Dissociation of Sulfur Hexafluoride Tracer Gas in the Presence of an Indoor Combustion Source

ABSTRACT

As an odorless, nontoxic, and inert compound, sulfur hexafluoride (SF₆) is one of the most widely used tracer gases in indoor air quality studies in both controlled and uncontrolled environments. This compound may be subject to reactions with water vapor under elevated temperature to form acidic inorganic compounds such as HF and H₂SO₄. Thus, in the presence of unvented combustion sources such as kerosene heaters, natural gas heaters, gas log fireplaces, candles, and lamps, the SF₆ dissociation may interfere with measurements of the emissions from these sources. Tests were conducted in a research house with a vent-free natural gas heater to investigate these potential interferences. It was observed that the heater operation caused about a 5% reduction of SF₆ concentration, which can be an error source for the ventilation rate measurement and consequently the estimated pollutant emission rates. Further analysis indicates that this error can be much greater than the observed 5% under certain test conditions because it is a function of the ventilation flow rate. Reducing the tracer gas concentration has no effect on this error. A simple theoretical model is proposed to estimate the magnitude of this error.

The second type of interference comes from the primary and secondary products of the SF₆ dissociation, mainly H₂SO₄, SO₂, HF, and fine particulate matter (PM). In the presence of ~5 ppm SF₆, the total airborne concentrations of these species increased by a factor of 4-10. The tests were performed at relatively high SF₆ concentrations, which is necessary to determine the interferences quantitatively. The second type of interference can be significantly reduced if the SF₆ concentration is kept at a low ppb level.     

Application of the tracer-aerosol gradient interpretive technique to sulfur attribution for the big bend regional aerosol and visibility observational study

A simple data analysis method called the Tracer-Aerosol Gradient Interpretive Technique (TAGIT) is used to attribute particulate S and SO2 at Big Bend National Park in Texas and nearby areas to local and regional sources. Particulate S at Big Bend is of concern because of its effects on atmospheric visibility. The analysis used particulate S, SO2, and perfluorocarbon tracer data from six 6-hr sampling sites in and near Big Bend National Park. The data were collected in support of the Big Bend Regional Aerosol and Visibility Observational (BRAVO) Study; the field portion was conducted from July through October 1999. Perfluorocarbon tracer was released continuously from a tower at Eagle Pass, TX, approximately 25 km northeast of two large coal-fired power plants (Carbon I and II) in Coahuila, Mexico, and approximately 270 km east-southeast of Big Bend National Park. The perfluorocarbon tracer did not properly represent the location of the emissions from the Carbon power plants for individual 6-hr sampling periods and attributed only 3% of the particulate S and 27% of the SO2 at the 6-hr sites in and near Big Bend to sources represented by the tracer. An alternative approach using SO2 to tag "local" sources such as the Carbon plants attributed 10% of the particulate S and 75% of the SO2 at the 6-hr sites to local sources. Based on these two approaches, most of the regional (65-86%) and a small fraction (19-31%) of the local SO2 was converted to particulate S. The analysis implies that substantial reductions in particulate S at Big Bend National Park cannot be achieved by only reducing emissions from the Carbon power plants; reduction of emissions from many sources over a regional area would be necessary.     

Abatement of sulfur hexafluoride emissions from the semiconductor manufacturing process by atmospheric-pressure plasmas

Sulfur hexafluoride (SF6) is an important gas for plasma etching processes in the semiconductor industry. SF6 intensely absorbs infrared radiation and, consequently, aggravates global warming. This study investigates SF6 abatement by nonthermal plasma technologies under atmospheric pressure. Two kinds of nonthermal plasma processes--dielectric barrier discharge (DBD) and combined plasma catalysis (CPC)--were employed and evaluated. Experimental results indicated that as much as 91% of SF6 was removed with DBDs at 20 kV of applied voltage and 150 Hz of discharge frequency for the gas stream containing 300 ppm SF6, 12% oxygen (O2), and 40% argon (Ar), with nitrogen (N2) as the carrier gas. Four additives, including Ar, O2, ethylene (C2H4), and H2O(g), are effective in enhancing SF6 abatement in the range of conditions studied. DBD achieves a higher SF6 removal efficiency than does CPC at the same operation condition. But CPC achieves a higher electrical energy utilization compared with DBD. However, poisoning of catalysts by sulfur (S)-containing species needs further investigation. SF6 is mainly converted to SOF2, SO2F4, sulfur dioxide (SO2), oxygen difluoride (OF2), and fluoride (F2). They do not cause global warming and can be captured by either wet scrubbing or adsorption. This study indicates that DBD and CPC are feasible control technologies for reducing SF6 emissions.     

Ammonia emissions from two mechanically ventilated UK livestock buildings

Ammonia emission rates from livestock buildings are required to construct an accurate emission inventory for the UK. Ventilation and ammonia emission rates from a fattening pig unit and a broiler house, both mechanically ventilated, were estimated using fan wheel anemometers and thermal converters with a chemiluminescence NO_x-analyser to measure the ventilation rate and the ammonia concentration, respectively. The estimated ammonia emission factors were 46.9 and 16.6 kg lu^-1 a^-1 for the fattening pig unit and the broiler house, respectively. Both emission factors were within the range reported in the literature. A tracer gas (CO) method, based on a constant tracer release rate, was validated for measuring ventilation rates from naturally ventilated livestock buildings. Air inlets and outlets were identified using the air temperature or tracer concentration in the opening. Tracer concentration was found to be a more suitable criterion than temperature. In both houses, a significant correlation between the estimated ventilation rate using the tracer method and the measured ventilation rate using fan wheel anemometers was found. The ventilation rate was underestimated by 12 and 6% for the piggery and broiler house, respectively. The instantaneous ammonia emission derived from the tracer gas method was lower than the ammonia emission derived from the fan wheel anemometer method by 14 and 16% for the piggery and broiler house, respectively. The ventilation and ammonia emission estimates using the tracer method were within acceptable range from the ventilation and emission rates measured using measuring fans, but because of its accuracy and simplicity the fan wheel anemometer method is preferred for long-term measurements of ventilation rate in mechanically ventilated buildings.     

Sulfur hexafluoride (SF6): global environmental effects and toxic byproduct formation

This work provides information concerning possible global environmental implications and personnel safety aspects that should be considered during the commercial uses of sulfur hexafluoride (SF6). SF6 is an anthropogenically produced compound, mainly used as a gaseous dielectric in gas insulated switchgear power installations. It is a potent greenhouse gas with a high global warming potential, and its concentration in the earth atmosphere is rapidly increasing. During its working cycle, SF6 decomposes under electrical stress, forming toxic byproducts that are a health threat for working personnel in the event of exposure. Several precautions are recommended to avoid personnel exposure to toxic byproducts: oxyfluoride levels or other byproduct concentrations in the operating gas matrix should be traced to predetermine the overall gas toxicity; contaminants should be systematically considered during maintenance, chamber evacuation and system opening process; small SF6 quantities leaking into air or stagnated pollutant concentrations in the operating field should be analyzed and compared to the threshold limit values and permissible exposure levels. New system design rules (i.e., hermetically sealed gas compartments, gas recycling or disposal in the field area) and different handling policies--both during maintenance and final disposal--now should be considered globally to provide for environmental and personnel safety.     

Decomposition of SF6 in an RF plasma environment

Sulfur hexafluoride (SFd)-contained gas is a common pollutant emitted during the etching process used in the semiconductor industry. This study demonstrated the application of radio-frequency (RF) plasma in the decomposition of SF6. The decomposition fraction of SF6 [etaSF6 (C(in)-C(out))/C(in) x 100%] and the mole fraction profile of the products were investigated as functions of input power and feed O2/SF6 ratio in an SiO2 reactor. The species detected in both SF6/Ar and SF6/O2/ Ar RF plasmas were SiF4, SO2, Fe2, SO2F2, SOF2, SOF4, S2F10, S2OF10, S2O2F10, and SF4. The results revealed that at 40 W, etaSF6 exceeded 99%, and the reaction products were almost all converted into stable compounds such as SiF4, SO2, and F2 with or without the addition of oxygen. Sulfur oxyfluorides such as SO2F2, SOF2, SOF4, S2OF10, and S2O2F10 were produced only below 40 W. The results of this work can be used to design a plasma/chemical system for online use in a series of a manufacturing process to treat SF6-containing exhaust gases.     

Effect of Gas and Kerosene Space Heaters on Indoor Air Quality: A Study in Homes of Santiago,Chile

Abstract

The impact of outdoor and indoor pollution sources on indoor air quality in Santiago, Chile was investigated. Toward this end, 16 homes were sampled in four sessions. Each session included an outdoor site and four homes using different unvented space heaters (electric or central heating, compressed natural gas, liquefied petroleum gas, and kerosene). Average outdoor fine particulate matter (PM_2.5) concentrations were very high (55.9 μg·m^-3), and a large fraction of these particles penetrated indoors. PM_2.5 and several PM_2.5 components (including sulfate, elemental carbon, organic carbon, metals, and polycyclic aromatic hydrocarbons) were elevated in homes using kerosene heaters. Nitrogen dioxide (NO₂) and ultrafine particles (UFPs) were higher in homes with combustion heaters as compared with those with electric heaters or central heating. A regression model was used to assess the effect of heater use on continuous indoor PM_2.5 concentrations when windows were closed. The model found an impact only for kerosene heaters (45.8 μg m^-3).     

Measurement of Hydrocarbon Emissions Fluxes from Refinery Wastewater Impoundments Using Atmospheric Tracer Techniques

Sulfur hexafluoride (SF6) tracer was used in a series of the experiments to simulate emissions of benzene, toluene, ethyl-benzene, and xylenes (BTEX) from a refinery wastewater basin. The ratio of the measured tracer release to the ambient tracer concentration established a dilution factor which was then used to calculate the mass flux of BTEX from the wastewater basin using the ambient BTEX concentration data. Measured fluxes of BTEX varied from 7 g/min to 70 g/min.

The CHEMDAT7 air emissions model was then used to predict emissions for comparison with the emissions measured using the tracer flux simulation. CHEMDAT7 typically overpredicted total measured BTEX emissions by factors of twelve to seventeen. The degree of overprediction varied both by the individual compound and the module of CHEMDAT7 used to predict emission fluxes.     

Investigation of a new approach to decompose two potent greenhouse gases: photoreduction of SF(6) and SF(5)CF(3) in the presence of acetone

In this paper, we addressed the utilization of photochemical method as an innovative technology for the destruction and removal of two potent greenhouse gases, SF(6) and SF(5)CF(3). The destruction and removal efficiency (DRE) of the process was determined as a function of excitation wavelength, irradiation time, initial ratio of acetone to SF(5)X (X represented F or CF(3)), initial SF(5)X concentration, additive oxygen and water vapor concentration. A complete removal was achieved by a radiation period of 55min and 120min for SF(6)-CH(3)COCH(3) system and SF(5)CF(3)-CH(3)COCH(3) system respectively under 184.9nm irradiation. Extra addition of water vapor can enhance DRE by approximately 6% points in both systems. Further studies with GC/MS and FT-IR proved that no hazardous products such as S(2)F(10), SO(2)F(2), SOF(2), SOF(4) were generated in this process.     

Total toxicity equivalents emissions of SF6, CHF3, and CCl2F2 decomposed in a RF plasma environment

Sulfur hexafluorine compound (SF6), trifluoromethane (CHF3) and diclorodifluoromethane (CCl2F2) are extensively used in the semiconductor industry. They are global warming gases. Most studies have addressed the effective decomposition of fluorine compounds, rather than the toxicity of decomposed by-products. Hence, the concepts of toxicity equivalents (TEQs) were applied in this work. The results indicated that HF and SiF4 were the two greatest contributors of TEQ to the SF6/H2/Ar plasma system, while F2 and SiF4 were the two greatest contributors to the SF6/O2/Ar system. Additionally, SiF4 and HF were the two greatest contributors of TEQ to both the CHF3/H2/Ar and CHF3/O2/Ar plasma systems. HF and HCl were the two greatest contributors of TEQ to the CCl2F2/H2/Ar plasma system, and Cl2 and COCl2 were the two greatest contributors to the CCl2F2/O2/Ar system. HCl and HF can be recovered using wet scrubbing, which reduces the toxicity of these emission gases. Consequently, the hydrogen-based plasma system was a better alternative for treating gases that contained SF6, CHF3 and CCl2F2 from the TEQs point of view.     

The Effects of Infiltration and Insulation on the Source Strengths and Indoor Air Pollution from Combustion Space Heating Appliances

Many energy conservation strategies for residences involve reducing house air exchange rates. Reducing the air exchange rate of a house can cause an increase in pollutant levels if there is an indoor pollution source and if the indoor pollutant source strength remains constant. However, if the indoor pollutant source strength can also be reduced, then it is possible to maintain or even improve indoor air quality. Increasing the insulation level of a house is a means of achieving energy conservation goals and, in addition, can reduce the need for space heating and thereby reduce the pollutant source strengths of combustion space heaters such as unvented kerosene space heaters, unvented gas space heaters, and wood stoves. In this paper, the indoor air quality trade-off between reduced infiltration and increased insulation in residences is investigated for combustion space heaters. Two similar residences were used for the experiment. One residence was used as a control and the other residence had infiltration and insulation levels modified. An unvented propane space heater was used as the source in this study. A model was developed to describe the dependence of both indoor air pollution levels and the appliance source strengths on house air exchange rates and house insulation levels. Model parameters were estimated by applying regression techniques to the data. Results show that indoor air pollution levels in houses with indoor combustion space heating pollution sources can be held constant (or lowered) by reducing the thermal conductance by an amount proportional to (or greater than) the reduction of the air exchange rate.     

Estimation of road traffic emission factors from a long term tracer study

Road traffic emissions, one of the largest source categories in megacity inventories, are highly uncertain. It is essential to develop methodologies to reduce these uncertainties to manage air quality more effectively. In this paper, we propose a methodology to estimate road traffic emission factors (EFs) from a tracer experiment and from roadside pollutants measurements. We emitted continuously during about 300 non-consecutive hours a passive tracer from a finite line source placed on one site of an urban street. At the same time, we measured continuously the resulting tracer concentrations at the other side of the street with a portable on-line gas chromatograph. We used n-propane contained in commercial liquid petroleum gas (LPG) as a passive tracer. Propane offers several advantages to traditional tracers (SF6, N2O, CFCs): low price, easily available, non-reactive, negligible global warming potential, and easy to detect with commercial on-line gas chromatographs.The tracer experiment was carried out from January to March 2007 in a busy street of Ho Chi Minh City (Vietnam). Traffic volume, weather information and pollutant concentrations were also measured at the measurement site. We used the results of the tracer experiment to calculate the dilution factors and afterwards we used these dilution factors, the traffic counts and the pollutant concentrations to estimate the EFs. The proposed method assumes that the finite emission line represents the emission produced by traffic in the full area of the street and therefore there is an error associated to this assumption. We use the Computational Fluids Dynamics (CFD) model MISKAM to calculate this error and to correct the HCMC EFs. EFs for 15 volatile organic compounds (VOCs) and NO are reported here. A comparison with available studies reveals that most of the EFs estimated here are within the range of EFs reported in other studies.     

Near-road multipollutant profiles: associations between volatile organic compounds and a tracer gas surrogate near a busy highway

This research characterizes associations between multiple pollutants in the near-road environment attributed to a roadway line source. It also examines the use of a tracer gas as a surrogate of mobile source pollutants. Air samples were collected in summa canisters along a 300 m transect normal to a highway in Raleigh, North Carolina for five sampling periods spanning four days. Samples were subsequently measured for volatile organic compounds (VOCs) using an electron capture gas chromatograph. Sulfur hexafluoride (SF6) was released from a finite line source adjacent to the roadway for two of the sampling periods, collected in the canisters and measured with the VOCs. Associations between each VOC, and between VOCs and the tracer, were quantified with Pearson correlation coefficients to assess the consistency of the multi-pollutant dispersion profiles, and assess the tracer as a potential surrogate for mobile source pollutants. As expected, benzene, toluene, ethylbenzene, and m,p- and o-xylenes (collectively, BTEX) show strong correlations between each other; further BTEX shows a strong correlation to SF6. Between 26 VOCs, correlation coefficients were greater than 0.8, and 14 VOCs had coefficients greater than 0.6 with the tracer gas. Even under non-downwind conditions, chemical concentrations had significant correlations with distance. Results indicate that certain VOCs are representative of a larger multi-pollutant mixture, and many VOCs are well-correlated with the tracer gas.     

Gas-phase mercury reduction to measure total mercury in the flue gas of a coal-fired boiler

Gaseous elemental and total (elemental + oxidized) mercury (Hg) in the flue gas from a coal-fired boiler was measured by a modified ultraviolet (UV) spectrometer. Challenges to Hg measurement were the spectral interferences from other flue gas components and that UV measures only elemental Hg. To eliminate interference from flue gas components, a cartridge filled with gold-coated sand removed elemental Hg from a flue gas sample. The Hg-free flue gas was the reference gas, eliminating the spectral interferences. To measure total Hg by UV, oxidized Hg underwent a gas-phase, thermal-reduction in a quartz cell heated to 750 degrees C. Simultaneously, hydrogen was added to flash react with the oxygen present forming water vapor and preventing Hg re-oxidation as it exits the cell. Hg concentration results are in parts per billion by volume Hg at the flue gas oxygen concentration. The modified Hg analyzer and the Ontario Hydro method concurrently measured Hg at a field test site. Measurements were made at a 700-MW steam turbine plant with scrubber units and selective catalytic reduction. The flue gas sampled downstream of the selective catalytic reduction contained 2100 ppm SO2 and 75 ppm NOx. Total Hg measured by the Hg analyzer was within 20% of the Ontario Hydro results.     

Household wood heater usage and indoor leakage of BTEX in Launceston,Australia: A null result

A study has been conducted in Launceston, Australia, to determine within households with wood heaters the effect of leakage from the heater and flue on the indoor air concentrations of the pollutants: benzene, toluene, ethylbenzene and xylene (BTEX). The study involved three classes: 28 households without wood heaters, 19 households with wood heaters compliant with the relevant Australian Standard and 30 households with non-compliant wood heaters. Outdoor and indoor BTEX concentrations were measured in each household for 7 days during summer when there was little or no wood heater usage, and for 7 days during winter when there was widespread wood heater usage. Each participant kept a household activity diary throughout their sampling periods. For wintertime, there were no significant differences of the indoor BTEX concentrations between the three classes of households. Also there were no significant relationships between BTEX indoor concentrations within houses and several measures of the amount of wood heater use within these houses. For the households sampled in this study, the use of a wood heater within a house did not lead to BTEX release within that house and had no direct detectable influence on the concentrations of BTEX within the house. We propose that the pressure differences associated with the both the leakiness or permeability of the building envelope and the draught of the wood heater have key roles in determining whether there will be backflow of smoke from the wood heater into the house. For a leaky house with a well maintained wood heater there should be no backflow of smoke from the wood heater into the house. However backflow of smoke may occur in well sealed houses.The study also found that wood heater emissions raise the outdoor concentrations of BTEX in winter in Launceston and through the mixing of outdoor air through the building envelopes into the houses, these emissions contribute to increases in the indoor concentrations of BTEX in winter in all houses in Launceston.     

Assessing the relationship between personal particulate and gaseous exposures of senior citizens living in Baltimore, MD

We conducted a multi-pollutant exposure study in Baltimore, MD, in which 15 non-smoking older adult subjects (> 64 years old) wore a multi-pollutant sampler for 12 days during the summer of 1998 and the winter of 1999. The sampler measured simultaneous 24-hr integrated personal exposures to PM2.5, PM10, SO4(2-), O3, NO2, SO2, and exhaust-related VOCs. Results of this study showed that longitudinal associations between ambient PM2.5 concentrations and corresponding personal exposures tended to be high in the summer (median Spearman's r = 0.74) and low in the winter (median Spearman's r = 0.25). Indoor ventilation was an important determinant of personal PM2.5 exposures and resulting personal-ambient associations. Associations between personal PM2.5 exposures and corresponding ambient concentrations were strongest for well-ventilated indoor environments and decreased with ventilation. This decrease was attributed to the increasing influence of indoor PM2.5 sources. Evidence for this was provided by SO4(2-) measurements, which can be thought of as a tracer for ambient PM2.5. For SO4(2-), personal-ambient associations were strong even in poorly ventilated indoor environments, suggesting that personal exposures to PM2.5 of ambient origin are strongly associated with corresponding ambient concentrations. The results also indicated that the contribution of indoor PM2.5 sources to personal PM2.5 exposures was lowest when individuals spent the majority of their time in well-ventilated indoor environments. Results also indicate that the potential for confounding by PM2.5 co-pollutants is limited, despite significant correlations among ambient pollutant concentrations. In contrast to ambient concentrations, PM2.5 exposures were not significantly correlated with personal exposures to PM2.5-10, PM2.5 of non-ambient origin, O3, NO2, and SO2. Since a confounder must be associated with the exposure of interest, these results provide evidence that the effects observed in the PM2.5 epidemiologic studies are unlikely to be due to confounding by the PM2.5 co-pollutants measured in this study.     

The joint action of sulphur dioxide and hydrogen fluoride on the yield and quality of wheat and barley

The effects of joint action of SO(2) and HF on the yield and quality of wheat and barley were studied by exposing them to combinations of <13,130 or 267 microg m(-3) SO(2) and 0.03 or 0.38 microg m(-3) HF in open top chambers for 90 days. At the concentrations used, SO(2) had greater effects than HF. All responses were marked by compensatory changes. The treatments had no effect on wheat yield, although SO(2) reduced shoot weight. SO(2) increased the growth and yield of barley, and HF or SO(2) increased the grain protein concentration of barley and wheat. The effects of mixtures of SO(2) and HF were complex, but often antagonistic, as the addition of HF counteracted the effect of SO(2) alone.     

Characterization and concentrations of polycyclic aromatic hydrocarbons in emissions from different heating systems in Damascus,Syria

Traffic has long been recognized as the major contributor to polycyclic aromatic hydrocarbon (PAH) emissions to the urban atmosphere. Stationary combustion sources, including residential space heating systems, are also a major contributor to PAH emissions. The aim of this study was to determine the profile and concentration of PAHs in stack flue gas emissions from different kinds of space heaters in order to increase the understanding of the scale of the PAH pollution problem caused by this source. This study set out to first assess the characteristics of PAHs and their corresponding benzo[a]pyrene equivalent emissions from a few types of domestic heaters and central heating systems to the urban atmosphere. The study, enabled for the first time, the characterization of PAHs in stationary combustion sources in the city of Damascus, Syria. Nine different types of heating systems were selected with respect to age, design, and type of fuel burned. The concentrations of 15 individual PAH compounds in the stack flue gas were determined in the extracts of the collected samples using high-performance liquid chromatography system (HPLC) equipped with ultraviolet–visible and fluorescence detectors. In general, older domestic wood stoves caused considerably higher PAH emissions than modern domestic heaters burning diesel oil. The average concentration of ΣPAH (sum of 15 compounds) in emissions from all types of studied heating systems ranged between 43?±?0.4 and 316?±?1.4 μg/m³. Values of total benzo[a]pyrene equivalent ranged between 0.61 and 15.41 μg/m³.     

Simultaneous absorption of NO and SO2 into hexamminecobalt(II)/iodide solution

An innovative catalyst system has been developed to simultaneously remove NO and SO2 from combustion flue gas. Such catalyst system may be introduced to the scrubbing solution using ammonia solution to accomplish sequential absorption and catalytic oxidation of both NO and SO2 in the same reactor. When the catalyst system is utilized for removing NO and SO2 from the flue gas, Co(NH3)(6)2+ ions act as the catalyst and I- as the co-catalyst. Dissolved oxygen, in equilibrium with the residual oxygen in the flue gas, is the oxidant. The overall removal process is further enhanced by UV irradiation at 365 nm. More than 95% of NO is removed at a feed concentration of 250-900 ppm, and nearly 100% of SO2 is removed at a feed concentration of 800-2500 ppm. The sulfur dioxide co-existing in the flue gas is beneficial to NO absorption into hexamminecobalt(II)/iodide solution. NO and SO2 can be converted to ammonium sulfate and ammonium nitrate that can be used as fertilizer materials. The process described here demonstrates the feasibility of removing SO2 and NO simultaneously only by retrofitting the existing wet ammonia flue-gas-desulfurization (FGD) scrubbers.     

The effect of coal combustion flue gas components on low-level chlorine speciation using EPA method 26A

U.S. Environmental Protection Agency (EPA) Method 26A is the recommended procedure for capturing and speciating halogen (X2) and hydrogen halide (HX) stack emissions from combustion sources. Previous evaluation studies of Method 26A have focused primarily on hydrogen chloride (HCl) speciation. Capture efficiency, bias, and the potential interference of Cl2 at high levels (> 20 ppm [microgram/m3]) and NH4Cl in the flue gas stream have been investigated. It has been suggested that precise Cl2 measurement and accuracy in quantifying HX or X2 using Method 26A are difficult to achieve at Cl2 concentrations < 5 ppm; however, no performance data exist to support this. Coal contains low levels of Cl, in the range of 5-2000 ppmw, which results in the presence of HCl and Cl2 in the products of combustion. HCl is the predominant Cl compound formed in the high-temperature combustion process, and it persists in the gas as the products of combustion cool. Concentrations of Cl2 in coal combustion flue gas at stack temperatures typically do not exceed 5 ppm. For this research, bench-scale experiments using simulated combustion flue gas were designed to validate the ability of Method 26A to speciate low levels of Cl2 accurately. This paper presents the results of the bench-scale tests. The effect of various flue gas components is discussed. The results indicate that SO2 is the only component in coal combustion flue gas that has an appreciable effect on Cl2 distribution in Method 26A impingers, and that Method 26A cannot accurately speciate HCl and Cl2 in coal combustion flue gas without modification.