Measuring the Organic Carbon Content of Source Emissions for Air Pollution Control

Measuring emissions of organic materials from such sources as paint bake ovens, degreas-ing operations, and printing processes is a necessy part of a control program for solvents. Over the intervening years since 1966 when Los Angeles first enacted its solvent Rule 66, a considerable number of tests have been performed and the present test method has gone through a period of experience and improvement. A sample is collected from a stack or vent in a freeze-out trap cooled with dry ice followed by an evacuated 8-liter tank. Analysis is done by a system of gas chromatography and catalytic combustion to yield the total organic carbon content. Representative industrial emission analysis results, which demonstrate the practical applicability of the system, are shown.     

Development of Instrumentation for Continuous On-line Monitoring of Non-Methane Organic Carbon in Air Emissions

ABSTRACT

Non-methane organic carbon (NMOC) is a measure of total organic carbon in an air emission, excluding that from methane. Thus, it measures the total amount of carbon, irrespective of the structure and functional groups in the molecule. The U.S. Environmental Protection Agency (EPA) Method 25 is used for quantification of NMOC in emission sources and in ambient air. This method involves laboratory analysis of collected air samples and cannot be used for real-time measurements. It is prone to interferences from CO₂, CH₄, and CO, as well as moisture. In this paper, a novel method for continuous, on-line monitoring of NMOC in air emissions and ambient air is presented. Detection limits are at ppb levels, and interference of permanent gases have been eliminated.     

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.     

Scientific Basis of an Improved EPA Policy on Control of Organic Emissions for Ambient Ozone Reduction

ABSTRACT

This article describes an effort to re-examine the scientific bases of the existing, more than two decades-old U.S. Environmental Protection Agency (EPA) policy on volatile organic compound reactivity in light of recent scientific knowledge and understanding. The existing policy allows “negligibly reactive” organic emissions, that is, emissions with ambient ozone production potential lower than that of ethane, to be exempted from all ozone regulations. It relies on use of k_OH and incremental reactivity data for determining whether an organic compound is negligibly reactive. Recent scientific evidence suggests that (1) exempting the negligibly reactive organic emissions from all regulations is unjustifiable, (2) the choice of ethane as the benchmark organic species for distinguishing reactive from negligibly reactive organics may be inappropriate, (3) the assumptions and methods used for classifying organic compounds as “reactive” and “negligibly reactive” should be reconsidered, and (4) the volatility factor should be considered, more appropriately, in much the same way as the reactivity factor.     

Models to Estimate Volatile Organic Hazardous Air Pollutant Emissions from Municipal Sewer Systems

Abstract

Emissions from municipal sewers are usually omitted from hazardous air pollutant (HAP) emission inventories. This omission may result from a lack of appreciation for the potential emission impact and/or from inadequate emission estimation procedures. This paper presents an analysis and comparison of the models available to estimate volatile organic HAP (VOHAP) emissions from sewers. Comparisons were made between the different theoretical foundations of the models, as well as between the emissions predicted by the models for a single sewer component. Sewer gas concentrations predicted by the models were also compared to measured sewer gas concentrations reported in the literature. Two of the models were compared in their ability to estimate sewer VOHAP emissions for a large U. S. city using National Pollution Discharge Effluent System data for the influent wastewater to the city's municipal wastewater treatment facilities. This estimate showed that, regardless of the model used, sewer emissions are a potentially significant source of VOHAP emissions in the urban environment. The choice of model, however, is thought to be less critical to sewer emission estimates than the source of sewer wastewater VOHAP concentration data.     

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).     

Fuel Oil Additives for Controlling Air Contaminant Emissions

An addition of additives to fuel oils prior to combustion is one way of reducing combustible contaminant emissions to the outer air. Reported test results show that some additives improve, moderately, the combustive properties of fuel oils. Combustion is also improved but to a lesser degree, in boiler systems that are deficient in operation and design. Being combustible, polynuclear hydrocarbons emissions would be reduced by use of additives. Other types of additives to reduce slagging and inhibit corrosion from combustion of fuel oils are also available. The cost of using additives is low. Improved additives are required, especially ones to better combustion in the deficient boiler systems. These can be found by research and literature surveys. Their effectiveness and nontoxicity would be confirmed by laboratory and field testing.     

A Strategy for Reduction of Particulate Emissions in the Boston Area

Initial implementation plans provided for particulate reduction largely through the imposition of emission limitations on industrial processes, large steam generators, and solid waste disposal, requiring, in turn, application of control equipment for compliance. In many urban areas, this approach is not adequate to achieve the secondary air quality standards so that a more general strategy must be employed. Such strategy may include restrictions on fuel burning, combustion equipment, maintenance programs, utility steam distribution, etc. The potential abatement achievable through such strategies is described using Boston as a case study. Cost and technical factors associated with each strategy are discussed.     

Incineration Techniques for Control of Volatile Organic Compound Emissions

A review of incineration techniques for control of volatile organic compound emissions is presented in two consecutive issues o/JAPCA. Part I presented an overview of the process including fundamentals and design considerations. Both thermal and catalytic incinerators were considered. Part IIpresents capital and annual operating cost estimates for both thermal and catalytic incinerator systems based on information received from a number of equipment manufacturers.     

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.     

The Development of Air Contaminant Emission Tables for Nonprocess Emissions

In New York State, the calculation of air contaminant emissions from a variety of sources is an essential part of comprehensive air pollution studies. The tables used to calculate emissions were obtained from an extensive literature search and modified to apply to New York State conditions. For example, sulfur dioxide emission factors for coal were selected to reflect the average sulfur content of the coal sold in New York State. Since the literature contains a wide array of emission factors, it was necessary to evaluate the factors and select those which would be most appropriate for the techniques used in conducting the comprehensive studies in New York State. This paper does not present the emission tables themselves but does outline the development of such tables for use in nonprocess calculations, i.e., combustion for heat and power of bituminous and anthracite coal, distillate and residual oil, natural and bottled gas; combustion of gasoline and diesel in internal combustion engines; burning of refuse in dumps and incinerators; and evaporation of gasoline from marketing operations.     

Treatment of Propylene Glycol Monomethyl Ether Acetate in Air Streams by a Biofilter Packed with Fern Chips

Abstract

This study aimed to develop a biofilter packed only with fern chips for the removal of airborne propylene glycol monomethyl ether acetate (PGMEA). Fern chips could avoid the shortcomings of traditional media, such as compaction, drying, and breakdown, which lead to the performance failure of the biofilters. In addition, the fern chip medium has the following merits: (1) simplicity in composition; (2) low pressure drop for gas ?ow (<20 mmH₂O?m^-1); (3) simple in humidification, nutrient addition, pH control, and metabolite removal; (4) economical (US$174–385?m^-3), and (5) low weight (wet basis around 290 kg?m^-3). A two-stage down?ow biofilter (2.18 m in height and 0.4×0.4 m in cross-sectional area) was constructed for the performance test. Both stages were packed with fern chips of 0.30 m in height and 0.40×0.40 m in cross-section. Results indicate that with operation conditions of media moisture content controlled in the range of 50–74%, media pH of 6.5–8.3, empty bed retention time (EBRT) of 0.27–0.4 min, in?uent PGMEA concentrations of 100–750 mg?m^-3, volu-metric organic loading of <170 ?m^-3 ?hr^-1, and nutrition rates of Urea-nitrogen 66 g?m^-3 ?day^-3, potassium dihydrogen phosphate (KH₂PO₄)-phosphorus 13.3 g ?m^-3 ?day^-3, and milk powder 1.00 g?m^-3?day^-1, the fern-chip-packed biofilter could achieve an overall PGMEA removal efficacy of around 94%. Instant milk powder or liquid milk was essential to the good and stable performance of the biofilter for PGMEA removal.     

Air Pollution Emissions from the Incineration of Hospital Waste

Since 1981, hospitals in Illinois have been prohibited from depositing hazardous infectious waste in landfills without first rendering the waste innocuous. The Illinois Pollution Control Board has adopted regulations indicating that incineration is an acceptable method for disposal of this waste. Emissions from incineration of the plastic-rich hospital waste are not well documented. Stack emissions of particles, hydrochloric acid, carbon monoxide, ethane, ethylene, propane and propylene were measured from a hospital incinerator where all of the hospital's waste (including hazardous infectious waste) was burned. Emission factors developed for each emission component were: particles 1.0–1.6 g/kg waste; hydrochloric acid 3.3–5.3 g/kg; carbon monoxide 1.4–1.8g/kg; ethane <0.002g/kg; ethylene <0.010g/kg; propane <0.012 g/kg; and propylene <0.011 g/kg     

Ambient Air Measurements of Petroleum Refinery Emissions

An ambient air monitoring program to characterize airborne emissions from the Exxon petroleum refinery at Benicia, California was conducted during September 8–22, 1975. Ground level sampling facilities and an instrumented aircraft provided an integrated, three-dimensional monitoring network. Measurements made during the study included ozone, oxides of nitrogen, methane, carbon monoxide, individual C₂-C₆ hydrocarbons, halocarbons, condensation nuclei, visual distance and various meteorological parameters. The study focused on three major areas: (1) the characterization of gaseous components within the refinery effluent, especially non-methane hydrocarbons and ozone, (2) natural sunlight bag irradiation experiments to determine the ozone forming potential of refinery emissions, and (3) an investigation of changes in plume chemistry as refinery emissions were transported downwind.     

An Evaluation of Techniques for the Determination of the Photochemical Reactivity of Organic Emissions

The concept that control of organic substances in emissions should be based on the relative ability to cause the effects associated with photochemical air pollution (reactivity) rather than on gross emission levels has gained wide acceptance. Two general types of reactivity response scales have been proposed. One of these is based on rates of hydrocarbon reaction or nitrogen dioxide formation. This scale covers a wide range because of the very high rates associated with olefins having internal double-bonds. The other scale is based on product yields combined with biological effect measurements. This type of scale is considered superior to one based on rates. This latter scale covers a narrow response range because olefins with internal double bonds have only slightly higher product yields and biological effects than do other reactive olefins and alkylbenzenes. Use of a response scale based on product yields and biological effects also permits use of less detailed instrumental procedures. A simple subtractive column technique combined with a flame ionization analyzer should be sufficient to estimate hydrocarbon emissions. Gas chromatographic analyses of hydrocarbon emissions are of value when used with either type of reactivity response scale. However, detailed gas chromatographic analyses are essential for a response scale based on rates. The response scale based on product yields and biological effects indicates much less improvement in reactivity from fuel composition changes than would be predicted from a response scale based on rates. The most desirable approach is to use a variety of control and engine modification techniques to reduce all reactive organics to the lowest level possible.     

Biofiltration of a Mixture of Volatile Organic Emissions

ABSTRACT

Air biofiltration is now under active consideration for the removal of the volatile organic compounds (VOCs) from polluted airstreams. To optimize this emerging environmental technology and to understand compound removal mechanisms, a biofilter packed with peat was developed to treat a complex mixture of VOCs: oxygenated, aromatic, and chlorinated compounds. The removal efficiency of this process was high. The maximum elimination capacity (ECmax) obtained was ~120 g VOCs/m³ peat/hr. Referring to each of the mixture's components, the ECmax showed the limits in terms of biodegradability of VOCs, especially for the halogenated compounds and xylene.

A stratification of biodegradation was observed in the reactor. The oxygenated compounds were metabolized before the aromatic and halogenated ones. Two assumptions are suggested. There was a competition between bacterial communities. Different communities colonized the peat-based biofilter, one specialized for the elimination of oxygenated compounds, the others more specialized for elimination of aromatic and halogenated compounds. There was also substrate competition. Bacterial communities were the same over the height of the column, but the more easily biodegradable compounds were used first for the microorganism metabolism when they were present in the gaseous effluent.     

Cost-Effective Reduction of NOx Emissions from Electricity Generation

ABSTRACT

This paper analyzes the benefits and costs of policies to reduce NO_x emissions from electricity generation in the United States. Because emissions of NOx contribute to the high concentration of atmospheric ozone in the eastern states associated with health hazards, the U.S. Environmental Protection Agency (EPA) has called on eastern states to formulate state implementation plans (SIPs) for reducing NO_x emissions. Our analysis considers three NO_x reduction scenarios: a summer seasonal cap in the eastern states covered by EPA's NO_x SIP Call, an annual cap in the same SIP Call region, and a national annual cap. All scenarios allow for emissions trading. Although EPA's current policy is to implement a seasonal cap in the SIP Call region, this analysis indicates that an annual cap in the SIP Call region would yield about $400 million more in net benefits (benefits less costs) than would a seasonal policy, based on particulate-related health effects only. An annual cap in the SIP Call region is also the policy that is most likely to achieve benefits in excess of costs. Consideration of omissions from this accounting, including the potential benefits from reductions in ozone concentrations, strengthens the finding that an annual program offers greater net benefits than does a seasonal program.     

Estimation of Organic Compound Emissions from Waste Lagoons

Abstract

With the recent focus on fine particle matter (PM_2.5),new, self-consistent data are needed to characterize emissions from combustion sources. Such data are necessary for health assessment and air quality modeling. To address this need, emissions data for gas-fired combustors are presented here, using dilution sampling as the reference.The dilution method allows for collection of emitted particles under conditions simulating cooling and dilution during entry from the stack into the air. The sampling and analysis of the collected particles in the presence of precursor gases, SO₂, nitrogen oxide, volatile organic compound, and NH₃ is discussed; the results include data from eight gas fired units, including a dual-fuel institutional boiler and a diesel engine powered electricity generator. These data are compared with results in the literature for heavy-duty diesel vehicles and stationary sources using coal or wood as fuels. The results show that the gas-fired combustors have very low PM_2.5 mass emission rates in the range of ～10_-4 lb/million Btu (MMBTU) compared with the diesel backup generator with particle filter, with ～5 × 10_-3 lb/MMBTU. Even higher mass emission rates are found in coal-fired systems, with rates of ～0.07 lb/MMBTU for a bag-filter-controlled pilot unit burning eastern bituminous coal. The characterization of PM_2.5 chemical composition from the gas-fired units indicates that much of the measured primary particle mass in PM_2.5 samples is organic or elemental carbon and, to a much less extent, sulfate. Metal emissions are quite low compared with the diesel engines and the coal- or woodfueled combustors. The metals found in the gas-fired combustor particles are low in concentration, similar in concentration to ambient particles. The interpretation of the particulate carbon emissions is complicated by the fact that an approximately equal amount of particulate carbon (mainly organic carbon) is found on the particle collector and a backup filter. It is likely that measurement artifacts, mostly adsorption of volatile organic compounds on quartz filters, are positively biasing “true” particulate carbon emission results.