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.     

Direct Measurement of Fugitive Emissions of Hydrocarbons from a Refinery

Abstract

Refineries are a source of emissions of volatile hydrocarbons that contribute to the formation of smog and ozone. Fugitive emissions of hydrocarbons are difficult to measure and quantify. Currently these emissions are estimated based on standard emission factors for the type and use of equipment installed. Differential absorption light detection and ranging (DIAL) can remotely measure concentration profiles of hydrocarbons in the atmosphere up to several hundred meters from the instrument. When combined with wind speed and direction, downwind vertical DIAL scans can be used to calculate mass fluxes of the measured gas leaving the site. Using a mobile DIAL unit, a survey was completed at a Canadian refinery to quantify fugitive emissions of methane, C₂₊ hydrocarbons, and benzene and to apportion the hydrocarbon emissions to the various areas of the refinery. Refinery fugitive emissions as measured with DIAL during this demonstration study were 1240 kg/hr of C₂₊ hydrocarbons, 300 kg/hr of methane, and 5 kg/hr of benzene. Storage tanks accounted for over 50% of the total emissions of C₂₊ hydrocarbons and benzene. The coker area and cooling towers were also significant sources. The C₂₊ hydrocarbons emissions measured during the demonstration amounted to 0.17% of the mass of the refinery hydrocarbon throughput for that period. If the same loss were repeated throughout the year, the lost product would represent a value of US$3.1 million/yr (assuming US$40/bbl). The DIAL-measured hourly emissions of C₂₊ hydrocarbons were 15 times higher than the emission factor estimates and gave a different perspective on which areas of the refinery were the main source of emissions. Methods, such as DIAL, that can directly measure fugitive emissions would improve the effectiveness of efforts to reduce emissions, quantify the reduction in emissions, and improve the accuracy of emissions data that are reported to regulators and the public.     

Photochemical Reactivity of Perchloroethylene: A New Appraisal

Perchloroethylene (PCE), a solvent used in dry cleaning, has been suspected of contributing significantly to photochemical ozone/oxidant (O₃/O_x) problems in urban atmospheres. Past evidence, however, was neither complete nor consistent. To interpret more conclusively the past evidence, and further understand PCE's role in the O₃O_x problem, a smog chamber testing program was conducted. The program's objectives were: (a) to explain the mechanism of the PCE reaction in smog chamber atmospheres, and (b) to extrapolate the smog chamber findings regarding PCE reactivity to the real atmosphere. Results showed that in smog chambers, PCE reacts and forms O₃/O_x following what appears to be a Cl instigated photooxidation mechanism rather than the OH initiated mechanism accepted in current smog chemistry. The evidence, collectively, strongly supported this conclusion even though the source of Cl atoms could not be identified with confidence. It was further concluded that in the real atmosphere neither the Cl instigated nor the OH instigated photooxidations of PCE can generate substantial concentrations of O₃/O_x. In fact, PCE contributes less to the ambient O₃/O_x problem than equal concentrations of ethane.     

Effects of Fuel Variables on Diesel Emissions

The body of information presented in this paper is directed towards engineers in the field of environmental sciences involved in measuring and/or evaluating the emissions from a variety of diesel engines or vehicles. This paper summarizes recent data obtained by EPA on identification and quantification of different emissions (i.e. characterization) from a variety of diesel engines.

Extensive work has been done comparing emissions from some light duty diesel and gasoline passenger cars. The work on the diesel vehicles was expanded to include tests with five different diesel fuels to determine how fuel composition affects emissions. This work showed that use of a poorer quality fuel frequently made emissions worse. The investigation of fuel composition continued with a project in which specific fuel parameters were systematically varied to determine their effect on emissions. EPA is presently testing a variety of fuels derived from coal and oil shale to determine their effects on emissions.

EPA has also tested a heavy duty Volvo diesel bus engine designed to run on methanol and diesel fuel, each injected through its own injection system. The use of the dual fuel resulted in a reduction in particulates and NO _x but an increase in HC and CO compared to a baseline Volvo diesel engine running on pure diesel fuel.

Finally, some Ames bioassay tests have been performed on samples from the diesel passenger cars operated on various fuels and blends. An increase in Ames test response (mutagenicity) was seen when the higher aromatic blend was used and also when a commercial cetane improver was used. Samples from the Volvo diesel bus engine fueled with methanol and diesel fuel showed that use of a catalyst increased the Ames response.     

An Intelligent Emissions Controller for Fuel Lean Gas Reburn in Coal-Fired Power Plants

ABSTRACT

The application of artificial intelligence techniques for performance optimization of the fuel lean gas reburn (FLGR) system is investigated. A multilayer, feedforward artificial neural network is applied to model static nonlinear relationships between the distribution of injected natural gas into the upper region of the furnace of a coal-fired boiler and the corresponding oxides of nitrogen (NO_x) emissions exiting the furnace. Based on this model, optimal distributions of injected gas are determined such that the largest NO_x reduction is achieved for each value of total injected gas. This optimization is accomplished through the development of a new optimization method based on neural networks. This new optimal control algorithm, which can be used as an alternative generic tool for solving multidimensional nonlinear constrained optimization problems, is described and its results are successfully validated against an off-the-shelf tool for solving mathematical programming problems. Encouraging results obtained using plant data from one of Commonwealth Edison's coal-fired electric power plants demonstrate the feasibility of the overall approach.

Preliminary results show that the use of this intelligent controller will also enable the determination of the most cost-effective operating conditions of the FLGR system by considering, along with the optimal distribution of the injected gas, the cost differential between natural gas and coal and the open-market price of NO_x emission credits. Further study, however, is necessary, including the construction of a more comprehensive database, needed to develop high-fidelity process models and to add carbon monoxide (CO) emissions to the model of the gas reburn system.     

An Evaluation of Emissions and Control Technologies for the Metal Decorating Process

A simple but effective sampling and analytical procedure is described for determining total organics, carbon dioxide, carbon monoxide, and methane emitted from web offset printing presses. Data are reported on a number of controlled and uncontrolled sources and emission levels are related to process variables such as press speed, ink coverage and dryer type. For controlled sources employing either catalytic or thermal incineration units, conversion efficiencies are reported as a function of temperature. Operational curves are presented for each control system studied indicating the dependency of carbon dioxide, NO_xt and organic output to incineration temperatures.     

An Evaluation of Emissions and Control Technologies for the Metal Decorating Process

Data are reported on a number of controlled and uncontrolled sources from various metal decorating operations. Emission levels are related to process variables such as ink coverage, coater speed, sheet size, and applied coating film weight. Results are presented depicting variation of organic emission levels from a coating process line with elapsed process time. For controlled sources employing either catalytic or thermal incineration, conversion efficiencies are reported as a function of temperature. Operational curves are presented for each control system studied indicating the dependence of carbon dioxide, NO_x, and organic output on incineration temperatures.     

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.     

Continuous Measurement of Diesel Particulate Emissions

Evaluation of emerging diesel particulate emissions control technology will require analytical procedures capable of continuous or “real-time” measurement of transient organic and elemental carbon emissions. Procedures based on the flame ionlzation properties of organic carbon and the opacity or light extinction properties of elemental carbon are described, and applied for measurement of particulate emissions from diesel engines. The Instrumentation provided adequate sensitivity and time resolution for observation of the transient emissions associated with typical automobile urban driving conditions. Analytical accuracy is evaluated by comparing Integrated average results to measurements using classical gravimetric filtration and solvent extraction procedures. Mass specifc extinction coefficients are evaluated using the Beer-Lambert law. A simplified linear model relating elemental carbon concentration to opacity is also evaluated.     

An Evaluation of the Tapered Element Oscillating Microbalance Method for Measuring Diesel Particulate Emissions

Abstract

We determined the usefulness of tapered element oscillating microbalances (TEOMs) for researchers and engineers involved with measuring diesel particulate mass. Two different test facilities were used for generating diesel particulates and comparing the TEOM to the commonly used U.S. Environmental Protection Agency (EPA) manual filter method. The EPA method is very labor-intensive and requires long periods of time to complete. The TEOM is an attractive approach because it has the potential to reduce the amount of time and labor required in diesel testing, as well as to provide real-time particulate-mass data that are not obtainable with the EPA method. It was found that the TEOM was a precise and easy-to-operate instrument that could measure the mass concentration (MC) of diesel particulate emissions in real time. Although the TEOM diesel particulate MC measurements were highly correlated with the manual filter measurements, the two techniques were not equivalent because the TEOM consistently reported MC results that were 20–25% lower than those obtained using the manual filter technique. In conclusion, the TEOM can be used to increase test-cell throughput and to measure transient values of diesel par-ticulate emissions at sites performing diesel-engine testing. However, unless EPA is able to certify the TEOM as an equivalent method, it cannot replace the manual filter method for diesel certification work.     

Photochemical Reactivities of Exhausts from 1966 Model Automobiles Equipped to Reduce Hydrocarbon Emissions

During the summer of 1966, a selected group of automobiles from the Cincinnati phase of the GSA study were used in an irradiation chamber study. The study was conducted to evaluate the photochemical air pollution potential of representative models of the equipped and unequipped automobiles. Only one set of automobiles, the unequipped Chevelles, produced exhaust capable upon irradiation of forming significant levels of oxidant and PAN. Neither the equipped Chevelles nor any of the Fords or Plymouths, whether equipped or unequipped, produced exhaust having the characteristics necessary to form oxidant or PAN upon irradiation. The eye irritation level reported by the panel upon irradiation of exhaust from unequipped Chevelles was much higher than that produced by the irradiated exhausts from any of the other types of automobiles. Overall, there does appear to be some small improvement with respect to eye irritation in comparing equipped with unequipped automobiles. To a large extent, the improvement in the air pollution potential of exhaust from equipped Chevelles compared to the unequipped Chevelles can be attributed to the reduction in the hydrocarbon to nitrogen oxide ratio. The irradiated exhaust from equipped Chevelles, except for aldehyde levels, is about the same in photochemical air pollution potential as are the exhausts from both equipped and unequipped Fords and Plymouths which are maintained under lean operating conditions. Such irradiation chamber measurements are related to exhaust not hydrocarbon reactivities. Hydrocarbon reactivities can be obtained by direct measurement of reactive and nonreactive hydrocarbons in the automotive emissions.     

Sensitivity Analysis and Evaluation of MicroFacCO: A Microscale Motor Vehicle Emission Factor Model for CO Emissions

ABSTRACT

This paper presents a sensitivity analysis of a microscale emission factor model (MicroFacCO) for predicting realtime site-specific motor vehicle CO emissions to input variables, as well as a limited field study evaluation of the model. The sensitivity analysis has shown that MicroFacCO emission estimates are very sensitive to vehicle fleet composition, speed, and ambient temperature. For the present U.S. traffic fleet, the CO emission rate (g/mi) is increased by more than 500% at 5 mph in comparison with a speed greater than 40 mph and by ~67% at ambient temperatures of 45 °F and ≥95 °F in comparison with an ambient temperature of 75 °F.     

A Comparative Analysis of Emissions Deterioration for In-Use Alternative Fuel Vehicles

Abstract

Although there have been several studies examining emissions from in–use alternative fuel vehicles (AFVs), little is known about the deterioration of these emissions over vehicle lifetimes and how this deterioration compares with deterioration from conventional vehicles (CVs). This paper analyzes emissions data from 70 AFVs and 70 CVs operating in the federal government fleet to determine whether AFV emissions deterioration differs significantly from CV emissions deterioration. An analysis is conducted on three alternative fuel types (natural gas, methanol, and ethanol) and on four pollutants (carbon monoxide, total hydrocarbons, non-methane hydrocarbons, and nitrogen oxides). The results indicate that for most cases studied, deterioration differences are not statistically significant; however, several exceptions (most notably with natural gas vehicles) suggest that air quality planners and regulators must further analyze AFV emissions deterioration to properly include these technologies in broader air quality management schemes.     

Measurement of Photochemical Air Pollution with a Sensitive Monitoring Plant

With newly developed monitoring techniques, investigators used the sensitive tobacco variety, Bel-W3, as a monitor for photochemical air pollution at different locations within 75 miles of Cincinnati, Ohio. Observations during the summers of 1966 through 1968 revealed almost daily injury to monitoring plants, fairly uniform total seasonal injury at all locations, and a marked variation in both oxidant and injury from one season to another within the city. The relationship between oxidant level and injury was not found to be consistent.     

Measurement of Indoor Air Emissions from Dry-Process Photocopy Machines

Abstract

Presently, no standard test method exists to evaluate the various emissions from office equipment (e.g., ozone, volatile organic compounds, inorganic gases, and particulates) so it is difficult to compare data from different studies.1 As a result, the authors are developing a standardized guidance document for measuring indoor air emissions from office equipment. The ultimate goal is to apply the test method to better understand emissions from office equipment and to develop lower emitting machines. This paper provides background information on indoor air emissions from office equipment with an emphasis on dry-process photocopy machines. The test method is described in detail, along with the results of a study to evaluate the test method using four dry-process photocopy machines.

The results from this study indicate that the test method provides acceptable performance for characterizing emissions; that it can adequately identify differences in emissions between machines both in compounds emitted and their emission rates; and that it is capable of measuring both intra- and inter-machine variability in emissions. Challenges and complications were encountered in developing and implementing the test method. These included heat generation, which can cause large increases in chamber temperature; finite paper supplies for photocopy machines, which limit test duration; varying power requirements that may require changes in chamber electrical supply; and remote starting of the machines, which is necessary to maintain chamber integrity.

Results show that dry-process photocopy machines can produce emissions of ozone and volatile organic compounds that can potentially have a significant impact on indoor air quality. For the four machines tested in this study, the compounds with the highest emission rates overall were ethylbenzene (28,000 µg/hour), m,p-xylenes (29,000 µg/hour), o-xylene (17,000 µg/hour), 2-ethyl-lhexanol (14,000 µg/hour), and styrene (12,000 fig/hour). Although many of the same compounds tended to be detected in emissions from each of the four photocopiers, the relative contribution of individual compounds varied considerably between machines, with differences greater than an order of magnitude for some compounds.     

Techniques and Procedures for the Measurement of Aircraft Gas Turbine Engine Emissions

In 1968 the Society of Automotive Engineers formed the Committee on Aircraft Exhaust Emissions Measurement (E-31) whose charge was the development of acceptable standards of measurement for the characterization of aircraft engine exhaust. This committee’s efforts have resulted in the issuance of two Aerospace Recommended Practices, ARP 1179 “Aircraft Gas Turbine Exhaust Smoke Measurement” and ARP 1256 “Procedure for the Continuous Sampling and Measurement of Gaseous Emissions from Aircraft Turbine Engines.” These Recommended Practices have in large part been adopted by the Environmental Protection Agency and promulgated in Federal Register Volume 38, Number 136, Tuesday, July 17, 1973.

For the past three years Pratt & Whitney Aircraft has been measuring emissions from aircraft gas turbine engines using on-line instrumentation systems designed both in accordance with these Aerospace Recommended Practices and in response to the operational needs of a large experimental engineering test facility. In addition to a discussion of these systems this paper describes the experience derived from continuous testing programs in support of this test facility with consideration being given to the specific problems of sampling, sample handling, system accuracy, and data recording and reduction. Comment is made as to the practical limitations of the recommended methods and procedures as applied to emission control technology programs and suggestions are presented for improving the measurement technology.     

The Effect of Ethanol Fuel on the Emissions of Vehicles over a Wide Range of Temperatures

ABSTRACT

The emissions from a fleet of 11 vehicles, including three from the State of Alaska, were tested at 75, 0, and -20 °F with base gasolines and E10 gasolines, that is, gasolines with 10% by volume ethanol added. The data for the changes in emissions for the test run at 75 °F are included, since most other studies on the effects of E10 gasoline on emissions were run at that temperature. The three Alaskan vehicles were also tested at 20 °F. The testing followed the Federal Test Procedure, and regulated emissions—CO, total hydrocarbons (THC), and nitrogen oxides (NO_x)—CO₂, speciated organics, and fuel economy were measured. A total of 490 FTP tests were run. The data obtained indicated that with most vehicles, at the temperatures tested, improvements in both CO and THC emissions were obtained with the use of E10 fuel. At the lowest temperature used, -20 °F, most vehicles had an increase in NO emissions with the use of E10 fuel. At the other temperatures, however, more vehicles showed a decrease in NO_x emissions with the use of E10. With all vehicles at all temperatures tested, the emissions of acetaldehyde increased significantly when E10 fuel was used. The highest increase was about 8 to 1. Benzene, formaldehyde, and 1,3 butadiene showed both increases and decreases in the emissions when using E10 fuel. Unexpected results were obtained with the fuel economy, with about half of the tests showing an increase in fuel economy with the use of E10 fuel.     

On-Road Measurement of Vehicle Tailpipe Emissions Using a Portable Instrument

Abstract

A study design procedure was developed and demonstrated for the deployment of portable onboard tailpipe emissions measurement systems for selected highway vehicles fueled by gasoline and E85 (a blend of 85% ethanol and 15% gasoline). Data collection, screening, processing, and analysis protocols were developed to assure data quality and to provide insights regarding quantification of real-world intravehicle variability in hot-stabilized emissions. Onboard systems provide representative real-world emissions measurements; however, onboard field studies are challenged by the observable but uncontrollable nature of traffic flow and ambient conditions. By characterizing intravehicle variability based on repeated data collection runs with the same driver/vehicle/route combinations, this study establishes the ability to develop stable modal emissions rates for idle, acceleration, cruise, and deceleration even in the face of uncontrollable external factors. For example, a consistent finding is that average emissions during acceleration are typically 5 times greater than during idle for hydrocarbons and carbon dioxide and 10 times greater for nitric oxide and carbon monoxide. A statistical method for comparing on-road emissions of different drivers is presented. Onboard data demonstrate the importance of accounting for the episodic nature of real-world emissions to help develop appropriate traffic and air quality management strategies.     

Measurement of Opacity and Particulate Emissions with an On-Stack Transmissometer

An on-stack transmissometer system which is designed to provide a precision measurement of the opacity of visible emissions is described. The sources of error in opacity measurements with regard to recent EPA emission monitoring requirements and planned specifications are discussed. Sources of error are voltage changes, temperature changes, light source and detector aging and effects of ambient light. Other major operational errors are caused by alignment drift and soiling drift. The methods employed to minimize these errors achieve an accuracy of ±3% of span and a maintenance free operational period of 3 months. The relationships between optical density, opacity and transmittance are described. The instrument measurement can be correlated with dust loading provided the particle size distribution is constant. Examples are given of correlations obtained between optical density and particulate concentration in the gas on various types of emission sources and the observed error margins are summarized.     

Airshed Model Evaluation of Reactivity Adjustment Factors Calculated with the Maximum Incremental Reactivity Scale for Transitional-Low Emission Vehicles

Abstract

The California Air Resources Board recently adopted regulations for light- and medium-duty vehicles that require reductions in the ozone-forming potential or “reactivity,” rather than the mass, of nonmethane organic gas (NMOG) emissions. The regulations allow sale of all alternatively fueled vehicles (AFVs) that meet NMOG exhaust emission standards equivalent in reactivity to those set for vehicles fueled with conventional gasoline. Reactivity adjustment factors (RAFs), the ratio of the reactivity (per gram) of the AFV exhaust to that of the conventionally fueled vehicle (CFV), are used to correct the stringent exhaust emission standards. Complete chemical speciation of the exhaust and conversion of each NMOG species to an appropriate mass of ozone using the maximum incremental reactivity (MIR) scale of Carter determines the RAF. The MIR approach defines reactivity where NMOG control is the most effective strategy in reducing ozone concentrations, and assumes it is not important to define reactivity at other conditions, i.e., where NO_x is the limiting precursor.

This study used the Carnegie/California Institute of Technology airshed model to evaluate whether the RAF-adjusted AFV emissions result in ozone impacts equivalent to those of CFV emissions. A matrix of two ozone episodes in the South Coast Air Basin (SoCAB) of California, two base emission inventories, and exhaust emissions from three alternative fuels that meet the first level of the low emission vehicle standards bounds the expected range of conditions. Although very good agreement was found previously for individual NMOG species,² this study noted deviations of up to ±15 percent from the equal ozone impacts for any vehicle/fuel combination required by the California regulations. These deviations appear to be attributable to differences in spatial and temporal patterns of emissions between vehicle fleets, rather than a problem with the MIR approach. The first formally adopted RAF, a value of 0.41 for 85 percent methanol/15 percent gasoline-fueled vehicles, includes a 10 percent increase based on the airshed modeling. The correction to the RAF is different for other fuels and may be different for air basins other than the SoCAB.