Evaluation of Method 25 Nonmethane Organic Analyzer Design

Under contract to the U.S. Environmental Protection Agency, Research Triangle Institute has been conducting research to improve the precision, accuracy and limit of detection attainable with the EPA Method 25 nonmethane organic (NMO) analyzer. In Method 25, volatile organic carbon (VOC) samples are collected by drawing gas from an emitting source through a dry ice cooled sample trap and into an evacuated collection tank. The hydrocarbon concentration emitted from the source is determined on a per-carbon basis by catalytically converting the trap and tank sample fractions to CO₂ and quantitating the amount of CO₂ produced using the NMO analyzer. A reduction catalyst evaluation led to the selection of an NMO analyzer reduction catalyst which operates at a moderate temperature and displays no appreciable effect on peak shape. A gas chromatographlc column system which provides better permanent gas separation and hydrocarbon quantitation was also selected for use in the NMO analyzer.     

Assessing Sorbents for Mercury Control in Coal-Combustion Flue Gas

Abstract

Sorbent injection for Hg control is one of the most promising technologies for reducing Hg emissions from power-generation facilities, particularly units that do not require wet scrubbers for SO₂ control. Since 1992, EPRI has been assessing the performance of Hg sorbents in pilot-scale systems installed at full-scale facilities. The initial tests were conducted on a 5000-acfm (142-m³/min) pilot baghouse. Screening potential sorbents at this scale required substantial resources for installation and operation and did not provide an opportunity to characterize sor-bents over a wide temperature range.

Data collected in the laboratory and in field tests indicate that sorbents are affected by flue gas composition and temperature. Tests carried out in actual flue gas at a number of power plants also have shown that sorbent performance can be site-specific. In addition, data collected at a field site often are different from data collected in the laboratory, with simulated flue gas mixed to match the major components in the site’s gas. To effectively estimate the costs of Hg sorbent systems at different plants, a measure of sorbent performance in the respective flue gases must be obtained. However, injection testing at multiple facilities with large pilot systems is not practical.

Over the past five years, fixed-bed characterization testing, modeling studies, and bench-scale injection testing have been undertaken to develop a low-cost technique to characterize sorbent performance in actual flue gas and subsequently to project normalized costs for Hg removal prior to full-scale demonstration. This article describes the techniques used and summarizes field-testing results from two plants burning Powder River Basin (PRB) coal for commercial activated carbon and several other sorbent types. Full-scale projections based on the results and data collected on larger-scale systems also are included.     

Laboratory and field investigations of particulate and carbon monoxide emissions from traditional and improved cookstoves

We implemented a program in which emission characterization is enabled through collaborations between academic, US and international non-governmental entities that focus on evaluation, dissemination, and in-use testing, of improved cookstoves. This effort resulted in a study of field and laboratory emissions from traditional and improved biofuel cookstoves. We found that field measured particulate emissions of actual cooking average three times those measured during simulated cooking in the laboratory. Emission factors are highly dependent on the care and skill of the operator and the resulting combustion; these do not appear to be accurately reproduced in laboratory settings. The single scattering albedo (SSA) of the emissions was very low in both lab and field measurements, averaging about 0.3 for lab tests and around 0.5 for field tests, indicating that the primary particles are climate warming. Over the course of three summers in Honduras, we measured field emissions from traditional cookstoves, relatively new improved cookstoves, and “broken-in” improved cookstoves. We found that well-designed improved cookstoves can significantly reduce PM and CO emission factors below traditional cookstoves. For improved stoves, the presence of a chimney generally resulted in lower emission factors but left the SSA unaffected. Traditional cookstoves had an average PM emission factor of 8.2 g kg^?1 – significantly larger than previous studies. Particulate emission factors for improved cookstoves without and with chimneys averaged about 6.6 g kg^?1 and 4.5 g kg^?1, respectively. The elemental carbon (EC) fraction of PM varied significantly between individual tests, but averaged about 25% for each of the categories.     

Summer and winter nonmethane hydrocarbon emissions from on-road motor vehicles in the Midwestern United States

On-road vehicle emission rates of nonmethane hydrocarbons (NMHCs) were measured in two tunnels in Milwaukee, WI, in summer 2000 and winter 2001. Seasonal ambient temperatures in the Midwestern United States vary more widely than in locations where most studies of NMHC emissions from vehicle fleets have been conducted. Ethanol is the added fuel oxygenate in the area, and, thus, emissions measured here are of interest as other regions phase out methyl tertiary butyl ether and increase the use of ethanol. Total emissions of NMHCs in three types of tunnel tests averaged 4560 +/- 800 mg L(-1) fuel burned (average +/- standard error). To investigate the impact of cold start on vehicle emissions, samples were collected as vehicles exited a parking structure in subzero temperatures. NMHC emissions in the subzero cold-start test were 8830 +/- 190 mg L(-1) fuel-nearly double the tunnel emissions. Comparison of ambient data for the Milwaukee area with tunnel emissions showed the impact of seasonal differences in fuels and emissions on the urban atmosphere. Composition of fuel samples collected from area gas stations in both seasons was correlated with vehicle emissions; the predominant difference was increased winter emissions of lighter hydrocarbons present in winter gasoline. A chemical mass balance model was used to determine the contributions of whole gasoline and gasoline headspace vapors to vehicle emissions in the tunnel and cold-start tests, which were found to vary with season. Results of the mass balance model also indicate that partially combusted components of gasoline are a major contributor to emissions of aromatic compounds and air toxic compounds, including benzene, toluene, xylenes, napthalene, and 1,3-butadiene, whereas air toxics hexane and 2,2,4-trimethylpentane are largely attributed to gasoline and headspace vapors.     

Field Reliability of the Orsat Analyzer

Results from four field based collaborative tests and from one laboratory based collaborative test of the Orsat analytical procedure are discussed. The results from the five collaborative tests demonstrate that routinely using Orsat data to convert particulate emissions from combustion sources to the reference conditions of 50 % excess air and 12% carbon dioxide may introduce sizeable errors in the corrected particulate loading. Ways to improve the Orsat apparatus and increase the reliability of the data are suggested.

Also reported are the results from field and laboratory studies on the reliability of using individual carbon dioxide and oxygen analyzers of the Fyrite* type to determine stack gas molecular weight. The laboratory study, which was done using three cylinders containing mixtures of carbon dioxide, oxygen, carbon monoxide, and nitrogen of known concentration, determined that these analyzers give carbon dioxide and oxygen analyses of sufficient reliability to yield accurate molecular weights. The results of the field studies, which were done on actual flue gas samples, also support this conclusion.     

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.     

Particulate,Carbon Monoxide,and Acid Emission Factors for Residential Wood Burning Stoves

Emissions from residential wood burning stoves are of Increasing concern in many areas. This concern is due to the magnitude of the emissions and the toxic and chemical characteristics of the pollutants. Recent testing of standard and new technology woodstoves has provided data for developing a family of particulate and carbon monoxide emission factor curves. This testing has also provided data illustrating the acidity of woodstove emissions. The particulate and carbon monoxide curves relate the actual stove emissions to the stove size and operating parameters of burn rate, fuel loading, and fuel moisture. Curves relating stove types to the acidity of emissions have also been constructed.

Test data show actual emissions vary from 3 to 50 grams per kilogram for particles and from 50 to 300 grams per kilogram for carbon monoxide. Since woodstove emissions are the largest single category of particulate emissions in many areas, it Is essential that these emissions be quantified specifically for geographic regions, allowing meaningful impact analysis modeling to be accomplished. Emission factors for particles and carbon monoxide are presented from several stove sizes and burn rates.

The acidic nature of woodstove emissions has been clearly demonstrated. Tests indicate woodstove flue gas condensate solutions to be predominantly in the 2.8 to 4.2 pH range. Condensate solutions from conventional woodstoves exhibited the characteristic buffering capacity of carboxylic acids when titrations were performed with a strong base. The environmental impact of buffered acidic woodstove emissions is not currently well understood; however, it is possible with the data presented here to make semi-quantitative estimates of acid emissions from particulate and carbon monoxide emission factors and wood use inventories.     

Comparison of on-road emissions for B-0, B-10, and B-20 in transit buses

Biodiesels are often marketed as being cleaner than regular diesel for emissions. Emission test results depend on the biodiesel blend, but laboratory tests suggest that biodiesels decrease particulate matter, carbon monoxide, hydrocarbons, and air toxins when compared to regular diesel. Results for the amount of oxides of nitrogen (NOx) have been less conclusive. Tests have also not evaluated the commonly available ranges of biodiesel blends in the laboratory. Additionally, little information is available from on-road studies, so the effectiveness of using biodiesels to reduce actual emissions is unknown. A more complex relationship exists between engine operation and the rate of emission production than is typically evaluated using engine or chassis dynamometer tests. On-road emissions can vary dramatically because emissions are correlated to engine mode. Additionally, activity such as idling, acceleration, deceleration, and operation against a grade can produce higher emissions than more stable engine operating modes. Because these modes are not well captured in a laboratory environment, understanding on-road relationships is critical in evaluating the emissions reductions that may be possible with biodiesels. More tests and quantifications of the effects of different blends on engine and vehicle performance are required to promote widespread use of biodiesel. The objective of this research was to conduct on-road tests to compare the emission impacts of different blends of biodiesel to regular diesel fuel under different operating conditions. The team conducted on-road tests that utilized a portable emissions monitoring system that was used to instrument transit buses. Regular diesel and different blends of biodiesel were evaluated during on-road engine operation by instrumenting three in-use transit buses, from the CyRide system of Ames, Iowa, along an existing transit route.     

Validation of a test method for the measurement of methanol emissions from stationary sources

Title III of the 1990 Clean Air Act Amendments designated methanol as a pollutant to be regulated. The U.S. Environmental Protection Agency (EPA), through a contract with Research Triangle Institute, has developed a method for measuring methanol emissions from stationary sources. The methanol sampling train (MST) consists of a glass-lined heated probe, two condensate knockout traps, and three sorbent cartridges packed with Anasorb 747. Samples are desorbed with a 1:1 mixture of carbon disulfide (CS2) and N,N-dimethylformamide (DMF). Condensate water and CS2/ DMF samples are analyzed by gas chromatography with flame ionization detection. The MST has a practical quantitation limit of approximately 3 ppm for a 20-L sample. Samples were shown to be stable for at least two weeks after collection. Field tests of the MST and the National Council of the Paper Industry for Air and Stream Improvement (NCASI) methanol sampling method were conducted at two pulp and paper mills. Sampling and analysis procedures followed EPA Method 301 requirements. The sampling location for the first field test was the inlet vent to a softwood bleach plant scrubber, where the methanol concentration was approximately 30 ppm. The mean recovery of spike was 108.3% for the MST method and 81.6% for the NCASI method. Although neither method showed significant bias at the 95% confidence level, the between-methods bias was significantly different. A second field test was conducted at a vent from a black liquor oxidation tank where the methanol concentration was approximately 350 ppm. Mean spike recoveries were 96.6 and 94.2% for the MST and NCASI methods, respectively. The biases of the two methods and the between-methods bias were not significantly different for the second field test.     

Assessing sorbents for mercury control in coal-combustion flue gas

Sorbent injection for Hg control is one of the most promising technologies for reducing Hg emissions from power-generation facilities, particularly units that do not require wet scrubbers for SO2 control. Since 1992, EPRI has been assessing the performance of Hg sorbents in pilot-scale systems installed at full-scale facilities. The initial tests were conducted on a 5,000-acfm (142-m3/min) pilot baghouse. Screening potential sorbents at this scale required substantial resources for installation and operation and did not provide an opportunity to characterize sorbents over a wide temperature range. Data collected in the laboratory and in field tests indicate that sorbents are affected by flue gas composition and temperature. Tests carried out in actual flue gas at a number of power plants also have shown that sorbent performance can be site-specific. In addition, data collected at a field site often are different from data collected     

The recovery of ammonia and hydrogen sulfide from ground-level area sources using dynamic isolation flux chambers: bench-scale studies

Controlled bench-scale laboratory experiments were conducted to evaluate the recovery of ammonia (NH3) and hydrogen sulfide (H2S) from dynamic isolation flux chambers. H2S (80-4000 ppb) and NH3 (5000-40,000 ppb) samples were diffused through the flux chamber to simulate ground level area source emissions while measuring the inlet and outlet flux chamber concentrations simultaneously. Results showed that the recovery of H2S during a 30-min sampling time was almost complete for concentrations >2000 ppb. At the lowest concentration of 80 ppb, 92.55% of the H2S could be recovered during the given sampling period. NH3 emissions exhibited similar behavior between concentrations of 5000-40,000 ppb. Within the 30-min sampling period, 92.62% of the 5000-ppb NH3 sample could be recovered. Complete recovery was achieved for concentrations >40,000 ppb. Predictive equations were developed for gas adsorption. From these equations, the maximum difference between chamber inlet and outlet concentrations of NH3 or H2S was predicted to be 7.5% at the lowest concentration used for either gas. In the calculation of emission factors for NH3 and H2S, no adsorption correction factor is recommended for concentrations >37,500 ppb and 2100 ppb for NH3 and H2S, respectively. The reported differences in outlet and inlet concentration above these ranges are outside the fullscale sensitivity of the gas sensing equipment. The use of 46-90 m of Teflon tubing with the flux chambers has apparently no effect on gas adsorption, because recovery was completed almost instantaneously at the beginning of the tests.     

Free Enterprise and Air Pollution Control

Abstract

Title III of the 1990 Clean Air Act Amendments designated methanol as a pollutant to be regulated. The U.S. Environmental Protection Agency (EPA), through a contract with Research Triangle Institute, has developed a method for measuring methanol emissions from stationary sources. The methanol sampling train (MST) consists of a glass-lined heated probe, two condensate knockout traps, and three sorbent cartridges packed with Anasorb® 747. Samples are desorbed with a 1:1 mixture of carbon disulfide (CS₂) and N, N-dimethylformamide (DMF). Condensate water and CS₂/ DMF samples are analyzed by gas chromatography with flame ionization detection. The MST has a practical quantitation limit of approximately 3 ppm for a 20-L sample. Samples were shown to be stable for at least two weeks after collection.

Field tests of the MST and the National Council of the Paper Industry for Air and Stream Improvement (NCASI) methanol sampling method were conducted at two pulp and paper mills. Sampling and analysis procedures followed EPA Method 301 requirements.

The sampling location for the first field test was the inlet vent to a softwood bleach plant scrubber, where the methanol concentration was approximately 30 ppm. The mean recovery of spike was 108.3% for the MST method and 81.6% for the NCASI method. Although neither method showed significant bias at the 95% confidence level, the betweenmethods bias was significantly different.

A second field test was conducted at a vent from a black liquor oxidation tank where the methanol concentration was approximately 350 ppm. Mean spike recoveries were 96.6 and 94.2% for the MST and NCASI methods, respectively. The biases of the two methods and the between-methods bias were not significantly different for the second field test.     

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.     

Woodstove smoke and CO emissions: comparison of reference methods with the VIP sampler

A new field sampler has been developed for measuring the particulate matter (PM) and carbon monoxide emissions of woodburning stoves. Particulate matter is determined by carbon balance and the workup of a sample train which is similar to a room-temperature EPA Method 5G train. A steel tank, initially evacuated, serves as the motive force for sampling and also accumulates a gas sample for post-test analysis of time-averaged stack CO and CO2 concentrations. Workup procedures can be completed within 72 hours of sampler retrieval. The system has been compared to reference methods in two laboratory test series involving six different woodburning appliances and two independent laboratories. The correlation of field sampler emission rates and reference method rates is strong.     

A New Audit Technique for EPA Method 25

A simple, inexpensive, and accurate technique for evaluating or auditing the sampling, recovery, and analytical phases of EPA Source Reference Method 25 has been developed. The technique involves spiking a U-shaped stainless steel cartridge containing Tenax® with known quantities of selected organic compounds and thermally desorbing them at temperatures from 160°C to 180°C to generate organic vapors quantitatively. The major advantages of this technique are that no other measurement methods can be used to determine the generated organic concentrations in lieu of Method 25; and that the cartridge can easily be taken to the field for evaluation. The organic compounds generated in test runs are collected and analyzed using the Method 25 procedure. The generation of organics is quantitative and recoveries were found to be 100 ± 10%. The time required for desorption of the majority of organics is generally less than forty-five minutes at a flow rate of 100 mL/min; however, based on laboratory experience the recommended sampling time is sixty minutes. These spiked cartridges are stable at room temperature over a two-month period. Results of interlaboratory studies showed close agreement with the expected concentrations based on calculations from the mass loadings and sample volumes.     

Woodstove Smoke and CO Emissions: Comparison of Reference Methods with the VPI Sampler

A new field sampler has been developed for measuring the particulate matter (PM) and carbon monoxide emissions of woodburning stoves. Particulate matter is determined by carbon balance and the workup of a sample train which is similar to a room-temperature EPA Method 5G train. A steel tank, initially evacuated, serves as the motive force for sampling and also accumulates a gas sample for post-test analysis of time-averaged stack CO and CO₂ concentrations. Workup procedures can be completed, within 72 hours of sampler retrieval. The system has been compared to reference methods in two laboratory test series involving six different woodburning appliances and two independent laboratories. The correlation of field sampler emission rates and reference method rates is strong.     

Characterization of emissions from diffusion flare systems

Emissions from flares typical of those found at oil-field battery sites in Alberta, Canada, were investigated to determine the degree to which the flared gases were burned and to characterize the products of combustion in the emissions. The study consisted of laboratory, pilot-scale, and field-scale investigations. Combustion of all hydrocarbon fuels in both laboratory and pilot-scale tests produced a complex variety of hydrocarbon products within the flame, primarily by pyrolytic reactions. Acetylene, ethylene, benzene, styrene, ethynyl benzene, and naphthalene were some of the major constituents produced by conversion of more than 10% of the methane within the flames. The majority of the hydrocarbons produced within the flames of pure gas fuels were effectively destroyed in the outer combustion zone, resulting in combustion efficiencies greater than 98% as measured in the emissions. The addition of liquid hydrocarbon fuels or condensates to pure gas streams had the largest effect on impairing the ability of the resulting flame to destroy the pyrolytically produced hydrocarbons, as well as the original hydrocarbon fuels directed to the flare. Crosswinds were also found to reduce the combustion efficiency (CE) of the co-flowing gas/condensate flames by causing more unburned fuel and the pyrolytically produced hydrocarbons to escape into the emissions. Flaring of solution gas at oil-field battery sites was found to burn with an efficiency of 62-82%, depending on either how much fuel was directed to flare or how much liquid hydrocarbon was in the knockout drum. Benzene, styrene, ethynyl benzene, ethynyl-methyl benzenes, toluene, xylenes, acenaphthalene, biphenyl, and fluorene were, in most cases, the most abundant compounds found in any of the emissions examined in the field flare testing. The emissions from sour solution gas flaring also contained reduced sulfur compounds and thiophenes.     

Methods of characterizing the distribution of exhaust emissions from light-duty, gasoline-powered motor vehicles in the U.S. fleet

Mobile sources significantly contribute to ambient concentrations of airborne particulate matter (PM). Source apportionment studies for PM10 (PM < or = 10 microm in aerodynamic diameter) and PM2.5 (PM < or = 2.5 microm in aerodynamic diameter) indicate that mobile sources can be responsible for over half of the ambient PM measured in an urban area. Recent source apportionment studies attempted to differentiate between contributions from gasoline and diesel motor vehicle combustion. Several source apportionment studies conducted in the United States suggested that gasoline combustion from mobile sources contributed more to ambient PM than diesel combustion. However, existing emission inventories for the United States indicated that diesels contribute more than gasoline vehicles to ambient PM concentrations. A comprehensive testing program was initiated in the Kansas City metropolitan area to measure PM emissions in the light-duty, gasoline-powered, on-road mobile source fleet to provide data for PM inventory and emissions modeling. The vehicle recruitment design produced a sample that could represent the regional fleet, and by extension, the national fleet. All vehicles were recruited from a stratified sample on the basis of vehicle class (car, truck) and model-year group. The pool of available vehicles was drawn primarily from a sample of vehicle owners designed to represent the selected demographic and geographic characteristics of the Kansas City population. Emissions testing utilized a portable, light-duty chassis dynamometer with vehicles tested using the LA-92 driving cycle, on-board emissions measurement systems, and remote sensing devices. Particulate mass emissions were the focus of the study, with continuous and integrated samples collected. In addition, sample analyses included criteria gases (carbon monoxide, carbon dioxide, nitric oxide/nitrogen dioxide, hydrocarbons), air toxics (speciated volatile organic compounds), and PM constituents (elemental/organic carbon, metals, semi-volatile organic compounds). Results indicated that PM emissions from the in-use fleet varied by up to 3 orders of magnitude, with emissions generally increasing for older model-year vehicles. The study also identified a strong influence of ambient temperature on vehicle PM mass emissions, with rates increasing with decreasing temperatures.     

Hazard assessment of chemicals in soil

Based on a stepwise (tiered) approach, degradation, adsorption and leaching tests as well as various effect tests (using plants, microorganisms and animals) are recommended for the testing of environmental chemicals. If, after the tests of tiers 1 and 2, the results of a monospecies-effect-test (including a safety factor) are within the range of the predicted exposure, the ecotoxicological hazard should be determined using a terrestrial model ecosystem. Some of the tests for the proposed strategy were selected from practical experience in testing environmental chemicals in the laboratory, and some on the basis of a comprehensive literature review.