DEVELOPMENT OF ANALYTICAL METHODS FOR THE QUANTIFICATION OF THE CHEMICAL FORMS OF MERCURY AND OTHER TARGET POLLUTANTS IN COAL-FIRED BOILER FLUE GAS

Abstract

Since approximately 55% of the electrical power produced in the U. S. is generated by coal-based power utility plants, there is serious concern about the massive amounts of coal combustion products emitted into the atmosphere annually. Furthermore, Title III of the 1990 Clean Air Act Amendments (CAAA) requires the measurement and inventory of a possible 189 hazardous air pollutants (HAPs) from any stationary source producing more than 10 tons per year of any one pollutant or more than 25 tons per year of total pollutants. Although power utilities are not presently included on the list of source categories, the CAAA requires the U. S. Environmental Protection Agency to carry out a study of emissions from electricity generation using fossil fuels. Since many of these HAPs are known to be present in coal derived flue gas, coal-fired electric power utilities may be subject to regulation following these studies if Congress considers it necessary. In a cooperative effort with the U. S. Environmental Protection Agency (EPA), the U. S. Department of Energy (DOE) through its Federal Energy Technology Center (FETC) initiated such a study in 1991. DOE-FETC commissioned five primary contractors to conduct emission studies at eight different coal-fired electric utilities. The eight sites represented a cross section of feed coal type, boiler designs, and particulate and gaseous pollutant control technologies. The major goal of these studies was to determine the sampling and analytical methodologies that could be used efficiently to perform these emission tests while producing representative and reliable emission data. The successful methodology could then be recommended to the EPA for use in compliance testing in the event the regulation of air toxic emissions from coal-fired power plants is implemented. A secondary purpose of the testing was to determine the effectiveness of the control technologies in reducing target hazardous air pollutants. Advanced Technology Systems, Inc. (ATS) as a secondary DOE contractor on this project, assessed the sampling and analytical plans and the emission reports of the five primary contractors to determine how successful the contractors were in satisfying their defined objectives. ATS identified difficulties and inconsistencies in a number of sampling and analytical methodologies in these studies. In particular there was uncertainty as to the validity of the sampling and analytical methods used to differentiate the chemical forms of mercury observed in coal flue gas. Considering the differences in the mercury species with regard to human toxicity, the rate of transport through the ecosystem and the design variations in possible emission control schemes, DOE sought an accurate and reliable means to identify and quantify the various mercury compounds emitted by coal-fired utility boilers. ATS, as a contractor for DOE, completed both bench- and pilot-scale studies on various mercury speciation methods. The final validation of the modified Ontario-Hydro Method, its acceptance by DOE and submission of the method for adoption by ASTM was a direct result of these studies carried out in collaboration with the University of North Dakota's Energy and Environmental Research Center (UNDEERC). This report presents the results from studies carried out at ATS in the development of analytical methods to identify and quantify various chemical species, particularly those of mercury, in coal derived flue gas. Laboratory- and pilot-scale studies, not only on mercury species, but also on other inorganics and organics present in coal combustion flue gas are reported.