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.     

Visitor impact on rocky shore communities of Qeshm Island, the Persian Gulf, Iran

The influence of visitors on macroinvertebrates of rocky intertidal shores was investigated in southern coasts of the Qeshm Island, the Persian Gulf, Iran. Qeshm Island located at the Strait of Hormuz, with an area of 1,491 km², is the largest island in the region. This island consists of a number of important natural habitat types including creeks, mangroves, corals, and sandy, muddy, and rocky shores that accommodate diverse marine flora and fauna communities. Two rocky shores were selected at the touristic beaches being visited regularly, and further two control locations selected at pristine shores. Intertidal macroinvertebrates were collected from six microhabitats including rock platforms, cobbles, boulders, crevices, sea walls, and rock pools during two different periods representing high and low tourist seasons. Species richness, density, and assemblage structure in heavily visited shores were compared with that of control locations. Striped barnacles (Balanus amphitrite) were present on platforms of all locations, thus the changes in their size were used as the obvious contrast associated with visitor’s impact. A total of 70 macroinvertebrate species from 11 phyla were recorded. Significant differences were detected in taxonomic richness, density, and assemblage structure of macroinvertebrates between heavily visited and pristine shores, suggesting that macroinvertebrates were adversely affected by visitors’ impact at heavily visited shores. The test of changes in species richness, density, and assemblage structure from high to low seasons yielded mixed results. The significant changes in density and assemblage structure from high to low seasons were only observed in one heavily visited shore. A significant reduction in size of striped barnacles was observed only in one heavily visited shore. The opportunistic or fugitive species (e.g., small macroalgae and barnacles) were dominant macroinvertebrates on heavily visited shores indicating early succession stage. The results presented here showed that macroinvertebrates were adversely affected by human activities in subtropical rocky shore.     

Screening for plants and rhizospheral fungi with bioremediation potency of petroleum-polluted soils in a Tehran oil refinery area

The contamination of soils by toxic and/or hazardous organic pollutants, especially with crude oil, is a widespread problem. This study was conducted in a petroleum-contaminated area in a Tehran oil refinery to find petroleum-resistant plants and their rhizospheral fungal strains with bioremediation potency. The plants growing in the oil-polluted area were collected and determined taxonomically. Root samples of the plant species were collected from a polluted area and fungal strains determined by laboratory methods and taxonomical keys. The growth ability of the isolated fungal strains was studied in media containing 1%–15% crude oil. Results showed that seven plant species were of the highest density in the contaminated area: Alhagi persarum, Hordeum marinum, Peganum harmala, Phragmites australis, Prosopis farcta, Salsola kali, and Senecio glaucus. The root-associated fungi were isolated and showed that the fungal variation in the oil-polluted area is higher than that in a non-polluted area. The growth assay of isolated fungal strains showed that all studied fungal strains were able to form colonies at the applied concentrations but Alternaria sp. and Rhizopus sp. were the most resistant ones. Some plants were resistant to oil pollution, which also had positive effects on the fungal strains.     

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.     

Contamination by organochlorine compounds in the edible tissue of four sturgeon species from the Caspian Sea (Iran)

This study focused on accumulation of organochlorine compounds (OCs), including dichloro-diphenyl-trichloroethanes (DDTs), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs), and polychlorinated biphenyls (PCBs) accumulation in the muscle of four sturgeon (Persian sturgeon, Acipenser persicus; Stellate sturgeon, Acipenser stellatus; Ship sturgeon, Acipenser nudiventris and Beluga sturgeon, Huso huso) from the southern Caspian Sea. The DDT group was prominent in all of the sturgeon muscle tested constituting almost half or more of the total organochlorine content. Contaminant concentration generally followed this order: DDTs>PCBs>HCHs>HCB. The OCs concentrations in Beluga sturgeon (H. huso) were the highest and over four times higher than in the next highest species (A. nudiventris). From an ecotoxicological point of view, the concentrations of OCs in experimental fishes do not reflect a comparatively clean and pollution-free environment; however, results from this study shown that the inflow of organic pollutants into the Caspian Sea has been reduced when compared with prior studies. Levels of measured OCs in sturgeon were relatively low, but the level of some OCs in some of the specimens tested exceeded the guidelines for food; therefore, the maximum allowable daily consumption rate for sturgeon from this watershed may be limited by DDTs and PCBs content for high risk populations.     

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.     

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.