Issues Related to Solution Chemistry in Mercury Sampling Impingers

ABSTRACT

Analysis of Hg speciation in combustion flue gases is often accomplished in standardized sampling trains in which the sample is passed sequentially through a series of aqueous solutions to capture and separate oxidized Hg (Hg²⁺) and elemental Hg (Hg⁰). Such methods include the Ontario Hydro (OH) and the Alkaline Mercury Speciation (AMS) methods, which were investigated in the laboratory to determine whether the presence of Cl₂ and other common flue gas species can bias the partitioning of Hg⁰ to front impingers intended to isolate Hg²⁺ species. Using only a single impinger to represent the front three impingers for each method, it was found that as little as 1-ppm Cl₂ in a simulated flue gas mixture led to a bias of approximately 10-20% of Hg⁰ misreported as Hg²+ for both the OH and the AMS methods. Experiments using 100-ppm Cl₂ led to a similar bias in the OH method, but to a 30-60% bias in the AMS method. These false readings are shown to be due to liquid-phase chemistry in the impinger solutions, and not necessarily to the gas-phase reactions between Cl₂ and Hg as previously proposed. The pertinent solution chemistry causing the interference     

Investigation of selective catalytic reduction impact on mercury speciation under simulated NOx emission control conditions

Selective catalytic reduction (SCR) technology increasingly is being applied for controlling emissions of nitrogen oxides (NOx) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury (Hg) in coal combustion flue gases. The speciation of Hg is an important factor influencing the control and environmental fate of Hg emissions from coal combustion. The vanadium and titanium oxides, used commonly in the vanadia-titania SCR catalyst for catalytic NOx reduction, promote the formation of oxidized mercury (Hg2+). The work reported in this paper focuses on the impact of SCR on elemental mercury (Hg0) oxidation. Bench-scale experiments were conducted to investigate Hg0 oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures with different concentrations of hydrogen chloride (HCl) and sulfur dioxide (SO2) for simulating the combustion of bituminous coals and subbituminous coals were tested in these experiments. The effects of HCl and SO2 in the flue gases on Hg0 oxidation under SCR reaction conditions were studied. It was observed that HCl is the most critical flue gas component that causes conversion of Hg0 to Hg2+ under SCR reaction conditions. The importance of HCl for Hg0 oxidation found in the present study provides the scientific basis for the apparent coal-type dependence observed for Hg0 oxidation occurring across the SCR reactors in the field.     

Effects of sulfur dioxide and nitric oxide on mercury oxidation and reduction under homogeneous conditions

This paper is particularly related to elemental mercury (Hg0) oxidation and divalent mercury (Hg2+) reduction under simulated flue gas conditions in the presence of nitric oxide (NO) and sulfur dioxide (SO2). As a powerful oxidant and chlorinating reagent, Cl2 has the potential for Hg oxidation. However, the detailed mechanism for the interactions, especially among chlorine (Cl)-containing species, SO2, NO, as well as H2O, remains ambiguous. Research described in this paper therefore focused on the impacts of SO2 and NO on Hg0 oxidation and Hg2+ reduction with the intent of unraveling unrecognized interactions among Cl species, SO2, and NO most importantly in the presence of H2O. The experimental results demonstrated that SO2 and NO had pronounced inhibitory effects on Hg0 oxidation at high temperatures when H2O was also present in the gas blend. Such a demonstration was further confirmed by the reduction of Hg2+ back into its elemental form. Data revealed that SO2 and NO were capable of promoting homogeneous reduction of Hg2+ to Hg0 with H2O being present. However, the above inhibition or promotion disappeared under homogeneous conditions when H2O was removed from the gas blend.     

A study of gas-phase mercury speciation using detailed chemical kinetics.

Mercury speciation in combustion-generated flue gas was modeled using a detailed chemical mechanism consisting of 60 reactions and 21 species. This speciation model accounts for the chlorination and oxidation of key flue-gas components, including elemental mercury (Hg0). Results indicated that the performance of the model is very sensitive to temperature. Starting with pure HCl, for lower reactor temperatures (less than approximately 630 degrees C), the model produced only trace amounts of atomic and molecular chlorine (Cl and Cl2), leading to a drastic underprediction of Hg chlorination compared with experimental data. For higher reactor temperatures, model predictions were in good accord with experimental data. For conditions that produce an excess of Cl and Cl2 relative to Hg, chlorination of Hg is determined by the competing influences of the initiation step, Hg + Cl = HgCl, and the Cl recombination reaction, 2Cl = Cl2. If the Cl recombination reaction is faster, Hg chlorination will eventually be dictated by the slower pathway Hg + Cl2 = HgCl2.     

Pilot-scale study of the effect of selective catalytic reduction catalyst on mercury speciation in Illinois and Powder River Basin coal combustion flue gases

A study was conducted to investigate the effect of selective catalytic reduction (SCR) catalyst on mercury (Hg) speciation in bituminous and subbituminous coal combustion flue gases. Three different Illinois Basin bituminous coals (from high to low sulfur [S] and chlorine [Cl]) and one Powder River Basin (PRB) subbituminous coal with very low S and very low Cl were tested in a pilot-scale combustor equipped with an SCR reactor for controlling nitrogen oxides (NOx) emissions. The SCR catalyst induced high oxidation of elemental Hg (Hg0), decreasing the percentage of Hg0 at the outlet of the SCR to values <12% for the three Illinois coal tests. The PRB coal test indicated a low oxidation of Hg0 by the SCR catalyst, with the percentage of Hg0 decreasing from approximately 96% at the inlet of the reactor to approximately 80% at the outlet. The low Cl content of the PRB coal and corresponding low level of available flue gas Cl species were believed to be responsible for low SCR Hg oxidation for this coal type. The test results indicated a strong effect of coal type on the extent of Hg oxidation.     

Predicting extents of mercury oxidation in coal-derived flue gases

The proposed mercury (Hg) oxidation mechanism consists of a 168-step gas phase mechanism that accounts for interaction among all important flue gas species and a heterogeneous oxidation mechanism on unburned carbon (UBC) particles, similar to established chemistry for dioxin production under comparable conditions. The mechanism was incorporated into a gas cleaning system simulator to predict the proportions of elemental and oxidized Hg species in the flue gases, given relevant coal properties (C/H/O/N/S/Cl/Hg), flue gas composition (O2, H2O, HCl), emissions (NO(X), SO(X), CO), the recovery of fly ash, fly ash loss-on-ignition (LOI), and a thermal history. Predictions are validated without parameter adjustments against datasets from lab-scale and from pilot-scale coal furnaces at 1 and 29 MWt. Collectively, the evaluations cover 16 coals representing ranks from sub-bituminous through high-volatile bituminous, including cases with Cl2 and CaCl2 injection. The predictions are, therefore, validated over virtually the entire domain of Cl-species concentrations and UBC levels of commercial interest. Additional predictions identify the most important operating conditions in the furnace and gas cleaning system, including stoichiometric ratio, NO(X), LOI, and residence time, as well as the most important coal properties, including coal-Cl.     

The importance of the location of sodium chlorite application in a multipollutant flue gas cleaning system

In this study, removing sulfur dioxide (SO2), nitrogen oxides (NO(x)), and mercury (Hg) from simulated flue gas was investigated in two laboratory-sized bubbling reactors that simulated an oxidizing reactor (where the NO and Hg(0) oxidation reactions are expected to occur) and a wet limestone scrubber, respectively. A sodium chlorite solution was used as the oxidizing agent. The sodium chlorite solution was an effective additive that enhanced the NO(x), Hg, and SO2 capture from the flue gas. Furthermore, it was discovered that the location of the sodium chlorite application (before, in, or after the wet scrubber) greatly influences which pollutants are removed and the amount removed. This effect is related to the chemical conditions (pH, absence/presence of particular gases) that are present at different positions throughout the flue gas cleaning system profile. The research results indicated that there is a potential to achieve nearly zero SO2, NO(x), and Hg emissions (complete SO2, NO, and Hg removals and -90% of NO(x) absorption from initial values of 1500 ppmv of SO2, 200 ppmv of NO(x), and 206 microg/m3 of Hg(0)) from the flue gas when sodium chlorite was applied before the wet limestone scrubber. However applying the oxidizer after the wet limestone scrubber was the most effective configuration for Hg and NO(x) control for extremely low chlorite concentrations (below 0.002 M) and therefore appears to be the best configuration for Hg control or as an additional step in NO(x) recleaning (after other NO(x) control facilities). The multipollutant scrubber, into which the chlorite was injected simultaneously with the calcium carbonate slurry, appeared to be the least expensive solution (when consider only capital cost), but exhibited the lowest NO(x) absorption at -50%. The bench-scale test results presented can be used to develop performance predictions for a full- or pilot-scale multipollutant flue gas cleaning system equipped with wet flue gas desulfurization scrubber.     

The effect of coal combustion flue gas components on low-level chlorine speciation using EPA method 26A

U.S. Environmental Protection Agency (EPA) Method 26A is the recommended procedure for capturing and speciating halogen (X2) and hydrogen halide (HX) stack emissions from combustion sources. Previous evaluation studies of Method 26A have focused primarily on hydrogen chloride (HCl) speciation. Capture efficiency, bias, and the potential interference of Cl2 at high levels (> 20 ppm [microgram/m3]) and NH4Cl in the flue gas stream have been investigated. It has been suggested that precise Cl2 measurement and accuracy in quantifying HX or X2 using Method 26A are difficult to achieve at Cl2 concentrations < 5 ppm; however, no performance data exist to support this. Coal contains low levels of Cl, in the range of 5-2000 ppmw, which results in the presence of HCl and Cl2 in the products of combustion. HCl is the predominant Cl compound formed in the high-temperature combustion process, and it persists in the gas as the products of combustion cool. Concentrations of Cl2 in coal combustion flue gas at stack temperatures typically do not exceed 5 ppm. For this research, bench-scale experiments using simulated combustion flue gas were designed to validate the ability of Method 26A to speciate low levels of Cl2 accurately. This paper presents the results of the bench-scale tests. The effect of various flue gas components is discussed. The results indicate that SO2 is the only component in coal combustion flue gas that has an appreciable effect on Cl2 distribution in Method 26A impingers, and that Method 26A cannot accurately speciate HCl and Cl2 in coal combustion flue gas without modification.     

Pilot-Scale Study of the Effect of Selective Catalytic Reduction Catalyst on Mercury Speciation in Illinois and Powder River Basin Coal Combustion Flue Gases

Abstract

A study was conducted to investigate the effect of selective catalytic reduction (SCR) catalyst on mercury (Hg) speciation in bituminous and subbituminous coal combustion flue gases. Three different Illinois Basin bituminous coals (from high to low sulfur [S] and chlorine [Cl]) and one Powder River Basin (PRB) subbituminous coal with very low S and very low Cl were tested in a pilot-scale combustor equipped with an SCR reactor for controlling nitrogen oxides (NO_x) emissions. The SCR catalyst induced high oxidation of elemental Hg (Hg⁰), decreasing the percentage of Hg⁰ at the outlet of the SCR to values <12% for the three Illinois coal tests. The PRB coal test indicated a low oxidation of Hg⁰ by the SCR catalyst, with the percentage of Hg⁰ decreasing from ～96% at the inlet of the reactor to ～80% at the outlet. The low Cl content of the PRB coal and corresponding low level of available flue gas Cl species were believed to be responsible for low SCR Hg oxidation for this coal type. The test results indicated a strong effect of coal type on the extent of Hg oxidation.     

Characterization of flue gas cleaning residues from European solid waste incinerators: assessment of various Ca-based sorbent processes

For the first time, a set of samples of European flue gas cleaning residues, mainly from the incineration of municipal solid waste (MSW), has undergone a mineralogical study. The residues are the result of the neutralization of acid flue gases by lime, the predominant method adopted in Europe, using dry and semi-dry washing processes. The study protocol combines physico-chemical analytical techniques (XRD, FTIR, DSC/TGA) and global chemical analysis enabling identification of the chemical composition of the main constituents, particularly chlorinated Ca-based phases, as well as establishment of modal distributions of the represented phases, both crystalline and amorphous. The samples are slightly hydrated and values vary for trapped Cl, S and even CO(2). The main crystalline phases are NaCl, KCl, CaSO(4), CaCO(3), Ca(OH)(2) and calcium hydroxychloride CaOHCl. CaOHCl is the main chlorine phase, regardless of the treatment process, filtration mode, and specific surface of the Ca-based sorbent. This phase develops during neutralization of HCl by excess lime present according to the reaction Ca(OH)(2)+HCl-->CaOHCl+H(2)O, to the detriment of a complete yield involving the two lime OH groups with formation of CaCl(2).2H(2)O. In addition, it seems that gas temperatures above 150 degrees C increase competition between lime-based neutralization of HCl, SO(2) acid flue gases and CO(2) trapping, thus reducing washing efficiency.     

Investigation of Selective Catalytic Reduction Impact on Mercury Speciation under Simulated NOx Emission Control Conditions

Abstract

Selective catalytic reduction (SCR) technology increasingly is being applied for controlling emissions of nitrogen oxides (NO_x) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury (Hg) in coal combustion flue gases. The speciation of Hg is an important factor influencing the control and environmental fate of Hg emissions from coal combustion. The vanadium and titanium oxides, used commonly in the vanadia-titania SCR catalyst for catalytic NO_x reduction, promote the formation of oxidized mercury (Hg²⁺).

The work reported in this paper focuses on the impact of SCR on elemental mercury (Hg⁰) oxidation. Bench-scale experiments were conducted to investigate Hg⁰ oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures with different concentrations of hydrogen chloride (HCl) and sulfur dioxide (SO₂) for simulating the combustion of bituminous coals and subbituminous coals were tested in these experiments. The effects of HCl and SO₂ in the flue gases on Hg⁰ oxidation under SCR reaction conditions were studied. It was observed that HCl is the most critical flue gas component that causes conversion of Hg⁰ to Hg²⁺ under SCR reaction conditions. The importance of HCl for Hg⁰ oxidation found in the present study provides the scientific basis for the apparent coal-type dependence observed for Hg⁰ oxidation occurring across the SCR reactors in the field.     

The impact of wet flue gas desulfurization scrubbing on mercury emissions from coal-fired power stations

This article introduces a predictive capability for Hg retention in any Ca-based wet flue gas desulfurization (FGD) scrubber, given mercury (Hg) speciation at the FGD inlet, the flue gas composition, and the sulphur dioxide (SO2) capture efficiency. A preliminary statistical analysis of data from 17 full-scale wet FGDs connects flue gas compositions, the extents of Hg oxidation at FGD inlets, and Hg retention efficiencies. These connections clearly signal that solution chemistry within the FGD determines Hg retention. A more thorough analysis based on thermochemical equilibrium yields highly accurate predictions for total Hg retention with no parameter adjustments. For the most reliable data, the predictions were within measurement uncertainties for both limestone and Mg/lime systems operating in both forced and natural oxidation mode. With the U.S. Environmental Protection Agency's (EPA) Information Collection Request (ICR) database, the quantitative performance was almost as good for the most modern FGDs, which probably conform to the very high SO2 absorption efficiencies assumed in the calculations. The large discrepancies for older FGDs are tentatively attributed to the unspecified SO2 capture efficiencies and operating temperatures and to the possible elimination of HCl in prescrubbers. The equilibrium calculations suggest that Hg retention is most sensitive to inlet HCl and O2 levels and the FGD temperature; weakly dependent on SO2 capture efficiency; and insensitive to HgCl2, NO, CA:S ratio, slurry dilution level in limestone FGDs, and MgSO3 levels in Mg/lime systems. Consequently, systems with prescrubbers to eliminate HCl probably retain less Hg than fully integrated FGDs. The analysis also predicts re-emission of Hg(O) but only for inlet O2 levels that are much lower than those in full-scale FGDs.     

Surface compositions of carbon sorbents exposed to simulated low-rank coal flue gases

Bench-scale testing of elemental mercury (Hg0) sorption on selected activated carbon sorbents was conducted to develop a better understanding of the interaction among the sorbent, flue gas constituents, and Hg0. The results of the fixed-bed testing under simulated lignite combustion flue gas composition for activated carbons showed some initial breakthrough followed by increased mercury (Hg) capture for up to approximately 4.8 hr. After breakthrough, the Hg in the effluent stream was primarily in an oxidized form (>90%). Aliquots of selected activated carbons were exposed to simulated flue gas containing Hg0 vapor for varying time intervals to explore surface chemistry changes as the initial breakthrough, Hg capture, and oxidation occurred. The samples were analyzed by X-ray photoelectron spectroscopy to determine changes in the abundance and forms of sulfur, chlorine, oxygen, and nitrogen moieties as a result of interactions of flue gas components on the activated carbon surface during the sorption process. The data are best explained by a competition between the bound hydrogen chloride (HCl) and increasing sulfur [S(VI)] for a basic carbon binding site. Because loss of HCl is also coincident with Hg breakthrough or loss of the divalent Hg ion (Hg2+), the competition of Hg2+ with S(VI) on the basic carbon site is also implied. Thus, the role of the acid gases in Hg capture and release can be explained.     

Stack Dust Sampling: in-Stack Filter or E.P.A. Train

The Environmental Protection Agency has recommended or specified methods for the measurement of participate concentrations in flue gases. The EPA Train for this measurement originally comprised two segments: the front half and the impinger train downstream from the filter proper. This review examines the controversial areas implicit in the use of this EPA Train or the revised EPA train which eliminates the impinger train.     

Gas-phase mercury reduction to measure total mercury in the flue gas of a coal-fired boiler

Gaseous elemental and total (elemental + oxidized) mercury (Hg) in the flue gas from a coal-fired boiler was measured by a modified ultraviolet (UV) spectrometer. Challenges to Hg measurement were the spectral interferences from other flue gas components and that UV measures only elemental Hg. To eliminate interference from flue gas components, a cartridge filled with gold-coated sand removed elemental Hg from a flue gas sample. The Hg-free flue gas was the reference gas, eliminating the spectral interferences. To measure total Hg by UV, oxidized Hg underwent a gas-phase, thermal-reduction in a quartz cell heated to 750 degrees C. Simultaneously, hydrogen was added to flash react with the oxygen present forming water vapor and preventing Hg re-oxidation as it exits the cell. Hg concentration results are in parts per billion by volume Hg at the flue gas oxygen concentration. The modified Hg analyzer and the Ontario Hydro method concurrently measured Hg at a field test site. Measurements were made at a 700-MW steam turbine plant with scrubber units and selective catalytic reduction. The flue gas sampled downstream of the selective catalytic reduction contained 2100 ppm SO2 and 75 ppm NOx. Total Hg measured by the Hg analyzer was within 20% of the Ontario Hydro results.     

The fate and behavior of mercury in coal-fired power plants

For the past 22 years in the Netherlands, the behavior of Hg in coal-fired power plants has been studied extensively. Coal from all over the world is fired in Dutch power stations. First, the Hg concentrations in these coals were measured. Second, the fate of the Hg during combustion was established by performing mass balance studies. On average, 43 +/- 30% of the Hg was present in the flue gases downstream of the electrostatic precipitator (ESP; dust collector). In individual cases, this figure can vary between 1 and 100%. Important parameters are the Cl content of the fuel and the flue gas temperature in the ESP. On average, 54 +/- 24% of the gaseous Hg was removed in the wet flue-gas desulfurization (FGD) systems, which are present at all Dutch coal-power stations. In individual cases, this removal can vary between 8% (outlier) and 72%. On average, the fate of Hg entering the power station in the coal was as follows: <1% in the bottom ash, 49% in the pulverized fuel ash (ash collected in the ESP), 16.6% in the FGD gypsum, 9% in the sludge of the wastewater treatment plant, 0.04% in the effluent of the wastewater treatment plant, 0.07% in fly dust (leaving the stack), and 25% as gaseous Hg in the flue gases and emitted into the air. The distribution of Hg over the streams leaving the FGD depends strongly on the installation. On average, 75% of the Hg was removed, and the final concentration of Hg in the emitted flue gases of the Dutch power stations was only -3 microg/m3(STP) at 6% O2. During co-combustion with biomass, the removal of Hg was similar to that during 100% coal firing. Speciation of Hg is a very important factor. An oxidized form (HgCl2) favors a high degree of removal. The conversion from Hg0 to HgCl2 is positively correlated with the Cl content of the fuel. A catalytic DENOX (SCR) favors the formation of oxidized Hg, and, in combination with a wet FGD, the total removal can be as high as 90%.     

Surface Compositions of Carbon Sorbents Exposed to Simulated Low-Rank Coal Flue Gases

Abstract

Bench-scale testing of elemental mercury (Hg⁰) sorption on selected activated carbon sorbents was conducted to develop a better understanding of the interaction among the sorbent, flue gas constituents, and Hg⁰. The results of the fixed-bed testing under simulated lignite combustion flue gas composition for activated carbons showed some initial breakthrough followed by increased mercury (Hg) capture for up to ～4.8 hr. After breakthrough, the Hg in the effluent stream was primarily in an oxidized form (>90%). Aliquots of selected activated carbons were exposed to simulated flue gas containing Hg⁰ vapor for varying time intervals to explore surface chemistry changes as the initial breakthrough, Hg capture, and oxidation occurred. The samples were analyzed by X-ray photoelectron spectroscopy to determine changes in the abundance and forms of sulfur, chlorine, oxygen, and nitrogen moieties as a result of interactions of flue gas components on the activated carbon surface during the sorption process. The data are best explained by a competition between the bound hydrogen chloride (HCl) and increasing sulfur [S(VI)] for a basic carbon binding site. Because loss of HCl is also coincident with Hg breakthrough or loss of the divalent Hg ion (Hg²⁺), the competition of Hg²⁺ with S(VI) on the basic carbon site is also implied. Thus, the role of the acid gases in Hg capture and release can be explained.     

Effect of NOx control processes on mercury speciation in utility flue gas

The speciation of Hg in coal-fired flue gas can be important in determining the ultimate Hg emissions as well as potential control options for the utility. The effects of NOx control processes, such as selective catalytic reduction (SCR) and selective non-catalytic reduction (SNCR), on Hg speciation are not well understood but may impact emissions of Hg. EPRI has investigated the reactions of Hg in flue gas at conditions expected for some NOx control processes. This paper describes the methodology used to investigate these reactions in actual flue gas at several power plants. Results have indicated that some commercial SCR catalysts are capable of oxidizing elemental Hg in flue gas obtained from the inlets of SCR or air heater units. Results are affected by various flue gas and operating parameters. The effect of flue gas composition, including the presence of NH3, has been evaluated. The influence of NH3 on fly ash Hg reactions also is being investigated.     

Mercury oxidation promoted by a selective catalytic reduction catalyst under simulated Powder River Basin coal combustion conditions

A bench-scale reactor consisting of a natural gas burner and an electrically heated reactor housing a selective catalytic reduction (SCR) catalyst was constructed for studying elemental mercury (Hg(o)) oxidation under SCR conditions. A low sulfur Powder River Basin (PRB) subbituminous coal combustion fly ash was injected into the entrained-flow reactor along with sulfur dioxide (SO2), nitrogen oxides (NOx), hydrogen chloride (HCl), and trace Hg(o). Concentrations of Hg(o) and total mercury (Hg) upstream and downstream of the SCR catalyst were measured using a Hg monitor. The effects of HCl concentration, SCR operating temperature, catalyst space velocity, and feed rate of PRB fly ash on Hg(o) oxidation were evaluated. It was observed that HCl provides the source of chlorine for Hg(o) oxidation under simulated PRB coal-fired SCR conditions. The decrease in Hg mass balance closure across the catalyst with decreasing HCl concentration suggests that transient Hg capture on the SCR catalyst occurred during the short test exposure periods and that the outlet speciation observed may not be representative of steady-state operation at longer exposure times. Increasing the space velocity and operating temperature of the SCR led to less Hg(o) oxidized. Introduction of PRB coal fly ash resulted in slightly decreased outlet oxidized mercury (Hg2+) as a percentage of total inlet Hg and correspondingly resulted in an incremental increase in Hg capture. The injection of ammonia (NH3) for NOx reduction by SCR was found to have a strong effect to decrease Hg oxidation. The observations suggest that Hg(o) oxidation may occur near the exit region of commercial SCR reactors. Passage of flue gas through SCR systems without NH3 injection, such as during the low-ozone season, may also impact Hg speciation and capture in the flue gas.     

Simultaneous control of Hg0, SO2, and NOx by novel oxidized calcium-based sorbents

Efforts to develop multipollutant control strategies have demonstrated that adding certain oxidants to different classes of Ca-based sorbents leads to a significant improvement in elemental Hg vapor (Hg0), SO2, and NOx removal from simulated flue gases. In the study presented here, two classes of Ca-based sorbents (hydrated limes and silicate compounds) were investigated. A number of oxidizing additives at different concentrations were used in the Ca-based sorbent production process. The Hg0, SO2, and NOx capture capacities of these oxidant-enriched sorbents were evaluated and compared to those of a commercially available activated carbon in bench-scale, fixed-bed, and fluid-bed systems. Calcium-based sorbents prepared with two oxidants, designated C and M, exhibited Hg0 sorption capacities (approximately 100 microg/g) comparable to that of the activated carbon; they showed far superior SO2 and NOx sorption capacities. Preliminary cost estimates for the process utilizing these novel sorbents indicate potential for substantial lowering of control costs, as compared with other processes currently used or considered for control of Hg0, SO2, and NOx emissions from coal-fired boilers. The implications of these findings toward development of multipollutant control technologies and planned pilot and field evaluations of more promising multipollutant sorbents are summarily discussed.