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.     

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.     

Aerosol Filtration by Sorbent Beds

Fixed beds of sorbent media are used for the evaluation of poiynuclear aromatic hydrocarbons (PAH) present in air. Twostage sampling and separate extraction and analyses of PAH associated with aerosol particles and those present in the vapor state are usually performed. The ability of commonly used sorbents to retain particulate matter introduces a potential for reducing the time and cost of PAH evaluation procedures.

The filtration efficiency of three sorbent media, Florisil, XAD-2, and polyurethanefoam (PUF), for particles in 0.1 to 1 µm size range was studied using airflow rates from 4 to 2501 /mm through a PS 1 sorbent cartridge. Theoretical considerations were used to identify the principal filtration mechanisms and to assess the predictability of the aerosol filtration performance of sorbent filters. The results of this study indicate XAD-2 to be an efficient filtration medium owing to the electrostatic enhancement of capturing and retaining aerosol particles.

As a result of theoretical considerations, Brownian diffusion and inertial deposition were found to be major filtration mechanisms accompanied by electrostatic effects. While the efficiency of the diffusional deposition mechanism was reasonably well predicted with available theories, modeling of submicron particle impaction at higher fluid velocities appeared to be inadequate. Further developments are suggested to improve our understanding of filtration phenomena in sorbent beds under high flow rate conditions.     

The Emissions and Dispersion Modeling System (EDMS): Its Development and Application at Airports and Airbases

A new complex source microcomputer model has been developed for use at civil airports and Air Force bases. This paper describes both the key features of this model and its application in evaluating the air quality impact of new construction projects at three airports: one in the United States and two in Canada.

The single EDMS model replaces the numerous models previously required to assess the air quality impact of pollution sources at airports. EDMS also employs a commercial data base to reduce the time and manpower required to accurately assess and document the air quality impact of airfield operations.

On July 20, 1993, the U.S. Environmental Protection Agency (EPA) issued the final rule (Federal Register, 7/20/93, page 38816) to add new models to the Guideline on Air Quality Models. At that time EDMS was incorporated into the Guideline as an Appendix A model.     

Characterization of summertime coarse particulate matter in the Desert Southwest—Arizona,USA

A year-long study was conducted in Pinal County, AZ, to characterize coarse (2.5 – 10 μm aerodynamic diameter, AD) and fine (< 2.5 μm AD) particulate matter (PMc and PMf, respectively) to further understand spatial and temporal variations in ambient PM concentrations and composition in rural, arid environments. Measurements of PMc and PMf mass, ions, elements, and carbon concentrations at one-in-six day resolution were obtained at three sites within the region. Results from the summer of 2009 and specifically the local monsoon period are presented.

The summer monsoon season (July – September) and associated rain and/or high wind events, has historically had the largest number of PM₁₀ NAAQS exceedances within a year. Rain events served to clean the atmosphere, decreasing PMc concentrations resulting in a more uniform spatial gradient among the sites. The monsoon period also is characterized by high wind events, increasing PMc mass concentrations, possibly due to increased local wind-driven soil erosion or transport. Two PM₁₀ NAAQS exceedances at the urban monitoring site were explained by high wind events and can likely be excluded from PM₁₀ compliance calculations as exceptional events. At the more rural Cowtown site, PM₁₀ NAAQS exceedances were more frequent, likely due to the impact from local dust sources.

PM mass concentrations at the Cowtown site were typically higher than at the Pinal County Housing and Casa Grande sites. Crustal material was equal to 52-63% of the PMc mass concentration on average. High concentrations of phosphate and organic carbon found at the rural Cowtown were associated with local cattle feeding operations. A relatively high correlation between PMc and PMf (R²?=?0.63) indicated that the lower tail of the coarse particle fraction often impacts the fine particle fraction, increasing the PMf concentrations. Therefore, reductions in PMc sources will likely also reduce PMf concentrations, which also are near the value of the 24-hr PM_2.5 NAAQS.

Implications: In the desert southwest, summer monsoons are often associated with above average PM₁₀ (<10 μm AD) mass concentrations. Competing influences of monsoon rain and wind events showed that rain suppresses ambient concentrations while high wind increase them. In this region, the PMc fraction dominates PM₁₀ and crustal sources contribute 52-63% to local PMc mass concentrations on average. Cattle feedlot emissions are also an important source and a unique chemical signature was identified for this source. Observations suggest monsoon wind events alone cannot explain PM₁₀ NAAQS exceedances, thus requiring these values to remain in compliance calculations rather than being removed as exceptional wind events.     

Aerosol species concentrations and source apportionment of ammonia at Rocky Mountain National Park

Changes in ecosystem function at Rocky Mountain National Park (RMNP) are occurring because of emissions of nitrogen and sulfate species along the Front Range of the Colorado Rocky Mountains, as well as sources farther east and west. The nitrogen compounds include both oxidized and reduced nitrogen. A year-long monitoring program of various oxidized and reduced nitrogen species was initiated to better understand their origins as well as the complex chemistry occurring during transport from source to receptor. Specifically, the goals of the study were to characterize the atmospheric concentrations of nitrogen species in gaseous, particulate, and aqueous phases (precipitation and clouds) along the east and west sides of the Continental Divide; identify the relative contributions to atmospheric nitrogen species in RMNP from within and outside of the state of Colorado; identify the relative contributions to atmospheric nitrogen species in RMNP from emission sources along the Colorado Front Range versus other areas within Colorado; and identify the relative contributions to atmospheric nitrogen species from mobile sources, agricultural activities, and large and small point sources within the state of Colorado. Measured ammonia concentrations are combined with modeled releases of conservative tracers from ammonia source regions around the United States to apportion ammonia to its respective sources, using receptor modeling tools.

Implications: Increased deposition of nitrogen in RMNP has been demonstrated to contribute to a number of important ecosystem changes. The rate of deposition of nitrogen compounds in RMNP has crossed a crucial threshold called the “critical load.” This means that changes are occurring to park ecosystems and that these changes may soon reach a point where they are difficult or impossible to reverse. Several key issues need attention to develop an effective strategy for protecting park resources from adverse impacts of elevated nitrogen deposition. These include determining the importance of previously unquantified nitrogen inputs within the park and identification of important nitrogen sources and transport pathways.     

Age-dating Diesel Fuel Spills: Using the European Empirical Time-based Model in the U.S.A.

In 1993, a paper was published by Christensen and Larsen that offered a method for determining the age of diesel oil spills in soil (Christensen and Larsen, 1993 Ground Water Mount. R . Fall , 142-149). It presented an empirical time-based model of the degradation of diesel fuel in soils using chemical data gathered at petroleum release sites in Denmark and the Netherlands. Now, evaluation of the validity of the application of this work to subsurface petroleum releases in other countries remains. In the U.S.A., investigations assessing date(s) of release of diesel fuel in soils, e.g. age dating of subsurface petroleum contamination, have considerable interest. Litigation-driven scientific investigations with accompanying expert testimony in a court of law are underway. The number of instances where application of the Christensen and Larsen empirical time-based model to petroleum-contaminated properties is growing in the U.S.A. This paper presents two case studies which evaluate the applicability of the Christensen and Larsen empirical time-based model to petroleum-contaminated properties in general. It illustrates the approach using gas chromatographic data from two recently-completed projects evaluating the applicability of the Christensen and Larsen model to a No. 2 fuel oil/diesel fuel surface spill in the U.S.A. Results showed that the application of the model to petroleum-contaminated soils was scientifically valid, provided its applicability was evaluated using hypothesis testing for specific changes in the characteristics of the petroleum hydrocarbon distribution in a number of soil samples collected over time at one site. The paper offers observations on the application of the Christensen and Larsen model to petroleum found in the light non-aqueous phase liquid (LNAPL) phase and groundwater.     

Addressing climate change: Determinants of consumers' willingness to act and to support policy measures

Consumers influence climate change through their consumption patterns and their support or dismissal of climate mitigation policy measures. Both climate-friendly actions and policy support comprise a broad range of options, which vary in manifold ways and, therefore, might be influenced by different factors. The aims of the study were, therefore, two-fold: first, we intended to find a meaningful way to classify different ways of addressing climate change. Second, we aimed to examine which determinants influence people's willingness to engage in these behaviors. We conducted a large-scale mail survey in Switzerland in which respondents rated, among other items, their willingness to act or support a range of possible actions and mitigations measures. A principal component analysis indicated that a distinction in terms of a behavior's directness as well as a differentiation according to perceived costs seem to be appropriate to classify climate-friendly actions. Multiple regression analyses showed that perceived costs and perceived climate benefit turned out to be the strongest predictors for willingness to act or to support climate policy measures. The strong influence of perceived climate benefit might reflect a strategy of reducing cognitive dissonance. As high-cost behaviors are more difficult to adopt, consumers may reduce dissonance by dismissing high-cost behaviors as not effective in terms of climate mitigation. Political affiliation proved to be another strong determinant of willingness to act or support. Participants on the right wing were less willing to show indirect climate-friendly behaviors, change their mobility behaviors, and to support any type of climate mitigation policy measures. Climate-friendly low-cost behaviors, however, were not influenced by political affiliation.     

Sustainability and emerging issues in scholarly (self-)publishing

In American academic circles, peer-reviewed hard-copy book publishing remains a crucial part of the tenure and promotion process as well as a method of bestowing prestige upon authors accepted by university presses and other mainstream venues. Although a few respected individuals self-published as early as the seventeenth century, the emergence of desktop publishing during the 1980s led to hard-copy and virtual (self-)publishing venues of several kinds, including PDF formatting and the establishment of POD (print on demand) firms. Online, PDF, POD printing, and other challenges to traditional academic publishing can save money and improve efficiency as well as help sustain our forests and other natural resources.