Continuous emissions monitoring using spark-induced breakdown spectroscopy

A new technology for monitoring airborne heavy metals on aerosols and particulates based on spark-induced breakdown spectroscopy (SIBS) was evaluated at a joint U.S. Environmental Protection Agency (EPA)/U.S. Department of Energy test at the rotary kiln incinerator simulator (RKIS) facility at EPA/Research Triangle Park, NC, in September 1997. The instrument was configured to measure lead and chromium in a simulated combustion flue gas in real time and in situ at target levels of 15 and 75 micrograms/dry standard cubic meters. Actual metal concentrations were measured during the tests using EPA Reference Method (RM) 29. The SIBS technology detected both lead and chromium at the low- and high-level concentrations. Additionally, the hardware performed without failure for more than 100 hr of operation and acquired data for 100% of the RM tests. The chromium data were well correlated with concentration increases resulting from duct operations and pressure fluctuations that are known to entrain dust.     

Thermal Encapsulation of Metals in Superfund Soils

Abstract

Superfund sites frequently contain both heavy metals and organic hazardous waste. If not properly controlled, the metals may be changed to a more leachable form and may also be emitted to the atmosphere via the exhaust stack. This paper documents a batch kiln R&D test program to solve these metal-related problems. It was performed under the U.S. EPA’s SITE (Superfund Innovative Technology Evaluation) Emerging Technology Program. Allis Mineral Systems has developed the Thermal Encapsulation Process. Metals with limits set by EPA’s TCLP (Toxicity Characteristic Leaching Procedure) test and BIF (boiler and industrial furnace) stack emission regulations, such as cadmium, chromium, and lead, are the initial target of this process. This process, while unproven in these areas, may also apply to mixed waste (EPA hazardous waste/low-level radioactive wastes) and may also benefit commercial hazardous waste or Superfund thermal treatment systems. The results of the SITE tests were positive: strong, durable nodules were produced with excellent crush strength and improved resistance to leaching. Feed preparation, particularly control of moisture content, was found to be a key element in initiation of agglomeration. A good correlation was found between decreasing TCLP metals leachate levels and increasing crush strength.     

Validation of the Digital Opacity Compliance System under Regulatory Enforcement Conditions

Abstract

U.S. Environmental Protection Agency (EPA) Emission Measurement Center in conjunction with EPA Regions VI and VIII, the state of Utah, and the U.S. Department of Defense have conducted a series of long-term pilot and field tests to determine the accuracy and reliability of a visible opacity monitoring system consisting of a conventional digital camera and a separate computer software application for plume opacity determination. This technology, known as the Digital Opacity Compliance System (DOCS), has been successfully demonstrated at EPA-sponsored Method-9 “smoke schools,” as well as at a number of government and commercially operated industrial facilities.

Results from the current DOCS regulatory pilot study demonstrated that, under regulatory enforcement conditions, the average difference in opacity measurement between the DOCS technology and EPA Reference Method 9 (Method 9) was 1.12%. This opacity difference, which was computed from the evaluation of 241 regulated air sources, was found to be statistically significant at the 99% confidence level. In evaluating only those sources for which a nonzero visible opacity level was recorded, the average difference in opacity measurement between the DOCS technology and Method 9 was 1.20%. These results suggest that the two opacity measurement methods are essentially equivalent when measuring the opacity of visible emissions.

Given the costs and technical limitations associated with use of Method 9, there is a recognized need to develop accurate, reproducible, and scientifically defensible alternatives to the use of human observers. The use of digital imaging/processing brings current technology to bear on this important regulatory issue. Digital technology offers increased accuracy, a permanent record of measurement events, lower costs, and a scientifically defensible approach for opacity determination.     

Mutagenicity evaluation of chemical pesticides

Abstract

Over the last few decades, the use of chemical pesticides has increased dramatically in the U.S. This relatively sudden increase greatly concerns the U.S. Environmental Protection Agency (EPA), since it has the responsibility for ensuring the safety of all pesticides used in the U.S. In response to this concern, EPA has established a review program, the Rebuttable Presumption Against Registration (RPAR), for periodically reassessing the mutagenic and carcinogenic potential of pesticide compounds.

This paper presents a review and evaluation of the data reported in the literature on six chemical pesticides suspect for mutagenic potential. The pesticide chemicals discussed are maleic hydrazide; rotenone; monuron; diallate; triallate, and benomyl.     

A Simple Methodology for the Determination of Back Trajectories

Abstract

This study comprehensively characterizes hourly fine particulate matter (PM_2.5) concentrations measured via a tapered element oscillating microbalance (TEOM), β-gauge, and nephelometer from four different monitoring sites in U.S. Environment Protection Agency (EPA) Region 5 (in U.S. states Illinois, Michigan, and Wisconsin) and compares them to the Federal Reference Method (FRM). Hourly characterization uses time series and autocorrelation. Hourly data are compared with FRM by averaging across 24-hr sampling periods and modeling against respective daily FRM concentrations. Modeling uses traditional two-variable linear least-squares regression as well as innovative nonlinear regression involving additional meteorological variables such as temperature and humidity. The TEOM shows a relationship with season and temperature, linear correlation as low as 0.7924 and nonlinear model correlation as high as 0.9370 when modeled with temperature. The β-gauge shows no relationship with season or meteorological variables. It exhibits a linear correlation as low as 0.8505 with the FRM and a nonlinear model correlation as high as 0.9339 when modeled with humidity. The nephelometer shows no relationship with season or temperature but a strong relationship with humidity is observed. A linear correlation as low as 0.3050 and a nonlinear model correlation as high as 0.9508 is observed when modeled with humidity. Nonlinear models have higher correlation than linear models applied to the same dataset. This correlation difference is not always substantial, which may introduce a tradeoff between simplicity of model and degree of statistical association. This project shows that continuous monitor technology produces valid PM_2.5 characterization, with at least partial accounting for variations in concentration from gravimetric reference monitors once appropriate nonlinear adjustments are applied. Although only one regression technically meets new EPA National Ambient Air Quality Standards (NAAQS) Federal Equivalent Method (FEM) correlation coefficient criteria, several others are extremely close, showing optimistic potential for use of this nonlinear adjustment model in garnering EPA NAAQS FEM approval for continuous PM_2.5 sampling methods.     

Air Pollution Control Measures for Hot Dip Galvanizing Kettles

ABSTRACT

Three commercially available conversion varnish coating “systems” (stain, sealer, and topcoat) were selected for an initial scoping study. The total volatile content of the catalyzed varnishes, as determined by U.S. Environmental Protection Agency (EPA) Method 24, ranged from 64 to 73 weight%. Uncombined (free) formaldehyde concentrations, determined by a sodium sulfite titration method, ranged from 0.15 to 0.58 weight% of the uncatalyzed varnishes. Each sealer and topcoat was also analyzed by gas chromatography (EPA Method 311). The primary volatile organic constituents included methyl ethyl ketone (MEK), isobutanol, n-butanol, methyl isobutyl ketone (MIBK), toluene, ethylbenzene, the xylenes, and 1,2,4-trimethylbenzene.     

Near-Field Dispersion Modeling for Regulatory Applications

Abstract

This paper evaluates the application of dispersion models to estimate near-field pollutant concentrations in two case studies. The Industrial Source Complex Short-Term Model (ISCST3) was evaluated with hexavalent chromium measurements collected within 100 m of two facilities in Barrio Logan, San Diego, CA. ISCST3 provided reasonable estimates for higher pollutant concentrations but underestimated lower concentrations. To understand the observed distribution of concentrations in Barrio Logan, a recently conducted tracer experiment was analyzed. The tracer, sulfur hexafluoride, was released at ambient temperature from an urban facility at the University of California at Riverside, and concentrations were measured within 20 m of the source. Modeling results indicated that Industrial Source Complex–Plume Rise Model Enhancement and American Meteorological Society/U.S. Environmental Protection Agency Regulatory Model–Plume Rise Model Enhancement overestimated high concentrations and underestimated low concentrations. A diagnostic study with a simple Gaussian dispersion model that incorporated site-specific meteorology was used to evaluate model results. This study found that incorporating lateral meandering for nonbuoyant urban plumes in Gaussian dispersion models could improve concentration estimates even when downwash is not considered. Incorporating a meandering component in ISCST3 resulted in improvements in estimating hexavalent chromium concentrations in Barrio Logan. Credible near-source concentration estimates depend on accurate characterization of emissions, onsite micrometeorology, and a method to account for lateral meandering in the near field.     

Potential Air Emission Impacts of Cellulosic Ethanol Production at Seven Demonstration Refineries in the United States

Abstract

This paper reports on the estimated potential air emissions, as found in air permits and supporting documentation, for seven of the first group of precommercial or “demonstration” cellulosic ethanol refineries (7CEDF) currently operating or planning to operate in the United States in the near future. These seven refineries are designed to produce from 330,000 to 100 million gal of ethanol per year. The overall average estimated air emission rates for criteria, hazardous, and greenhouse gas pollutants at the 7CEDF are shown here in terms of tons per year and pounds per gallon of ethanol produced. Water use rates estimated for the cellulosic ethanol refineries are also noted. The air emissions are then compared with similar estimates from a U.S. cellulosic ethanol pilot plant, a commercial Canadian cellulosic ethanol refinery, four commercial U.S. corn ethanol refineries, and U.S. petroleum refineries producing gasoline. The U.S. Environmental Protection Agency (EPA) air pollution rules that may apply to cellulosic ethanol refineries are also discussed. Using the lowest estimated emission rates from these cellulosic ethanol demonstration facilities to project air emissions, EPA’s major source thresholds for criteria and hazardous air pollutants might not be exceeded by cellulosic ethanol refineries that produce as high as 25 million gal per year of ethanol (95 ML). Emissions are expected to decrease at cellulosic ethanol refineries as the process matures and becomes more commercially viable.     

Removal of PCBs from a Contaminated Soil Using CF-Systems® Solvent Extraction Process

ABSTRACT

The U.S. Environmental Protection Agency’s (EPA) Superfund Technical Assistance Response Team (START) in cooperation with EPA’s Superfund Innovative Technology Evaluation (SITE) program evaluated a pilot scale solvent extraction process developed by CF-Systems. This process uses liquefied propane to extract organic contaminants from soils, sludges, and sediments. A pilot-scale evaluation was conducted in Golden, CO at Hazen Research, Inc., using CF-Systems’ trailer-mounted organics extraction unit. Approximately 1,000 pounds of soil, with an average poly-chlorinated biphenyl (PCB) concentration of 260 mg/kg, was obtained from a remote Superfund site. Six 100-pound batches of the contaminated soil were extracted using multiple extraction sequences. Three of the six batch runs were subjected to three extraction sequences each, so that process variability could be evaluated. Results showed that PCB removal efficiencies varied between 91.4 and 99.4%, with the propane-extracted soils retaining low concentrations of PCBs (19.0–1.8 mg/kg). Removal efficiencies of oil and grease (O&G) were found to be 96.0 to 99.6% with propane-extracted soils retaining O&G concentrations from 279 to <20 mg/kg. Overall extraction efficiency was found to be dependant upon the numberof extraction cycles used.     

Thermal Immobilization of Lead Contaminants in Soils Treated in a Fixed- and Fluidized-Bed Incinerator at Moderate Temperatures

Abstract

Artificially lead-contaminated soils with different lead contents (200, 450, 600, and 900 ppm) were thermally immobilized in both fixed-bed and fluidized-bed modes at moderate treating temperatures (less than 500 °C) for various retention times. Cement powder and brick powder were added to the artificially contaminated soils to enhance lead immobilization. Results indicate that increasing treating temperature and time increases the extent of lead immobilization, as determined by the U.S. Environmental Protection Agency's (U.S. EPA) Toxicity Characteristics Leachability Procedure (TCLP). The percentage of lead leached from the soil/ cement mixtures was in the range of less than 0.251%, compared with the range between 13.6% and 40.7% for the corresponding soil/brick mixtures. As the amount of brick dust added to the Pb-doped soil was increased, the specific Pb immobilization effectiveness increased from 0.0675 to 0.149 mg Pb/g brick (for the 20- and 50-gram brick addition, respectively). An increase in air flow rate from 2 to 40 L/min caused a slight decrease in the Pb leaching percentage from 14.96% to 11.59%. Both the Freundlich and Langmuir isotherms give a satisfactory fit (r = 0.945 ~ 0.998) for the data derived from a TCLP test of the thermally-treated soil samples (105 °C and 500 °C) that contained lead contaminants. Sorption of lead contaminants in soil and sorbent matrices was the primary type of chemisorption. The kinetic results indicated that the Pb-doped soil system was too complicated to be described by a simple calculation.     

Source Apportionment of PM10 and PM25 in Five Chilean Cities Using Factor Analysis

ABSTRACT

Chile is a fast-growing country with important industrial activities near urban areas. In this study, the mass and elemental concentrations of PM₁₀ and PM_2.5 were measured in five major Chilean urban areas. Samples of particles with diameter less than 10 um (PM₁₀) and 2.5 um (PM_2.5) were collected in 1998 in Iquique (northern Chile), Valparaiso, Vina del Mar, Rancagua (central Chile), and Temuco (southern Chile). Both PM₁₀ and PM₂₅ annual mean concentrations (PM₁₀: 56.9-77.6 u,g/m³; PM₂₅: 22.4-42.6 u.g/m³) were significantly higher than the corresponding European Union (EU) and U.S. Environmental Protection Agency (EPA) air quality standards. Moreover, the 24-hr PM₁₀ and PM₂₅ U.S. standards were exceeded infrequently for some of the cities (Rancagua and Valparaiso).     

1992 Update of U.S. EPA’s Superfund Innovative Technology Evaluation (SITE) Emerging Technology Program

The Superfund Innovative Technology Evaluation (SITE) Emerging Technology Program (ETP) has encouraged and financially supported further development of bench- and pilot-scale testing and evaluation of innovative technologies suitable for use at hazardous waste sites for five years. The ETP was established under the Superfund Amendments and Reauthorization Act (SARA) of 1986. The ETP complies with the goal of the SITE Program to promote, accelerate and make commercially available the development ofalternative /innovative treatment technologies for use at Superfund sites.

Technologies are submitted to the ETP through yearly solicitations for Preproposals. Following a technical review, chosen applicants are asked to submit a detailed project proposal and a cooperative agreement application that requires Developer I EPA cost sharing. EPA co-funds selected Developers for one to two years. Second-year funding requires documentation of significant progress during the first year. Facilities, equipment, data collection, performance and development are monitored throughout the project. The U. S. Department of Energy (DOE) and the U. S. Air Force (USAF) are participants in the ETP. DOE has co-funded ETP projects since 1990 and the USAF since 1991.

A primary goal of the ETP is to move developed technologies to the field-demonstration stage. Therefore, a developer may be considered for participation in the SITE Demonstration Program provided performance in the ETP indicates the technology is field-ready for demonstration and evaluation.

Six technology categories: biological, chemical, materials handling, physical, solidification/ stabilization and thermal, are presently in the ETP.

Technologies of primary interest to EPA are those that can treat complex mixtures of hazardous organic and inorganic contaminants and provide improved solids handling and/orpretreatment.

An account of the background and progress of the ETP’s first five years is presented in this paper. Technologies currently in the ETP, including those selected from the fifth (EOS) solicitation, are noted, and developers, along with EPA Project Managers, are listed.     

Multiple-year black carbon measurements and source apportionment using Delta-C in Rochester,New York

Black carbon (BC), an important component of the atmospheric aerosol, has climatic, environmental, and human health significance. In this study, BC was continuously measured using a two-wavelength aethalometer (370 nm and 880 nm) in Rochester, New York, from January 2007 to December 2010. The monitoring site is adjacent to two major urban highways (I-490 and I-590), where 14% to 21% of the total traffic was heavy-duty diesel vehicles. The annual average BC concentrations were 0.76 μg/m³, 0.67 μg/m³, 0.60 μg/m³, and 0.52 μg/m³ in 2007, 2008, 2009, and 2010, respectively. Positive matrix factorization (PMF) modeling was performed using PM_2.5 elements, sulfate, nitrate, ammonia, elemental carbon (EC), and organic carbon (OC) data from the U.S. Environmental Protection Agency (EPA) speciation network and Delta-C (UVBC_370nm – BC_880nm) data. Delta-C has been previously shown to be a tracer of wood combustion factor. It was used as an input variable in source apportionment models for the first time in this study and was found to play an important role in separating traffic (especially diesel) emissions from wood combustion emissions. The result showed the annual average PM_2.5 concentrations apportioned to diesel emissions in 2007, 2008, 2009, and 2010 were 1.34 μg/m³, 1.25 μg/m³, 1.13 μg/m³, and 0.97 μg/m³, respectively. The BC conditional probability function (CPF) plots show a large contribution from the highway diesel traffic to elevated BC concentrations. The measurements and modeling results suggest an impact of the U.S Environmental Protection Agency (EPA) 2007 Heavy-Duty Highway Rule on the decrease of BC and PM_2.5 concentrations during the study period.

Implications: This study suggests that there was an observable impact of the U.S EPA 2007 Heavy-Duty Highway Rule on the ambient black carbon concentrations in Rochester, New York. Aethalometer Delta-C was used as an input variable in source apportionment models and it allowed the separation of traffic (especially diesel) emissions from wood combustion emissions.     

Empirical Evaluation of Ambient Ozone Interpolation Procedures to Support Exposure Models

ABSTRACT

An intercomparison study has been performed with six empirical ozone interpolation procedures to predict hourly concentrations in ambient air between monitoring stations. The objective of the study is to use monitoring network data to empirically identify an improved procedure to estimate ozone concentrations at subject exposure points. Four of the procedures in the study are currently used in human exposure models (nearest monitors daily mean and maximum, regression estimate used in the U.S. Environmental Protection Agency's (EPA) pNEM, and inverse distance weighting), and two are being evaluated for this purpose (kriging in space and kriging in space and time). The study focused on spatial estimation during June 1-June 5, 1996, with relatively high observed ozone levels over Houston, Texas. The study evaluated these procedures at three types of locations with monitors of varying proximity. Results from the empirical evaluation indicate that kriging in space and time provides excellent estimates of ozone concentrations within a monitoring network, while the more often used techniques failed to capture observed pollutant concentrations. Improved estimation of pollutant concentrations within the region, and thus at subject locations, should result in improved exposure modeling.     

Fluldized-Bed Combustion

The Fourth International Conference on Fluidized Bed Combustion (FBC) was held at The MITRE Corporation in McLean, VA, December 9 to 11, 1975. With attendees from Great Britain, West Germany, Japan, Canada, and Sweden, the conference apparently fulfilled its international scope and intent.

The objectives of the conference were to review the current state of technology in FBC, to promote technical information exchange on FBC and related areas, and to generate a useful technical information base for further FBC development. Throughout the conference, the goal of commercialization was repeatedly emphasized.

Sponsored by the U.S. Energy Research and Development Administration (ERDA) and coordinated by MITRE, this meeting was the most comprehensive event in the seven year series of conferences on this subject according to attendees. ERDA, the government’s lead agency in FBC technology development, is the principal sponsor and coordinator of the National Fluidized Bed Combustion Program with the goal of advancing the commercialization time frame for FBC. Prior conferences in this series were hosted by the Environmental Protection Agency (EPA) at about two year intervals at Hueston Woods, Ohio. The last EPA conference was held in October 1972.     

Mercury Measurement and Its Control: What We Know,Have Learned,and Need to Further Investigate

ABSTRACT

Based on the available evidence of health effects, the U.S. Environmental Protection Agency (EPA) has been evaluating the need to regulate mercury releases to the environment. In response to the congressional mandates in The 1990 Clean Air Act Amendments (CAAA), the EPA has issued the Mercury Study Report and the Study of Hazardous Air Pollutant Emissions from Electric Utility Steam Generating Units Report. In spite of the enormous effort represented by these reports, as well as the efforts of both the U.S. Department of Energy (DOE) and the Electric Power Research Institute (EPRI), in conducting the field measurement programs that form the basis for these reports, a definitive answer on the need for mercury regulation has not been found. However, the EPA, as well as other regulatory agencies and health researchers, have suggested a “plausible link” between anthropogenic sources emitting mercury and the methylation, bioaccumulation in the food chain, and adverse health effects in humans and wildlife.

Policy-makers have recognized that regulations must be based on good science and that a number of issues still remain. These issues can generally be grouped into four main categories: emissions inventory, control technology, fate of releases, and health effects. This paper will discuss recent, ongoing, and planned studies to address the remaining issues regarding the presence of mercury in the environment, with an emphasis on those studies that are directly related to the DOE/Federal Energy Technology Center’s (FETC) programmatic effort.     

Mercury Measurement and Its Control: What We Know,Have Learned,and Need to Further Investigate

ABSTRACT

Based on the available evidence of health effects, the U.S. Environmental Protection Agency (EPA) has been evaluating the need to regulate mercury releases to the environment. In response to the congressional mandates in The 1990 Clean Air Act Amendments (CAAA), the EPA has issued the Mercury Study Report and the Study of Hazardous Air Pollutant Emissions from Electric Utility Steam Generating Units Report. In spite of the enormous effort represented by these reports, as well as the efforts of both the U.S. Department of Energy (DOE) and the Electric Power Research Institute (EPRI), in conducting the field measurement programs that form the basis for these reports, a definitive answer on the need for mercury regulation has not been found. However, the EPA, as well as other regulatory agencies and health researchers, have suggested a "plausible link" between anthropogenic sources emitting mercury and the methylation, bioaccumulation in the food chain, and adverse health effects in humans and wildlife.     

Mercury Emissions from a Hazardous Waste Incinerator Equipped with a State-of-the-Art Wet Scrubber

Abstract

Over a six-week period, eleven tests were performed at the U.S. EPA Incineration Research Facility (IRF) in Jefferson, Arkansas to evaluate the fate of trace metals fed to a rotary kiln incinerator equipped with a Calvert Flux-Forcer/Condensation Scrubber pilot plant as the primary air pollution control system (APCS). Test variables were kiln temperature, ranging from 538 °C to 927 °C; waste feed chlorine content, ranging from 0% to 3.4%; and scrubber pressure drop, ranging from 8.2 kPa to 16.9 kPa. Mercury was among the six hazardous constituent trace metals fed to the IRF’s pilotscale rotary kiln incineration system as part of a synthetic waste feed. This paper focuses on the test results solely with respect to mercury.

As expected, mercury behaved as a very volatile metal throughout the tests; it was not detected in any kiln ash samples. Scrubber collection efficiency for mercury ranged from 67% to >99%, averaging 87%; this was somewhat lower than expected and may be attributable to low scrubber loadings.

The ability to collect and analyze representative scrubber water samples appears to have been affected by the waste feed chlorine content; detection of mercury at higher concentrations during high waste-chlorine-content tests is thought to be largely the result of the formation of mercuric chloride, a more water-soluble species, during those tests. As a result, no firm conclusions may be drawn regarding the true impact of waste feed chlorine content on mercury partitioning to the scrubber water. As expected, no significant relationship was observed between kiln exit-gas temperature and mercury partitioning, nor was there a significant relationship with scrubber pressure drop.     

Interlaboratory Study of a Test Method Measuring Total Volatile Organic Compound Content of Consumer Products

Abstract

Consumer products are potentially significant sources of volatile organic compounds (VOCs), which are precursors to the formation of ozone in photochemical smog. To address the problem of ozone formation in ambient air, the U.S. Environmental Protection Agency (EPA) has been involved in the development of test methods for measuring the VOC content of consumer products. This paper describes results of an interlaboratory study to estimate the repeatability (precision of analyses performed by a single laboratory) and reproducibility (precision of analyses performed by different laboratories) of the consumer products’ VOC measurement method based on EPA Method 24 (for VOCs in surface coatings).

The mean method repeatability was 2.7 wt % VOC, and the mean method reproducibility was 4.8 wt % VOC. Method repeatability ranged from 0.2 to 4.4 wt % VOC, and reproducibility ranged from 0.6 to 11.9 weight percent VOC. The precision of the VOC method for consumer

products is similar to the precision of EPA Method 24 for surface coatings.     

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.