Continuous Emissions Monitoring Using Spark-Induced Breakdown Spectroscopy

ABSTRACT

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

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

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.     

Static Leaching of Solidified/Stabilized Hazardous Waste from the Soliditech Process

WILT, ANS 16.1 and TCLP leach tests were performed on solidified/stabilized (s/s) wastes treated by Soliditech, Inc. of Houston, Texas as part of a U.S. EPA SITE demonstration project conducted in December 1988 at the Imperial Oil Company/ Champion Chemical Company Superfund site in Morganville, New Jersey. All three leaching tests performed on the s/s wastes indicated that the primary contaminants of concern (lead and PCBs) were not leachable. The ANS 16.1 static leach test for the s/s wastes provided diffusion coefficients (D_e) for Al, Ca, and Na that were comparable to those obtained from the WILT test. However, plots of the ANS 16.1 data indicated that wetting of the samples confounded the static leaching process. The large column WILT D_e was used to estimate that less than 0.8 μg/cm² lead would leach from a one-cubic yard block of s/s waste in contact with groundwater over a 60-month leaching period. This corresponds to concentrations less than 10 μg/L lead in the water contacting the block of s/s waste.     

Targeting lead in the multimedia environment in the continental United States

The U.S. Environmental Protection Agency's (EPA) lead attainment strategy for air is being expanded to address geographic areas with the potential for multimedia, multipathway exposures to lead. Geographic Information Systems (GIS) technology is used to coordinate information from various databases to identify areas of potential concern. The data retrieval and decision processes used in identifying priority sources from each medium and in evaluating identified areas of concern are described in this paper. Only EPA databases with reliable locational information were used to facilitate accurate mapping and allow correlation with other data sources. The sources of lead loadings to air, water, and soils were mapped using either latitude and longitude or zip code, or county centroids for data lacking longitudinal and latitudinal coordinates (such as the drinking water data). A multimedia cluster of lead sources was identified at the county level, since all the facility data in the five databases could be mapped to this level. An impact factor and weighting system was devised to combine the information on the number of facilities and their relative size in developing a ranking of the multimedia lead clusters of concern in each region. The counties with the highest number of points were considered clusters of highest concern for multimedia lead sources. Two separate lists of the clusters were developed according to a point system. One identified 10 multimedia lead clusters in each of the 10 EPA regions, and the other identified the 100 clusters of highest concern in the country as a whole. The project is designed to be a first step in targeting future efforts to identify potential environmental problems associated with lead. The analyses presented in this paper provide a first look at the areas in the country where there is a potential for multimedia exposure to lead. A more refined analysis at the zip code level was subsequently developed to provide a good understanding of the issues pertaining to potential exposure at the neighborhood level. The results of this analysis will ultimately help the EPA and the states to target implementation and enforcement in areas of high potential lead exposures.     

Impact of underestimating the effects of cold temperature on motor vehicle start emissions of air toxics in the United States

Analyses of U.S. Environmental Protection Agency (EPA) certification data, California Air Resources Board surveillance testing data, and EPA research testing data indicated that EPA's MOBILE6.2 emission factor model substantially underestimates emissions of gaseous air toxics occurring during vehicle starts at cold temperatures for light-duty vehicles and trucks meeting EPA Tier 1 and later standards. An unofficial version of the MOBILE6.2 model was created to account for these underestimates. When this unofficial version of the model was used to project emissions into the future, emissions increased by almost 100% by calendar year 2030, and estimated modeled ambient air toxics concentrations increased by 6-84%, depending on the pollutant. To address these elevated emissions, EPA recently finalized standards requiring reductions of emissions when engines start at cold temperatures.     

Validation of the digital opacity compliance system under regulatory enforcement conditions

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     

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.     

Correction methods for organic carbon artifacts when using quartz-fiber filters in large particulate matter monitoring networks: the regression method and other options

Sampling and handling artifacts can bias filter-based measurements of particulate organic carbon (OC). Several measurement-based methods for OC artifact reduction and/or estimation are currently used in research-grade field studies. OC frequently is not artifact-corrected in large routine sampling networks (e.g., U.S. Environmental Protection Agency (EPA)'s Chemical Speciation Network). In some cases, the OC artifact has been corrected using a regression method (RM) for artifact estimation. In this method, the gamma-intercept of the regression of the OC concentration on the fine particle (PM2.5) mass concentration is taken to be an estimate of the average OC sampling artifact (net of positive and negative artifacts). This paper discusses options for artifact correction in large routine sampling networks. Specifically, the goals are to (1) articulate the assumptions and limitations inherent to the RM, (2) describe other artifact correction approaches, and (3) suggest a cost-effective method for artifact correction in large monitoring networks. The RM assumes a linear relationship between measured OC and PM mass: a constant slope (OC mass fraction) and a constant intercept (RM artifact estimate). These assumptions are not always valid. Additionally, outliers and other individual data points can have a large influence on the RM artifact estimates. The RM yields results within the range of measurement-based methods for some datasets and not for others. Given that the adsorption of organic gases increases with atmospheric concentrations of organics, subtraction of an average artifact from all samples (e.g., across multiple sites) will underestimate OC for lower-concentration samples (e.g., clean sites) and overestimate OC for higher-concentration samples (e.g., polluted sites). For relatively accurate, simple, and cost-effective artifact OC estimation in large networks, the authors suggest backup filter sampling on at least 10% of sampling days at all sites with artifact correction on a sample-by-sample basis as described herein.     

Use of a general toxicity test to predict heavy metal concentrations in residential soils

Significant clusters of developmental delay and mental retardation (DD/MR) were identified in children born in South Carolina. Although it is difficult to identify one factor that causes DD/MR, environmental insult including exposure of pregnant women to heavy metals can induce DD/MR in their children. Because it is expensive to measure the concentrations of individual metals in large numbers of environmental samples, the general Microtox toxicity test was used to identify highly toxic soil samples. Approximately 100 soil samples were collected from residential areas and analyzed to determine an effective concentration (EC(50)) of soil required to inhibit 50% light emission of the luminescent bacterial test organism (Vibrio fischeri). The EC(50) values were then transformed to relative toxicity units (RTU). A subset of 56 high and low toxicity soil samples was then analyzed by inductively coupled plasma-atomic emission spectrometry (EPA method 6010) for arsenic, lead, and chromium, which are known neurotoxins. The highest measured arsenic concentration was 30 times higher than the South Carolina residential soil limit. Significant correlations were found between the RTU and soil arsenic and chromium concentrations. Microtox also identified some low arsenic and chromium samples as toxic, presumably because additional unidentified toxicants were present in the soil. In general, however, the Microtox test was effective in identifying soils with elevated concentrations of arsenic and chromium, even in residential neighborhoods where limited soil toxicity was expected.     

Bioleaching of zinc and copper from anaerobically digested swine manure: effect of sulfur levels and solids contents.

Anaerobically digested swine manure (ADSM) generally contains high concentrations of zinc (Zn) and copper (Cu). These metals levels exceed the land application regulations of municipal biosolids of many European countries and are on the borderline of exceptional quality in the U.S. Environmental Protection Agency (U.S. EPA) 40 CFR part 503 standards. From this perspective, a series of batch tests were conducted to evaluate the feasibility of bioleaching of Zn and Cu from ADSM so that the produced biosolids could safely be applied to land. The effect of different substrate levels (sulfur) and total solids content (as high as 9%) on metal solubilization was investigated. The results showed that metal solubilization efficiency for both Zn and Cu declined significantly with an increase in total solids from 3 to 6% and then to 9% at the same substrate level. Metal solubilization increased proportionately with increases in substrate concentration up to 6% of total solids content. However, at 9% total solids content, metal solubilization was insignificant at all substrate levels tested. At a 6% total solids level and 10 000 mg/L of substrate, 94% of Zn and 72% of Cu were solubilized. Bioleaching was also found to be effective in destruction of pathogens with approximately 2.5 log-scale reduction. The residual biosolid was found to meet the Class A biosolids standands of U.S. EPA 40 CFR part 503.     

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.     

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.     

Biosolids-amended soils: Part II. Chemical lability as a measure of contaminant bioaccessability.

Biosolids recycling by amending agricultural soils has increased significantly over the last few decades. The presence of contaminants in small, bioavailable quantities has generated concerns about health threats resulting from accumulation of potential toxins in the food chain. In this study, land application of biosolids was evaluated for environmental risk. Chemical lability tests for metals were used for the test soils and included analyses for water soluble, exchangeable, and metals extractable by the physiologically based extraction test. Chemical extractions detected slight increases in labile metal concentrations for many of the treated soils, particularly those receiving long-term applications of 5 years or more. Significantly higher metal concentrations were observed in the soils that had been exposed to biosolids before the U.S. Environmental Protection Agency (Washington, D.C.) 503 Rule (U.S. EPA, 2004) was implemented.     

SITE Demonstration of the Basic Extractive Sludge Treatment Process

The Superfund Innovative Technology Evaluation (SITE) Program, in cooperation with EPA Region 5, the Great Lakes National Program Office (GLNPO), and the U.S. Army Corps of Engineers (COE) planned and executed a pilot-scale evaluation of the Basic Extractive Sludge Treatment (B.E.S.T.®) process on sediment samples obtained from the Grand Calumet River in Gary, Indiana. Two separate sampling locations were selected based upon previous data. One location had sediments with total polychlorinated biphenyl (PCB) concentrations averaging 10 mg/kg, and total polynuclear aromatic hydrocarbon (PAH) concentrations averaging 520 mg/kg. The other location had sediments with average total PCB and PAH concentrations of 427 mg/kg and 72,000 mg/kg, respectively. The sediment samples were segregated by location, then screened, homogenized, and stored prior to treatment. A total of ten batches of sediments were treated (five for each sample location).

Results showed that of the samples which had low original contaminants concentrations, 96 percent of the PAHs and >99 percent of the PCBs were removed following seven sequential extractions. Treated samples which had high original contaminant concentrations were found to have removal efficiencies of >99 percentfor both PAHs and PCBs. Costs for applying this technology were estimated at $94.19/ton (assuming the system is on-line 80 percent of the time) excluding fixed costs associated with system mobilization/ demobilization and setup, and profit.     

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.     

A Comparison of Two Techniques for the Collection and Analysis of Polynuclear Aromatic Compounds in Ambient Air

A demonstration of the GHEMFIX solidification/stabilization process was conducted under the United States Environmental Protection Agency’s (EPA) Superfund Innovative Technology Evaluation (SITE) program. The demonstration was conducted in March 1989, at the Portable Equipment Salvage Company (PESC) uncontrolled hazardous waste site in Clackamas, Oregon. Waste containing lead, copper, and polychlorinated biphenyls (PCBs) from four different areas of the site were treated. Results showed substantial reduction of leachable lead and copper between the untreated waste and treated waste utilizing the EPA Toxicity Characteristics Leaching Procedure (TCLP) test. The effectiveness of this process for immobilizing PCBs could not be determined since the raw waste did not leach PCBs at high concentrations, utilizing the TCLP test. Data from other leaching tests for lead and copper would need to be utilized as input into a site specific groundwater model to determine whether solidification/stabilization would be an acceptable remedy for the site. Physical testing results indicated durability in exposed conditions.     

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.     

Near-field dispersion modeling for regulatory applications

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.     

Issues with ozone attainment methodology for Houston, TX

To comply with the federal 8-hr ozone standard, the state of Texas is creating a plan for Houston that strictly follows the U.S. Environmental Protection Agency's (EPA) guidance for demonstrating attainment. EPA's attainment guidance methodology has several key assumptions that are demonstrated to not be completely appropriate for the unique observed ozone conditions found in Houston. Houston's ozone violations at monitoring sites are realized as gradual hour-to-hour increases in ozone concentrations, or by large hourly ozone increases that exceed up to 100 parts per billion/hr. Given the time profiles at the violating monitors and those of nearby monitors, these large increases appear to be associated with small parcels of spatially limited plumes of high ozone in a lower background of urban ozone. Some of these high ozone parcels and plumes have been linked to a combination of unique wind conditions and episodic hydrocarbon emission events from the Houston Ship Channel. However, the regulatory air quality model (AQM) does not predict these sharp ozone gradients. Instead, the AQM predicts gradual hourly increases with broad regions of high ozone covering the entire Houston urban core. The AQM model performance can be partly attributed to EPA attainment guidance that prescribes the removal in the baseline model simulation of any episodic hydrocarbon emissions, thereby potentially removing any nontypical causes of ozone exceedances. This paper shows that attainment of all monitors is achieved when days with observed large hourly variability in ozone concentrations are filtered from attainment metrics. Thus, the modeling and observational data support a second unique cause for how ozone is formed in Houston, and the current EPA methodology addresses only one of these two causes.     

Human health risk assessment of lead from mining activities at semi-arid locations in the context of total lead exposure

Lead from historical mining and mineral processing activities may pose potential human health risks if materials with high concentrations of bioavailable lead minerals are released to the environment. Since the Joint Expert Committee on Food Additives of Food and Agriculture Organization/World Health Organization withdrew the Provisional Tolerable Weekly Intake of lead in 2011, an alternative method was required for lead exposure assessment. This study evaluated the potential lead hazard to young children (0–7 years) from a historical mining location at a semi-arid area using the U.S. EPA Integrated Exposure Uptake Biokinetic (IEUBK) Model, with selected site-specific input data. This study assessed lead exposure via the inhalation pathway for children living in a location affected by lead mining activities and with specific reference to semi-arid conditions and made comparison with the ingestion pathway by using the physiologically based extraction test for gastro-intestinal simulation. Sensitivity analysis for major IEUBK input parameters was conducted. Three groups of input parameters were classified according to the results of predicted blood concentrations. The modelled lead absorption attributed to the inhalation route was lower than 2 % (mean?±?SE, 0.9 %?±?0.1 %) of all lead intake routes and was demonstrated as a less significant exposure pathway to children’s blood, compared with ingestion. Whilst dermal exposure was negligible, diet and ingestion of soil and dust were the dominant parameters in terms of children’s blood lead prediction. The exposure assessment identified the changing role of dietary intake when house lead loadings varied. Recommendations were also made to conduct comprehensive site-specific human health risk assessment in future studies of lead exposure under a semi-arid climate.