Effectiveness of Photocatalytic Filter for Removing Volatile Organic Compounds in the Heating,Ventilation, and Air Conditioning System

Abstract

Nowadays, the heating, ventilation, and air conditioning (HVAC) system has been an important facility for maintaining indoor air quality. However, the primary function of typical HVAC systems is to control the temperature and humidity of the supply air. Most indoor air pollutants, such as volatile organic compounds (VOCs), cannot be removed by typical HVAC systems. Thus, some air handling units for removing VOCs should be added in typical HVAC systems. Among all of the air cleaning techniques used to remove indoor VOCs, photocatalytic oxidation is an attractive alternative technique for indoor air purification and deodorization. The objective of this research is to investigate the VOC removal efficiency of the photocatalytic filter in a HVAC system. Toluene and formaldehyde were chosen as the target pollutants. The experiments were conducted in a stainless steel chamber equipped with a simplified HVAC system. A mechanical filter coated with Degussa P25 titania photocatalyst and two commercial photocatalytic filters were used as the photo-catalytic filters in this simplified HVAC system. The total air change rates were controlled at 0.5, 0.75, 1, 1.25, and 1.5 hr^?1, and the relative humidity (RH) was controlled at 30%, 50%, and 70%. The ultraviolet lamp used was a 4-W, ultraviolet-C (central wavelength at 254 nm) strip light bulb. The first-order decay constant of toluene and form-aldehyde found in this study ranged from 0.381 to 1.01 hr^?1 under different total air change rates, from 0.34 to 0.433 hr^?1 under different RH, and from 0.381 to 0.433 hr^?1 for different photocatalytic filters.     

Destruction of Volatile Organic Compounds Using Catalytic Oxidation

Catalytic oxidation is an air pollution control technique in which volatile organic compounds (VOCs) and vapor-phase air toxics in an air emission stream are oxidized with the help of a catalyst Design of catalytic systems for control of point source emissions is based on stream-specific characteristics and desired control efficiency. This paper discusses the key emission stream characteristics and VOC characteristics that affect the applicability of catalytic oxidation. The application of catalytic oxidation technology to four types of air emission sources is discussed: (1) groundwater stripping operations; (2) graphic arts facilities; (3) flexographic printing plants; and (4) latex monomer production. The characteristics of each of these emissions are discussed along with the catalytic technology used to control these emissions.     

Evaluation of Chemical Exposures in the Hazardous Waste Industry

Abstract

The assessment of personnel exposure to volatile solvent vapors is an important aspect in any comprehensive health and safety program. This is particularly true at Treatment, Storage, and Disposal Facilities (TSDFs) and for industries dealing with volatile solvents. This paper presents organic vapor monitoring data from seven TSDFs and from several routine small business and household activities. It shows that proper controls at TSDFs effectively reduce personnel vapor exposure. Through an examination of data from a specialized business such as a TSDF, along with data from more routine activities, a different perspective arises regarding potential hazards associated with hazardous waste disposal activities.     

An Evaluation of the Semi-VOST Method for Determining Emissions from Hazardous Waste Incinerators

The Semi-Volatile Organic Sampling Train method was investigated to determine its reliability and to determine the bias and precision of the method when used to determine emissions from hazardous waste incinerators. Experiments showed that the matrix and sampling variables usually involved in sampling emissions from a hazardous waste incinerator had no significant effect on the recovery of 11 different organic compounds. Significant losses of the sampled compounds can occur during sample preparation. The degree of loss appears to be directly related to the compounds, vapor pressure. These losses can be corrected for by adding deuterated surrogates to the sample and analyzing the surrogates along with the native compounds.

The bias determination was based on dynamic spiking of the sampling train with five deuterated organic compounds selected from Appendix VIII of the Resource Conservation and Recovery Act regulations. The results show biases of from -1 ± 8 percent to -18 ± 27 percent for chlorinated and nonchlorinated compounds. Pyridine, a water-soluble compound, showed a larger bias of-29 ± 13 percent. Particular attention to the recovery of water soluble compounds is necessary to minimize bias in their determinations. Further work is needed to determine the reliability of laboratory-determined retention volumes that are used to determine sampling conditions.