Low Concentration Mercury Sorption Mechanisms and Control by Calcium-Based Sorbents: Application in Coal-Fired Processes

ABSTRACT

The capture of elemental mercury (Hg⁰) and mercuric chloride (HgCl₂) by three types of calcium (Ca)-based sor-bents was examined in this bench-scale study under conditions prevalent in coal-fired utilities. Ca-based sorbent performances were compared with that of an activated carbon. Hg⁰ capture of about 40% (nearly half that of the activated carbon) was achieved by two of the Ca-based sorbents. The presence of sulfur dioxide (SO₂) in the simulated coal combustion flue gas enhanced the Hg⁰ capture from about 10 to 40%. Increasing the temperature in the range of 65-100 °C also caused an increase in the Hg⁰ capture by the two Ca-based sorbents. Mercuric chloride (HgCl₂) capture exhibited a totally different pattern. The presence of SO₂ inhibited the HgCl₂ capture by Ca-based sorbents from about 25 to less than 10%. Increasing the temperature in the studied range also caused a decrease in HgCl₂ capture. Upon further pilot-scale confirmations, the results obtained in this bench-scale study can be used to design and manufacture more cost-effective mercury sorbents to replace conventional sorbents already in use in mercury control.     

A Methodological Approach for Exposure Assessment Studies in Residences Using Volatile Organic-Compound-Contaminated Water

Abstract

This paper presents a methodological approach for assessing total exposures to volatile organic compounds (VOCs) in residences using contaminated water supplies. This approach is founded on assessment of ingestion, inhalation, and dermal exposures; both long-term (i.e., 12 to 24 hr) lowlevel exposures and short-term (i.e., =10 min) high-level exposures are considered.

The methodology is based on the collection of water samples to establish the identity of the contaminants, maximum source terms, and possible dermal and ingestion exposures; integrated whole-air samples are collected to assess long- and short-term inhalation exposures; whole-air grab samples are used to confirm peak and typical inhalation exposures; and alveolar breath samples are used to confirm exposures and to estimate contaminant concentrations in the blood of the test subjects. While we do not suggest that this methodology should supersede any current investigative approach, this material is primarily offered as a consolidated reference to the many people or organizations who might contemplate a study of this type. Application of this investigative protocol should provide detailed exposure assessment information, while it supplies critical real world data for risk assessment specialists, toxicologists, and modeling experts. Data from a recent field study assessing exposures to trichloroethylene are presented to illustrate the utility and some of the limitations of this strategy.     

Modeling of Solid Particle Flow and Heat Transfer in Rotary Kiln Calciners

Abstract

Contaminated solid wastes exist in many industrial sites, gas plants, and oil refineries. One method of decontaminating the soil is to subject it to high temperatures in a rotary calciner in an anaerobic environment. Preliminary results from a computational model are presented in this paper for the flow and heat transfer from granular solid particles under treatment in a rotary kiln calciner. A fluidization model using kinetic theory of granular flow has been employed to solve the particle flow and heat transfer problem. While a two-dimensional model is used to predict the rotation induced flow of the solid particles, a pseudo three-dimensional model for heat transfer is developed where the axial bulk temperature gradient is obtained from a one-dimensional energy balance model. The model predictions indicate interesting features of the flow and temperature fields in the bed material. Future tasks include the development of a devolatilization model to study the decontamination of waste soil in the rotary calciner.     

Comparison of Computer Simulations of Total Lung Deposition to Human Subject Data in Healthy Test Subjects

ABSTRACT

A mathematical model was used to predict the deposition fractions (DF) of PM within human lungs. Simulations using this computer model were previously validated with human subject data and were used as a control case. Human intersubject variation was accounted for by scaling the base lung morphology dimensions based on measured functional residual capacity (FRC) values. Simulations were performed for both controlled breathing (tidal volumes [V_T] of 500 and 1000 mL, respiratory times [T] from 2 to 8 sec) and spontaneous breathing conditions. Particle sizes ranged from 1 to 5 um. The deposition predicted from the computer model compared favorably with the experimental data. For example, when V_T = 1000 mL and T = 2 sec, the error was 1.5%. The errors were slightly higher for smaller tidal volumes. Because the computer model is deterministic (i.e., derived from first principles of physics), the model can be used to predict deposition fractions for a range of situations (i.e., for different ventilatory parameters and particle sizes) for which data are not available. Now that the model has been validated, it may be applied to risk assessment efforts to estimate the inhalation hazards of airborne pollutants.     

Development of a Sample Equilibration System for the TEOM Continuous PM Monitor

ABSTRACT

In recent years, scientific discussion has included the influence of thermodynamic conditions (e.g., temperature, relative humidity, and filter face velocity) on PM retention efficiency of filter-based samplers and monitors. Method-associated thermodynamic conditions can, in some instances, dramatically influence the presence of particle-bound water and other light-molecular-weight chemical components such as particulate nitrates and certain organic compounds. The measurement of fine particle mass presents a new challenge for all PM measurement methods, since a relatively greater fraction of the mass is semi-volatile.

The tapered element oscillating microbalance (TEOM) continuous PM monitor is a U.S. Environmental Protection Agency (EPA) PM₁₀ equivalent method (EQPM-1090-079). Several hundred of these monitors are deployed throughout the United States. The TEOM monitor has the unique characteristic of providing direct PM mass measurement without the calibration uncertainty inherent in mass surrogate methods. In addition, it provides high-precision, near-real-time continuous data automatically. Much attention has been given to semi-volatile species retention of the TEOM method.

While using this monitor, it is desirable to maintain as low an operating temperature as practical and to remove unwanted particle-bound water. A new sample equilibration system (SES) has been developed to allow conditioning of the PM sample stream to a lower humidity and temperature level. The SES incorporates a special low-particle-loss Nafion dryer. This paper discusses the configuration and theory of the SES. Performance results include high time-resolved PM_2.5 data comparison between a 30 °C sample stream TEOM monitor with SES and a standard 50 °C TEOM monitor. In addition, 24-hr integrated data are compared with data collected using an EPA PM_2.5 Federal Reference Method (FRM)-type sampler. The SES is a significant development because it can be applied easily to existing TEOM monitors.     

The 1999 Fresno Particulate Matter Exposure Studies: Comparison of Community,Outdoor, and Residential PM Mass Measurements

ABSTRACT

Two collaborative studies have been conducted by the U.S. Environmental Protection Agency (EPA) National Exposure Research Laboratory (NERL) and National Health and Environmental Effects Research Laboratory to determine personal exposures and physiological responses to par-ticulate matter (PM) of elderly persons living in a retirement facility in Fresno, CA. Measurements of PM and other criteria air pollutants were made inside selected individual residences within the retirement facility and at a central outdoor site on the premises. In addition, personal PM exposure monitoring was conducted for a subset of the participants, and ambient PM monitoring data were available for comparison from the NERL PM research monitoring platform in central Fresno. Both a winter (February 1-28, 1999) and a spring (April 19-May 16, 1999) study were completed so that seasonal effects could be     

Estimates of Particle Hygroscopicity during the Southeastern Aerosol and Visibility Study

ABSTRACT

Aerosol water content was determined from relative humidity controlled optical particle counter (ASASP-X) size distribution measurements made during the Southeastern Aerosol and Visibility Study (SEAVS) in the Great Smoky Mountains National Park during summer 1995. Since the scattering response function of the ASASP-X is sensitive to particle refractive index, a technique for calibrating the ASASP-X for any real refractive index was developed. A new iterative process was employed to calculate water mass concentration and wet refractive index as functions of relative humidity. Experimental water mass concentrations were compared to theoretically predicted values assuming only ammonium sulfate compounds were hygroscopic. These comparisons agreed within experimental uncertainty. Estimates of particle hygroscopicity using a rural aerosol model of refractive index as a function of relative humidity demonstrated no significant differences from those made with daily varying refractive index estimates. Although aerosol size parameters were affected by the assumed chemical composition, forming ratios of these parameters nearly canceled these effects.     

Supply Curves for Using Powder River Basin Coal to Reduce Sulfur Emissions

Abstract

Supply curves were prepared for coal-fired power plants in the contiguous United States switching to Wyoming's Powder River Basin (PRB) low-sulfur coal. Up to 625 plants, representing ～44% of the nameplate capacity of all coal-fired plants, could switch. If all switched, more than $8.8 billion additional capital would be required and the cost of electricity would increase by up to $5.9 billion per year, depending on levels of plant derating. Coal switching would result in sulfur dioxide (SO₂) emissions reduction of 4.5 million t/yr. Increase in cost of electricity would be in the range of 0.31-0.73 cents per kilowatt-hour. Average cost of S emissions reduction could be as high as $1298 per t of SO₂. Up to 367 plants, or 59% of selected plants with 32% of 44% nameplate capacity, could have marginal cost in excess of $1000 per t of SO₂. Up to 73 plants would appear to benefit from both a lowering of the annual cost and a lowering of SO₂ emissions by switching to the PRB coal.     

Integrated Assessment Modeling of Atmospheric Pollutants in the Southern Appalachian Mountains. Part I: Hourly and Seasonal Ozone

Abstract

Recently, a comprehensive air quality modeling system was developed as part of the Southern Appalachians Mountains Initiative (SAMI) with the ability to simulate meteorology, emissions, ozone, size- and composition-resolved particulate matter, and pollutant deposition fluxes. As part of SAMI, the RAMS/EMS-95/URM-1ATM modeling system was used to evaluate potential emission control strategies to reduce atmospheric pollutant levels at Class I areas located in the Southern Appalachians Mountains. This article discusses the details of the ozone model performance and the methodology that was used to scale discrete episodic pollutant levels to seasonal and annual averages. The daily mean normalized bias and error for 1-hr and 8-hr ozone were within U.S. Environment Protection Agency guidance criteria for urban-scale modeling. The model typically showed a systematic overestimation for low ozone levels and an underestimation for high levels. Because SAMI was primarily interested in simulating the growing season ozone levels in Class I areas, daily and seasonal cumulative ozone exposure, as characterized by the W126 index, were also evaluated. The daily ozone W126 performance was not as good as the hourly ozone performance; however, the seasonal ozone W126 scaled up from daily values was within 17% of the observations at two typical Class I areas of the SAMI region. The overall ozone performance of the model was deemed acceptable for the purposes of SAMI’s assessment.     

Mitigation of odor causing emissions—Bench-scale investigation

Emissions of malodors are considered to be the greatest threat to the compost industry. In work presented here, several simple odor mitigation alternatives were investigated for their effectiveness in preventing the release of common odorants, such as terpenes, ammonia, and reduced sulfur compounds. The mitigation methods studied included the use of a blanket of finished compost, compost amendment mixed within the feedstock, odor neutralizing agents (ONAs), and oxygen release compounds (ORCs). Among the mitigation alternatives investigated in this study, the use of finished compost as a blanket and finished compost as an amendment yielded the most conclusive and significant results. Both of these alternatives yielded a substantial emission reduction for terpenes, ammonia, and reduced sulfur compounds. The application of finished compost blanket resulted in up to 95% reduction of terpene and 25% reduction of ammonia emissions. Blending the feedstock with finished compost also provided substantial reduction of terpene emissions ranging from 73.6 to 93.1% at the 24% blending ratio, and up to 85% ammonia reduction a the 35% blending ratio. Use of finished compost also provided 75% lower reduced sulfur compound emissions at the 12% blending ratio. Misting and application of odor neutralizing agents did not result in any consistent reduction in emissions for any of the odorous compounds tested.

Implications The odor emissions from composting are often considered to be the biggest threat to composting facilities. Because most facilities cannot afford enclosures and contained composting vessels, there is a need to inexpensively and effectively control the odor emissions from composting facilities. The findings of this research can lead the way for efforts to control odor easily and cost effectively. In fact, the application of a compost blanket for odor control is already gaining acceptance by the composting industry.