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.     

Current Technology for Continuous Monitoring of Gaseous Emissions

The purpose of this paper is to present a discussion of the latest developments in continuous gaseous emissions measurement. Subject areas include extractive and in-situ measurement. An exhaustive discussion of all instrumental methods currently available for use is neither appropriate nor productive in that several reviews have already been published in this area. Current needs for the development of new instrumentation in support of pending EPA regulations will be noted.     

Current Technology for Continuous Monitoring of Particulate Emissions

Particulate matter is characterized by its physical and chemical properties. Federal and state emission standards identify two important physical properties, opacity (visible emissions) and particulate mass concentration. In addition, particle size and particle composition are characteristics that play a significant role in the assessment of health effects, visibility, and control strategy. Systems to monitor these particle characteristics are in various stages of development. Opacity monitors have the longest history of commercial availability and of applicability to various source emissions. Particulate mass monitors have a short history as commercially available systems and are under evaluation in various source applications. Particle size monitors are mainly in the advanced prototype development stage undergoing evaluation. Particle composition monitors are in the early stages of development as research prototypes. Real time size monitoring systems will eventually be wedded to real time particle composition analyzers to give a monitoring system for particle size distributions of chemical constituents.     

Continuous Emissions Monitoring Using Spark-Induced Breakdown Spectroscopy

ABSTRACT

A new technology for monitoring airborne heavy metals on aerosols and particulates based on spark-induced breakdown spectroscopy (SIBS) was evaluated at a joint U.S. Environmental Protection Agency (EPA)/U.S. Department of Energy test at the rotary kiln incinerator simulator (RKIS) facility at EPA/Research Triangle Park, NC, in September 1997. The instrument was configured to measure lead and chromium in a simulated combustion flue gas in real time and in situ at target levels of 15 and 75 u, g/dry standard cubic meters. Actual metal concentrations were measured during the tests using EPA Reference Method (RM) 29.

The SIBS technology detected both lead and chromium at the low- and high-level concentrations. Additionally, the hardware performed without failure for more than 100 hr of operation and acquired data for 100% of the RM tests. The chromium data were well correlated with concentration increases resulting from duct operations and pressure fluctuations that are known to entrain dust.     

Treatment of Halogenated Organic Vent Streams for the Reduction of Air Emissions

Abstract

This work presents a three-stage treatment system to process halogenated organic vent streams for compliance with the Hazardous Organic NESHAP (HON) Rule. The three stages are incineration, energy recovery, and wet scrubbing. In particular, this work concentrates on the design of the scrubber, which the HON Rule states must remove at least 99% of any halogens or hydrogen halides generated during the combustion step. Computerized process simulation was found to be ineffective in designing a scrubber for this application, so laboratory data on the partial pressure of the hydrogen halide species over aqueous solutions was employed. The number of overall gas transfer units required for 99% removal was found to be slightly less than 5, and the overall gas transfer unit height was found to be approximately 0.5 m.     

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.     

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.     

Development of Criteria for Siting Air Monitoring Stations

A critical problem arises if one attempts to compare data from air monitoring stations in different cities, because there are so many differences in monitoring site locations. Some air monitoring stations are on the 6 th and 8 th floors of tall buildings in downtown areas; some are at ground level beside streets with heavy traffic; some are in residential areas with little traffic or industry; and some are in suburban or nonurban areas. Unfortunately, there is ample evidence that the location of a monitoring station relative to nearby sources (such as highways) affects the values observed at the station, particularly for carbon monoxide and other vehicular pollutants. Thus, a standardized system of site selection, such as the one proposed here, appears essential to improve the comparability and meaningfulness of data obtained from different air monitoring stations throughout the Nation.     

Near Surface Soil Vapor Clusters for Monitoring Emissions of Volatile Organic Compounds from Soils

ABSTRACT

The overall objective of this research was to develop and test a method of determining emission rates of volatile organic compounds (VOCs) and other gases from soil surfaces. Soil vapor clusters (SVCs) were designed as a low dead volume, robust sampling system to obtain vertically resolved profiles of soil gas contaminant concentrations in the near surface zone. The concentration profiles, when combined with a mathematical model of porous media mass transport, were used to calculate the contaminant flux from the soil surface. Initial experiments were conducted using a mesoscale soil remediation system under a range of experimental conditions. Helium was used as a tracer and trichloroethene was used as a model VOC. Flux estimations using the SVCs were within 25% of independent surface flux estimates and were comparable to measurements made using a surface isolation flux chamber (SIFC). In addition, method detection limits for the SVC were an order of magnitude lower than detection limits with the SIFC. Field trials, conducted with the SVCs at a bioventing site, indicated that the SVC method could be easily used in the field to estimate fugitive VOC emission rates. Major advantages of the SVC method were its low detection limits, lack of required auxiliary equipment, and ability to obtain realtime estimates of fugitive VOC emission rates.     

Monitoring of Benzene in Ambient Air with Organic Vapor Badges

The original Texas Intersection Model (TEXIN) for air quality near street intersections has been widely adopted across the nation. At the request of transportation agencies from several states, the TEXIN model was revised to improve its performance and flexibility. The new capabilities include T-intersections, one-way streets, four-way stops, inspection/maintenance capabilities, anti-tampering programs and a short-cut emissions algorithm. TEXIN2 uses the CMA procedures for estimating traffic flow parameters, MOBILE3 to determine free flowing traffic cruise emissions, and CALINE3 to model the pollutant distribution downwind of an intersection. The new model, TEXIN2, offers the user more accurate simulations with enhanced versatility while still requiring a minimal amount of input data.     

Determination of Motor Vehicle Profiles for Non-Methane Organic Compounds in the Mexico City Metropolitan Area

ABSTRACT

Non-methane organic compound (NMOC) profiles for on-road motor vehicle emissions were measured in a downtown tunnel and parking garages in Mexico City during 1996. Hydrocarbon samples from the tunnel and ambient air samples (C2-C12) were collected using stainless steel canisters, and carbonyl compounds were collected using 2,4-dinitrophenylhydrazine (DNPH) impregnated cartridges. Canister samples were analyzed by gas chromatog-raphy/flame ionization detection (GC/FID) to ascertain detailed hydrocarbon composition. DNPH samples were analyzed by high performance liquid chromatography (HPLC). NMOC source profiles were quantified for evaporative emissions from refueling, cold start, and hot soak, and on-road operating conditions. The ultimate purpose will be to determine the apportionment of ambient NMOC concentrations using the Chemical Mass Balance (CMB) model. The tunnel profile contained 42.3 ppbC% of alkanes, 20.6 ppbC% of unsaturated compounds, and 22.4 ppbC% of aromatics. The most abundant species were acetylene with 7.22 ppbC%, followed by ipentane with 5.69 ppbC%, and toluene with 5.42 ppbC%. These results were compared with those from studies in the United States. The cold start profile was found to be similar to the tunnel profile, although there were differences in the content of acetylene, isopentane, and oxygenates. The abundance of saturated NMOC in the hot soak profile was similar to gasoline head space profiles; it was also much larger than saturated NMOC in the roadway profile.     

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.     

Regional Monitoring of Ambient Air Carbon Monoxide in Fairbanks,Alaska

A method employing the timed fill of Mylar bags was used to obtain average carbon monoxide concentration values for ten locations in the Fairbanks, Alaska, area. The method is shown to be accurate, reliable, and inexpensive. The correlation coefficient between the bag sampling method and a continuous carbon monoxide analyzer was 0.945; correlation of carbon monoxide data from several locations to a reference in downtown Fairbanks showed a general decrease with distance from the reference analyzer. Analysis of data from Fairbanks shows that carbon monoxide concentrations during the winter months may have to be reduced 50-75% to achieve the State and National Ambient Air Quality Standards; the high levels of carbon monoxide are the result of emissions from automobile traffic during periods of severe inversion in the Fairbanks basin.     

Development of a PM2 5 Emissions Inventory for the South Coast Air Basin

ABSTRACT

With the promulgation of a national PM_2.5 ambient air quality standard, it is important that PM_2.5 emissions inventories be developed as a tool for understanding the magnitude of potential PM2.5 violations. Current PM₁₀ inventories include only emissions of primary particulate matter (1 ^ï PM), whereas, based on ambient measurements, both PM₁₀ and PM2.5 emissions inventories will need to include sources of both 1^ï PM and secondary particulate matter (2^ï PM). Furthermore, the U. S. Environmental Protection Agency’s (EPA) current edition of AP-42 includes size distribution data for 1o PM that overestimate the PM_2.5 fraction of fugitive dust sources by at least a factor of 2 based on recent studies.

This paper presents a PM_2.5 emissions inventory developed for the South Coast Air Basin (SCAB) that for the first time includes both 1^ï PM and 2^ï PM. The former is calculated by multiplying PM₁₀ emissions estimates by the PM_2.5/PM₁₀ ratios for different sources. The latter is calculated from estimated emission rates of gas-phase aerosol precursor and gas to aerosol conversion rates consistent with the measured chemical composition of ambient PM_2.5 concentrations observed in the SCAB. The major finding of this PM_2.5 emissions inventory is that the ^2ï aerosol component is more than twice the ^1ï aerosol component, which may result in widely different control strategies being required for fine PM and coarse PM.     

Development and Use of a Disaggregated Emissions Inventory for Air Quality Planning in Washington,DC

The Metropolitan Washington Council of Governments (COG) is responsible for developing an Air Quality Plan which will produce attainment of the O₃ and 8 h CO standards in the Washington area by 1987. In order to define as precisely as possible the sources of emissions in the area, a disaggregated emissions inventory was prepared. For mobile sources, this included classification of vehicle type, portion of the trip cycle, and purpose of trip. For nonhighway sources, individual source types were identified. All emissions were assigned to 5 km × 5 km grids and summed to obtain local, state, and/or regional totals. The inventory, although expensive and time-consuming, is a useful tool for decision makers who are responsible for implementing measures to control emissions.     

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.     

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.     

Continuous Determination of Carbon Monoxide and Hydrocarbons in Air by a Modified Infrared Analyzer

The original goals of this project¹ were to establish the shape of a smoke curve for fine suspended particulates in New York City comparable to the International Smoke Curve used in British and other European practice, and to relate two commonly used reporting units of surface concentration, μg/m³ (European practice) and Coh/1000 lineal feet (United States practice), to each other. While not directly a goal of the project, it was essential in the course of work to study the relationship between particulate density readings taken for one hour and two hour sampling periods. Progress toward achievement of these goals is presented in the following pages.