Validation of Three New Methods for Determination of Metal Emissions Using a Modified Environmental Protection Agency Method 301

Abstract

Three new methods applicable to the determination of hazardous metal concentrations in stationary source emissions were developed and evaluated for use in U.S. Environmental Protection Agency (EPA) compliance applications. Two of the three independent methods, a continuous emissions monitor-based method (Xact) and an X-ray-based filter method (XFM), are used to measure metal emissions. The third method involves a quantitative aerosol generator (QAG), which produces a reference aerosol used to evaluate the measurement methods. A modification of EPA Method 301 was used to validate the three methods for As, Cd, Cr, Pb, and Hg, representing three hazardous waste combustor Maximum Achievable Control Technology (MACT) metal categories (low volatile, semivolatile, and volatile). The modified procedure tested the methods using more stringent criteria than EPA Method 301; these criteria included accuracy, precision, and linearity. The aerosol generation method was evaluated in the laboratory by comparing actual with theoretical aerosol concentrations. The measurement methods were evaluated at a hazardous waste combustor (HWC) by comparing measured with reference aerosol concentrations. The QAG, Xact, and XFM met the modified Method 301 validation criteria. All three of the methods demonstrated precisions and accuracies on the order of 5%. In addition, correlation coefficients for each method were on the order of 0.99, confirming the methods’ linear response and high precision over a wide range of concentrations. The measurement methods should be applicable to emissions from a wide range of sources, and the reference aerosol generator should be applicable to additional analytes. EPA recently approved an alternative monitoring petition for an HWC at Eli Lilly’s Tippecanoe site in Lafayette, IN, in which the Xact is used for demonstrating compliance with the HWC MACT metal emissions (low volatile, semivolatile, and volatile). The QAG reference aerosol generator was approved as a method for providing a quantitative reference aerosol, which is required for certification and continuing quality assurance of the Xact.     

Dilution-based emissions sampling from stationary sources: Part 1--Compact sampler methodology and performance

This paper presents the design and performance of a compact dilution sampler (CDS) for characterizing fine particle emissions from stationary sources. The sampler is described, along with the methodology adopted for its use. Dilution sampling has a number of advantages, including source emissions that are measured under conditions simulating stack gas entry and mixing in the ambient atmosphere. This is particularly important for characterizing the semivolatile species in effluents as a part of particulate emissions. The CDS characteristics and performance are given, along with sampling methodology. The CDS was compared with a reference dilution sampler. The results indicate that the two designs are comparable for tests on gas-fired units and a diesel electrical generator. The performance data indicate that lower detection limits can be achieved relative to current regulatory methods for particulate emissions. Test data for the fine particulate matter (PM2.5) emissions are provided for comparison with U.S. Environment Protection Agency (EPA) Conditional Test Method 040 for filterable particulate matter (FPM) and the EPA Method 202 for condensable particulate matter. This comparison showed important differences between methods, depending on whether a comparison is done between in situ FPM determinations or the sum of such values with condensable PM from liquid filled impingers chilled in an ice bath. These differences are interpretable in the light of semivolatile material present in the stack effluent and, in some cases, differences in detection and quantification limits. Determination of emissions from combustors using liquid fuels can be readily achieved using 1-hr sampling with the CDS. Emissions from gasfired combustors are very low, requiring careful attention to sample volumes. Sampling volumes corresponding with 6-hr operation were used for the combined mass and broad chemical speciation. Particular attention to dilution sampler operation with clean dilution air also is essential for gas-fired sources.     

Overview of the U.S. Environmental Protection Agency's Hazardous Air Pollutant Early Reduction Program.

Under provision of the Clean Air Act Amendments of 1990 Title III, the EPA has proposed a regulation (Early Reduction Program) to allow a six-year compliance extension from Maximum Achievable Control Technology (MACT) standards for sources that voluntarily reduce emissions of Hazardous Air Pollutants (HAPs) by 90 percent or more (95 percent or more for particulates) from a base year of 1987 or later. The emission reduction must be made before the applicable MACT standard is proposed for the source category or be subject to an enforceable commitment to achieve the reduction by January 1, 1994 for sources subject to MACT standards prior to 1994. The primary purpose of this program is to encourage reduction of HAPs emissions sooner than otherwise required. Industry would be allowed additional time in evaluating emission reduction options and developing more cost-effective compliance strategies, although, under strict guidelines to ensure actual, significant and verifiable emission reductions occur.     

Performance evaluation of laser-induced breakdown spectrometry as a multimetal continuous emission monitor

Laser-induced breakdown spectroscopy (LIBS) has been evaluated as a multimetal continuous emissions monitor (CEM) at the U.S. Environmental Protection Agency (EPA) rotary kiln incinerator simulator (RKIS) facility in Raleigh, NC. Two detection systems with a bifurcated optical fiber bundle were used for simultaneously monitoring the concentrations of Be, Cd, Cr, and Hg in the test. Two calibration techniques were evaluated in the laboratory for the field measurements. On-line calibration of relative metal concentration was also performed in the simulated incinerator gas stream. Toxic metal concentrations measured with LIBS have been compared with the EPA reference method (RM) results.     

Carbon bed mercury emissions control for mixed waste treatment

Mercury has various uses in nuclear fuel reprocessing and other nuclear processes, and so it is often present in radioactive and mixed (radioactive and hazardous) wastes. Compliance with air emission regulations such as the Hazardous Waste Combustor (HWC) Maximum Achievable Control Technology (MACT) standards can require off-gas mercury removal efficiencies up to 99.999% for thermally treating some mixed waste streams. Test programs have demonstrated this level of off-gas mercury control using fixed beds of granular sulfur-impregnated activated carbon. Other results of these tests include (1) the depth of the mercury control mass transfer zone was less than 15-30 cm for the operating conditions of these tests; (2) MERSORB carbon can sorb mercury up to 19 wt % of the carbon mass; and (3) the spent carbon retained almost all (98.3-99.99%) of the mercury during Toxicity Characteristic Leachability Procedure (TCLP) tests, but when even a small fraction of the total mercury dissolves, the spent carbon can fail the TCLP test when the spent carbon contains high mercury concentrations.     

A review of the role of plastics in energy recovery

This report reviews the major scientific investigations that have been reported world wide over the last ten years on the effect of plastics on the process and emission performance of energy from waste (EFW) facilities. Concentrations of contaminants in air emissions and other process residues measured during tests with added plastics are compared with concentrations during normal operations and with the stringent emission limits stipulated in municipal waste combustor standards and guidelines in Canada, the United States and the European Union. The emission limits in these standards and guidelines are based on the use of the best technology available (Maximum Achievable Control Technology (MACT) standards in North America and Best Available Technology (BAT) standards in Europe) and are amongst the most stringent in the world.     

Demonstration of In Situ Steam and Hot-Air Stripping Technology

Between September 5 and October 5,1989 a field demonstration of the NovaTerra, Inc. Detoxifier [formerly called Toxic Treatment (USA)] was performed by the U.S. EPA under the Superfund Innovative Technology Evaluation (SITE) program. The NovaTerra Detoxifier process injects steam and hot air directly into the ground to vaporize and strip volatile and semivolatile organics. Two augers loosen and homogenize the soil during the stripping process. The steam, hot air and organics are carried to the soil surface and collected for treatment.

The field demonstration was performed at the GATX Annex Terminal located at the Port of Los Angeles, San Pedro, California. Approximately 17 percent of the 5.2 acre site is contaminated with chlorinated solvents, plasticizers, coatings, adhesives and paint additives, and other miscellaneous chemicals from aboveground storage tanks and transfer operations to railroad cars.

The objectives of this SITE Demonstration were to determine the in situ soil concentrations before and after treatment, quantify process stream emissions (fugitive and sidestreams), determine process operating conditions, and determine if vertical migration of contaminants is occurring. Results from the SITE demonstration showed that a substantial amount of the VOCs were removed, about half the SVOCs were removed, there was very little fugitive air emissions from the operation, and what little downward migration occured (if any) was inconsequential.     

Relative accuracy testing of an X-ray fluorescence-based mercury monitor at coal-fired boilers

The relative accuracy (RA) of a newly developed mercury continuous emissions monitor, based on X-ray fluorescence, was determined by comparing analysis results at coal-fired plants with two certified reference methods (American Society for Testing and Materials [ASTM] Method D6784-02 and U.S. Environment Protection Agency [EPA] Method 29). During the first determination, the monitor had an RA of 25% compared with ASTM Method D6784-02 (Ontario Hydro Method). However, the Ontario Hydro Method performed poorly, because the mercury concentrations were near the detection limit of the reference method. The mercury in this exhaust stream was primarily elemental. The second test was performed at a U.S. Army boiler against EPA Reference Method 29. Mercury and arsenic were spiked because of expected low mercury concentrations. The monitor had an RA of 16% for arsenic and 17% for mercury, meeting RA requirements of EPA Performance Specification 12a. The results suggest that the sampling stream contained significant percentages of both elemental and oxidized mercury. The monitor was successful at measuring total mercury in particulate and vapor forms.     

Dilution-based emissions sampling from stationary sources: Part 2--Gas-fired combustors compared with other fuel-fired systems

With the recent focus on fine particle matter (PM2.5), new, self-consistent data are needed to characterize emissions from combustion sources. Such data are necessary for health assessment and air quality modeling. To address this need, emissions data for gas-fired combustors are presented here, using dilution sampling as the reference. The dilution method allows for collection of emitted particles under conditions simulating cooling and dilution during entry from the stack into the air. The sampling and analysis of the collected particles in the presence of precursor gases, SO2 nitrogen oxide, volatile organic compound, and NH3 is discussed; the results include data from eight gas fired units, including a dual-fuel institutional boiler and a diesel engine powered electricity generator. These data are compared with results in the literature for heavy-duty diesel vehicles and stationary sources using coal or wood as fuels. The results show that the gas-fired combustors have very low PM2.5 mass emission rates in the range of approximately 10(-4) lb/million Btu (MMBTU) compared with the diesel backup generator with particle filter, with approximately 5 x 10(-3) lb/MMBTU. Even higher mass emission rates are found in coal-fired systems, with rates of approximately 0.07 lb/MMBTU for a bag-filter-controlled pilot unit burning eastern bituminous coal. The characterization of PM2.5 chemical composition from the gas-fired units indicates that much of the measured primary particle mass in PM2.5 samples is organic or elemental carbon and, to a much less extent, sulfate. Metal emissions are quite low compared with the diesel engines and the coal- or wood-fueled combustors. The metals found in the gas-fired combustor particles are low in concentration, similar in concentration to ambient particles. The interpretation of the particulate carbon emissions is complicated by the fact that an approximately equal amount of particulate carbon (mainly organic carbon) is found on the particle collector and a backup filter. It is likely that measurement artifacts, mostly adsorption of volatile organic compounds on quartz filters, are positively biasing "true" particulate carbon emission results.     

The MACT for petroleum refinery FCCs is a fraud!

This paper is a continuation of the author's research on the MACT regulation for abating pollution from Petroleum Refinery FCCs in the US. This paper highlights the flaws in the recently promulgated MACT for NSPS and non-NSPS FCC units. It details the inadequacies and the potential for perversity in the New Source Performance Standards (NSPS) that are an integral part of the FCC MACT. It elaborates upon the potential for multi-media risk-exacerbations under the NSPS resulting from changes in feedstock quality, 'unit conversion', advances in cracking technology (that favour inferior crudes and feedstock), lack of NSPS standards for NO_x emissions, inter-unit transfer of contaminants/pollutants within a refinery, and the blind eye turned by RCRA to the disposal of spent FCC catalyst waste to landfills. The paper also questions EPA's motives as regards sub-categorisation of FCCs and SBREFA concessions. This paper proposes four standards that remedy these deficiencies. The first standard controls heavy metals, PM, and SO_x (along with SO₂), while the second proposes an integrated percentile control standard for CO (VOC) and NO_x emissions. The paper also proposes a percentile standard for opacity and a spent catalyst tax to control environmental risk posed by disposal of spent FCC catalyst waste to landfills. It explains the calibration of the proposed standards using a novel strategy to bridge the regulatory gap between NSPS, MACT and Residual Risk standards and demonstrates how the calibrated standards apply to FCCs processing feedstock of different qualities. The paper concludes by urging the US EPA to rescind the NSPS and the MACT for FCCs and re-promulgate an integrated set of standards for criteria and toxic pollutants along the lines proposed in this paper.     

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.     

National review of ambient air toxics observations

Ambient air observations of hazardous air pollutant (HAPs), also known as air toxics, derived from routine monitoring networks operated by states, local agencies, and tribes (SLTs), are analyzed to characterize national concentrations and risk across the nation for a representative subset of the 187 designated HAPs. Observations from the National Air Toxics Trend Sites (NATTS) network of 27 stations located in most major urban areas of the contiguous United States have provided a consistent record of HAPs that have been identified as posing the greatest risk since 2003 and have also captured similar concentration patterns of nearly 300 sites operated by SLTs. Relatively high concentration volatile organic compounds (VOCs) such as benzene, formaldehyde, and toluene exhibit the highest annual average concentration levels, typically ranging from 1 to 5 µg/m³. Halogenated (except for methylene chloride) and semivolatile organic compounds (SVOCs) and metals exhibit concentrations typically 2–3 orders of magnitude lower. Formaldehyde is the highest national risk driver based on estimated cancer risk and, nationally, has not exhibited significant changes in concentration, likely associated with the large pool of natural isoprene and formaldehyde emissions. Benzene, toluene, ethylbenzene, and 1,3-butadiene are ubiquitous VOC HAPs with large mobile source contributions that continue to exhibit declining concentrations over the last decade. Common chlorinated organic compounds such as ethylene dichloride and methylene chloride exhibit increasing concentrations. The variety of physical and chemical attributes and measurement technologies across 187 HAPs result in a broad range of method detection limits (MDLs) and cancer risk thresholds that challenge confidence in risk results for low concentration HAPs with MDLs near or greater than risk thresholds. From a national monitoring network perspective, the ability of the HAPs observational database to characterize the multiple pollutant and spatial scale patterns influencing exposure is severely limited and positioned to benefit by leveraging a variety of emerging measurement technologies.

Implications:?Ambient air toxics observation networks have limited ability to characterize the broad suite of hazardous air pollutants (HAPs) that affect exposures across multiple spatial scales. While our networks are best suited to capture major urban-scale signals of ubiquitous volatile organic compound HAPs, incorporation of sensing technologies that address regional and local-scale exposures should be pursued to address major gaps in spatial resolution. Caution should be exercised in interpreting HAPs observations based on data proximity to minimum detection limit and risk thresholds.     

Assessment of volatile organic compound and hazardous air pollutant emissions from oil and natural gas well pads using mobile remote and on-site direct measurements

Emissions of volatile organic compounds (VOCs) and hazardous air pollutants (HAPs) from oil and natural gas production were investigated using direct measurements of component-level emissions on pads in the Denver-Julesburg (DJ) Basin and remote measurements of production pad-level emissions in the Barnett, DJ, and Pinedale basins. Results from the 2011 DJ on-site study indicate that emissions from condensate storage tanks are highly variable and can be an important source of VOCs and HAPs, even when control measures are present. Comparison of the measured condensate tank emissions with potentially emitted concentrations modeled using E&P TANKS (American Petroleum Institute [API] Publication 4697) suggested that some of the tanks were likely effectively controlled (emissions less than 95% of potential), whereas others were not. Results also indicate that the use of a commercial high-volume sampler (HVS) without corresponding canister measurements may result in severe underestimates of emissions from condensate tanks. Instantaneous VOC and HAP emissions measured on-site on controlled systems in the DJ Basin were significantly higher than VOC and HAP emission results from the study conducted by Eastern Research Group (ERG) for the City of Fort Worth (2011) using the same method in the Barnett on pads with low or no condensate production. The measured VOC emissions were either lower or not significantly different from the results of studies of uncontrolled emissions from condensate tanks measured by routing all emissions through a single port monitored by a flow measurement device for 24 hr. VOC and HAP concentrations measured remotely using the U.S. Environmental Protection Agency (EPA) Other Test Method (OTM) 33A in the DJ Basin were not significantly different from the on-site measurements, although significant differences between basins were observed.

Implications: VOC and HAP emissions from upstream production operations are important due to their potential impact on regional ozone levels and proximate populations. This study provides information on the sources and variability of VOC and HAP emissions from production pads as well as a comparison between different measurement techniques and laboratory analysis protocols. On-site and remote measurements of VOC and HAP emissions from oil and gas production pads indicate that measurable emissions can occur despite the presence of control measures, often as a result of leaking thief hatch seals on condensate tanks. Furthermore, results from the remote measurement method OTM 33A indicate that it can be used effectively as an inspection technique for identifying oil and gas well pads with large fugitive emissions.     

Estimation of Organic Compound Emissions from Waste Lagoons

Abstract

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

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.     

Use of Bioassay Methods to Evaluate Mutagenicity of Ambient Air Collected Near a Municipal Waste Combustor

An ambient air sampling study was conducted around a municipal waste combustor; a primary goal was to develop procedures and methods to evaluate the emissions of organic mutagens resulting from incomplete combustion of municipal waste. The products of Incomplete combustion from incineration include complex mixtures of organics, particularly polycycllc aromatic compounds, which are present after atmospheric dilution and cooling In emissions as semi-volatile or particle bound organic compounds. Combustion emissions are generally recognized as a potential cancer risk since they contain many carcinogenic and mutagenlc polycyclic aromatic hydrocarbons. Analyzing such a complex mixture for the presence of even a few selected chemicals is difficult and provides risk information on only a fraction of the chemicals present. Bioassay methods, however, may be directly applied to evaluate the mutagenic and potential carcinogenic activity of the complex organics from combustion emissions. The Salmonella (Ames) assay was used to determine the mutagenicity associated with particles from ambient air collected near a municipal waste combustor. Dose-response data was generated, and mutagenicity concentrations were calculated to demonstrate the utility of bioassay In assessing the potential Impact of emissions from municipal waste combustion. This phase of study quantified mutagenicity concentrations In ambient air but did not detect organic mutagens that could be attributed to Incinerator emissions.     

Source attribution for mercury deposition in the contiguous United States: regional difference and seasonal variation

Quantifying the contribution of emission sources responsible for mercury deposition in specific receptor regions helps develop emission control strategies that alleviate the impact on ecosystem and human health. In light of the maximum available control technology (MACT) rules proposed by U.S. Environmental Protection Agency (EPA) and the ongoing intergovernmental negotiation coordinated by United Nations Environmental Programme (UNEP) for mercury, the Community Multiscale Air Quality Modeling System (CMAQ-Hg) was applied to estimate the source contribution in six subregions of the contiguous United States (CONUS). The considered source categories include electric generating units (EGU), iron and steel industry (IRST), other industrial point sources excluding EGU and IRST (OIPM), the remaining anthropogenic sources (RA), natural processes (NAT), and out-of-boundary transport (BC). It is found that, on an annual basis, dry deposition accounts for two-thirds of total annual deposition in CONUS (474 Mg yr(-1)), mainly contributed by reactive gaseous mercury (about 60% of total deposition). The contribution from large point sources can be as high as 75% near the emission sources (< 100 km), indicating that emission reduction may result in direct deposition decrease near the source locations. Out-of-boundary transport contributes from 68% (Northeast) to 91% (West Central) of total deposition. Excluding the contribution from out-of boundary transport, EGU contributes to about 50% of deposition in the Northeast, Southeast, and East Central regions, whereas emissions from natural processes are more important in the Pacific and West Central regions (contributing up to 40% of deposition). This suggests that the implementation of the new EPA MACT standards will significantly benefit only these three regions. Emission speciation is a key factor for local deposition. The source contribution exhibits strong seasonal variation. Deposition is greater in warm seasons due to stronger Hg0 oxidation. However, the contribution from anthropogenic sources is smaller in warm seasons because of larger emissions from natural processes and stronger vertical mixing that facilitates transport.     

epa’s research program for controlling residential wood combustion emissions

A recently completed study has shown that emissions of participate, carbon monoxide, and organics (including polycyclic organic matter) are relatively high from residential woodburning stoves and fireplaces when compared to emissions from residential gas- and oil-fired furnaces. Since these emissions include a number of potentially hazardous compounds; the trend toward greater residential wood usage can have a negative impact on local ambient air quality. EPA is currently studying ways to operate existing stoves and design new stoves to minimize air pollutant emissions.     

Use of subsampled traffic data to estimate roadway emissions, including conversion to MOBILE6 vehicle classifications

Air quality is degraded by many factors, among which the emissions from on-road vehicles play a significant role. Timely and accurate estimate of such emissions becomes very important for policy-making and effective control measures. However, lack of traffic data and outdated emission software make this task difficult. This research has demonstrated a new method that facilitates the vehicular emission inventories at the local level by using shorter-time Highway Performance Monitoring System (HPMS) traffic data along with the latest U.S. Environment Protection Agency (EPA) emission modeling software, MOBILE6. The conversion methodology was developed for converting readily available HPMS traffic volume data into EPA MOBILE-based traffic classifications, and a corresponding software program was written for automating the process. EPA MOBILE6 model was used to obtain emissions of nitrogen oxides (NOx), volatile organic compound (VOC), and cabon monoxide (CO) emitted by the parent traffic and subsampled traffic data, and these emissions were additionally compared. The case study has shown that the difference of the magnitude between the emission estimates produced by certain subsampled and parent traffic data are minor, indicating that subsampled HPMS data can be used for reporting parent traffic emissions. It was also observed that traffic emissions follow a Weibull distribution, and NOx emissions were more sensitive to the traffic data composition than VOC and CO. Lastly, use of average emission values of 20 or 30 consecutive minutes appears to be valid for representing hourly emissions.     

Prediction of dioxin/furan incinerator emissions using low-molecular-weight volatile products of incomplete combustion

Emissions of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) from incinerators and other stationary combustion sources are of environmental concern because of the toxicity of certain PCDD/F congeners. Measurement of trace levels of PCDDs/Fs in combustor emissions is not a trivial matter. Development of one or more simple, easy-to-measure, reliable indicators of stack PCDD/F concentrations not only would enable incinerator operators to economically optimize system performance with respect to PCDD/F emissions, but could also provide a potential technique for demonstrating compliance status on a more frequent basis. This paper focuses on one approach to empirically estimate PCDD/F emissions using easy-to-measure volatile organic C2 chlorinated alkene precursors coupled with flue gas cleaning parameters. Three data sets from pilot-scale incineration experiments were examined for correlations between C2 chlorinated alkenes and PCDDs/Fs. Each data set contained one or more C2 chloroalkenes that were able to account for a statistically significant fraction of the variance in PCDD/F emissions. Variations in the vinyl chloride concentrations were able to account for the variations in the PCDD/F concentrations strongly in two of the three data sets and weakly in one of the data sets.