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.     

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.     

Adsorption of mercury by activated carbon prepared from dried sewage sludge in simulated flue gas

Conversion of sewage sludge to activated carbon is attractive as an alternative method to ocean dumping for the disposal of sewage sludge. Injection of activated carbon upstream of particulate matter control devices has been suggested as a method to remove elemental mercury from flue gas. Activated carbon was prepared using various activation temperatures and times and was tested for their mercury adsorption efficiency using lab-scale systems. To understand the effect of the physical property of the activated carbon, its mercury adsorption efficiency was investigated as a function of its Brunauer–Emmett–Teller (BET) surface area. Two simulated flue gas conditions, (1) without hydrogen chloride (HCl) and (2) with 20 ppm HCl, were used to investigate the effect of flue gas composition on the mercury adsorption capacity of activated carbon. Despite very low BET surface area of the prepared sewage sludge activated carbons, their mercury adsorption efficiencies were comparable under both simulated flue gas conditions to those of pinewood and coal activated carbons. After injecting HCl into the simulated flue gas, all sewage sludge activated carbons demonstrated high adsorption efficiencies, that is, more than 87%, regardless of their BET surface area.

Implications: We tested activated carbons prepared from dried sewage sludge to investigate the effect of their physical properties on their mercury adsorption efficiency. Using two simulated flue gas conditions, we conducted mercury speciation for the outlet gas. We found that the sewage sludge activated carbon had mercury adsorption efficiency comparable to pinewood and coal activated carbons, and the presence of HCl minimized the effect of physical property of the activated carbon on its mercury adsorption efficiency.     

Ultra-high adsorption of Hg0 using impregnated activated carbon by selenium

Activated carbon was one of the main adsorptions utilized in elemental mercury (Hg⁰) removal from coal combustion flue gas. However, the high cost and low physical adsorption efficiency of activated carbon injection (ACI) limited its application. In this study, an ultra-high efficiency (nearly 100%) catalyst sorbent-Se_x/Activated carbon (Se_x/AC) was synthesized and applied to remove Hg⁰ in the simulated flue gas, which exhibited 120 times outstanding adsorption performance versus the conventional activated carbon. The Se_x/AC reached 17.98 mg/g Hg⁰ adsorption capacity at 160 °C under the pure nitrogen atmosphere. Moreover, it maintained an excellent mercury adsorption tolerance, reaching the efficiency of Hg⁰ removal above 85% at the NO and SO₂ conditions in a bench-scale fixed-bed reactor. Characterized by the multiple methods, including BET, XRD, XPS, kinetic and thermodynamic analysis, and the DFT calculation, we demonstrated that the ultrahigh mercury removal performance originated from the activated Se species in Se_x/AC. Chemical adsorption plays a dominant role in Hg⁰ removal: Selenium anchored on the surface of AC would capture Hg⁰ in the flue gas to form an extremely stable substance-HgSe, avoiding subsequent Hg⁰ released. Additionally, the oxygen-containing functional groups in AC and the higher BET areas promote the conversion of Hg⁰ to HgO. This work provided a novel and highly efficient carbon-based sorbent -Se_x/AC to capture the mercury in coal combustion flue gas.

Selenium-modified porous activated carbon and the interface functional group promotes the synergistic effect of physical adsorption and chemical adsorption to promote the adsorption capacity of Hg⁰.

     

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.     

Performance of Copper Chloride-Impregnated Sorbents on Mercury Vapor Control in an Entrained-Flow Reactor System

Abstract

An entrained-flow system has been designed and constructed to simulate in-flight mercury (Hg) capture by sorbent injection in ducts of coal-fired utility plants. The test conditions of 1.2-sec residence time, 140 °C gas temperature, 6.7 m/sec (22 ft/sec) gas velocity, and 0–0.24 g/m³ (0–15 lbs of sorbent per 1 million actual cubic feet of flue gas [lb/MMacf]) sorbent injection rates were chosen to simulate conditions in the ducts. Four kinds of sorbents were used in this study. Darco Hg-LH served as a benchmark sorbent with which Hg control capability of other sorbents could be compared. Also, Darco-FGD was used as a representative raw activated carbon sorbent. Two different copper chloride-impregnated sorbents were developed in our laboratory and tested in the entrained-flow system to examine the possibility of using these sorbents at coal-fired power plants. The test results showed that one of the copper chloride sorbents has remarkable elemental mercury (Hg⁰) oxidation capability, and the other sorbent demonstrated a better performance in Hg removal than Darco Hg-LH.     

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     

Simultaneous Control of Hg0, SO2, and NOx by Novel Oxidized Calcium-Based Sorbents

Abstract

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 NO_x 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 NO_x 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 sorp-tion capacities (~100 μg/g) comparable to that of the activated carbon; they showed far superior SO₂ and NO_x 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 NO_x 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.     

高温载硫活性炭的制备及脱汞能力研究

研究了载硫温度、硫炭比(简称S/C),吸附温度等因素对载硫活性炭的硫含量、脱汞能力以及硫损失的影响,探讨载硫活性炭制备的工艺条件优化。结果表明,不同载硫温度下制备的载硫活性炭的气态Hg0吸附能力远强于原料活性炭;载硫温度不同时,负载到活性炭孔隙或表面上的硫的形态不同,导致了脱汞能力的差异,较合适的载硫温度为350℃;S/C为5%(质量分数,下同)时,随着吸附温度的升高,载硫活性炭的气态Hg0吸附量降低;在一定的载硫温度下,原料中S/C越高时,制备的载硫活性炭的硫含量越高、气态Hg0吸附能力越强,但其硫损失率也越高,从实际的使用效果来看,较合适的S/C为10%。     

Gas-phase elemental mercury removal in a simulated combustion flue gas using TiO2 with fluorescent light

A previously proposed technology incorporating TiO₂ into common household fluorescent lighting was further tested for its Hg⁰ removal capability in a simulated flue-gas system. The flue gas is simulated by the addition of O₂, SO₂, HCl, NO, H₂O, and Hg⁰, which are frequently found in combustion facilities such as waste incinerators and coal-fired power plants. In the O₂ + N₂ + Hg⁰ environment, a Hg⁰ removal efficiency (η_Hg) greater than 95% was achieved. Despite the tendency for η_Hg to decrease with increasing SO₂ and HCl, no significant drop was observed at the tested level (SO₂: 5–300 ppm_v, HCl: 30–120 ppm_v). In terms of NO and moisture, a significant negative effect on η_Hg was observed for both factors. NO eliminated the OH radical on the TiO₂ surface, whereas water vapor caused either the occupation of active sites available to Hg⁰ or the reduction of Hg₀ by free electron. However, the negative effect of NO was minimized (η_Hg > 90%) by increasing the residence time in the photochemical reactor. The moisture effect can be avoided by installing a water trap before the flue gas enters the Hg⁰ removal system.

Implications: This paper reports a novel technology for a removal of gas-phase elemental mercury (Hg⁰) from a simulated flue gas using TiO₂-coated glass beads under a low-cost, easily maintainable household fluorescent light instead of ultraviolet (UV) light. In this study, the effects of individual chemical species (O₂, SO₂, HCl, NO, and water vapor) on the performance of the proposed technology for Hg⁰ removal are investigated. The result suggests that the proposed technology can be highly effective, even in real combustion environments such as waste incinerators and coal-fired power plants.     

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.     

Distribution of mercury in the combustion products from coal-fired power plants in Guizhou,southwest China

Method 30B and the Ontario Hydro Method (OHM) were used to sample the mercury in the flue gas discharged from the seven power plants in Guizhou Province, southwest China. In order to investigate the mercury migration and transformation during coal combustion and pollution control process, the contents of mercury in coal samples, bottom ash, fly ash, and gypsum were measured. The mercury in the flue gas released into the atmosphere mainly existed in the form of Hg°. The precipitator shows a superior ability to remove Hg^p (particulate mercury) from flue gas. The removal efficiency of Hg²⁺ by wet flue gas desulfurization (WFGD) was significantly higher than that for the other two forms of mercury. The synergistic removal efficiency of mercury by the air pollution control devices (APCDs) installed in the studied power plants is 66.69–97.56%. The Hg mass balance for the tested seven coal-fired power plants varied from 72.87% to 109.67% during the sampling time. After flue gas flowing through APCDs, most of the mercury in coal was enriched in fly ash and gypsum, with only a small portion released into the atmosphere with the flue gas. The maximum discharge source of Hg for power plants was fly ash and gypsum instead of Hg emitted with flue gas through the chimney into the atmosphere. With the continuous upgrading of APCDs, more and more mercury will be enriched in fly ash and gypsum. Extra attention should be paid to the re-release of mercury from the reutilization of by-products from APCDs.

Implications: Method 30B and the Ontario Hydro Method (OHM) were used to test the mercury concentration in the flue gas discharged from seven power plants in Guizhou Province, China. The concentrations of mercury in coal samples, bottom ash, fly ash, and gypsum were also measured. By comparison of the mercury content of different products, we found that the maximum discharge source of Hg for power plants was fly ash and gypsum, instead of Hg emitted with flue gas through the chimney into the atmosphere. With the continuous upgrading of APCDs, more and more mercury will be enriched in fly ash and gypsum. Extra attention should be paid to the re-release of mercury from the reutilization of by-products from APCDs.     

Effects of Sulfur Dioxide and Nitric Oxide on Mercury Oxidation and Reduction under Homogeneous Conditions

Abstract

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.     

Study on the removal of elemental mercury from simulated flue gas by Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-CeO<Subscript>2</Subscript>/AC at low temperature

Fe₂O₃ and CeO₂ modified activated coke (AC) synthesized by the equivalent-volume impregnation were employed to remove elemental mercury (Hg⁰) from simulated flue gas at a low temperature. Effects of the mass ratio of Fe₂O₃ and CeO₂, reaction temperature, and individual flue gas components including O₂, NO, SO₂, and H₂O (g) on Hg⁰ removal efficiency of impregnated AC were investigated. The samples were characterized by Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Results showed that with optimal mass percentage of 3 % Fe₂O₃ and 3 % CeO₂ on Fe3Ce3/AC, the Hg⁰ removal efficiency could reach an average of 88.29 % at 110 °C. Besides, it was observed that O₂ and NO exhibited a promotional effect on Hg⁰ removal, H₂O (g) exerted a suppressive effect, and SO₂ showed an insignificant inhibition without O₂ to some extent. The analysis of XPS indicated that the main species of mercury on used Fe3Ce3/AC was HgO, which implied that adsorption and catalytic oxidation were both included in Hg⁰ removal. Furthermore, the lattice oxygen, chemisorbed oxygen, and/or weakly bonded oxygen species made a contribution to Hg⁰ oxidation.     

Airborne Emissions of Mercury from Municipal Solid Waste. II: Potential Losses of Airborne Mercury before Landfill

Abstract

Waste distribution and compaction at the working face of municipal waste landfills releases mercury vapor (Hg⁰) to the atmosphere, as does the flaring of landfill gas. Waste storage and processing before its addition to the landfill also has the potential to release Hg⁰ to the air if it is initially present or formed by chemical reduction of Hg^II to Hg⁰ within collected waste. We measured the release of Hg vapor to the atmosphere during dumpster and transfer station activities and waste storage before landfilling at a municipal landfill operation in central Florida. We also quantified the potential contribution of specific Hg-bearing wastes, including mercury (Hg) thermometers and fluorescent bulbs, and searched for primary Hg sources in sorted wastes at three different landfills. Surprisingly large fluxes were estimated for Hg losses at transfer facilities (～100 mg/hr) and from dumpsters in the field (～30 mg/hr for 1,000 dumpsters), suggesting that Hg emissions occurring before landfilling may constitute a significant fraction of the total emission from the disposal/landfill cycle and a need for more measurements on these sources. Reducing conditions of landfill burial were obviously not needed to generate strong Hg⁰ signals, indicating that much of the Hg was already present in a metallic (Hg⁰) form. Attempts to identify specific Hg sources in excavated and sorted waste indicated few readily identifiable sources; because of effective mixing and diffusion of Hg⁰, the entire waste mass acts as a source. Broken fluorescent bulbs and thermometers in dumpsters emitted Hg⁰ at 10 to >100 μg/hr and continued to act as near constant sources for several days.     

Characterization of Activated Carbon Fiber Filters for Pressure Drop,Submicrometer Particulate Collection,and Mercury Capture

ABSTRACT

The use of activated carbon fiber (ACF) filters for the capture of particulate matter and elemental Hg is demonstrated. The pressure drop and particle collection efficiency characteristics of the ACF filters were established at two different face velocities and for two different aerosols: spherical NaCl and combustion-generated silica particles. The clean ACF filter specific resistance was 153 kg m^-2 sec^-1. The experimental specific resistance for cake filtration was 1.6 × 10⁶ sec^-1 and 2.4 × 10⁵ sec^-1 for 0.5- and 1.5-μm mass median diameter particles, respectively. The resistance factor R was approximately 2, similar to that for the high-efficiency particulate air filters. There was a discrepancy in the measured particle collection efficiencies and those predicted by theory. The use of the ACF filter for elemental Hg capture was illustrated, and the breakthrough characteristic was established. The capacity of the ACF filter for Hg capture was similar to other powdered activated carbons.     

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.     

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.     

A reactive transport model for mercury fate in soil—application to different anthropogenic pollution sources

Soil systems are a common receptor of anthropogenic mercury (Hg) contamination. Soils play an important role in the containment or dispersion of pollution to surface water, groundwater or the atmosphere. A one-dimensional model for simulating Hg fate and transport for variably saturated and transient flow conditions is presented. The model is developed using the HP1 code, which couples HYDRUS-1D for the water flow and solute transport to PHREEQC for geochemical reactions. The main processes included are Hg aqueous speciation and complexation, sorption to soil organic matter, dissolution of cinnabar and liquid Hg, and Hg reduction and volatilization. Processes such as atmospheric wet and dry deposition, vegetation litter fall and uptake are neglected because they are less relevant in the case of high Hg concentrations resulting from anthropogenic activities. A test case is presented, assuming a hypothetical sandy soil profile and a simulation time frame of 50 years of daily atmospheric inputs. Mercury fate and transport are simulated for three different sources of Hg (cinnabar, residual liquid mercury or aqueous mercuric chloride), as well as for combinations of these sources. Results are presented and discussed with focus on Hg volatilization to the atmosphere, Hg leaching at the bottom of the soil profile and the remaining Hg in or below the initially contaminated soil layer. In the test case, Hg volatilization was negligible because the reduction of Hg²⁺ to Hg⁰ was inhibited by the low concentration of dissolved Hg. Hg leaching was mainly caused by complexation of Hg²⁺ with thiol groups of dissolved organic matter, because in the geochemical model used, this reaction only had a higher equilibrium constant than the sorption reactions. Immobilization of Hg in the initially polluted horizon was enhanced by Hg²⁺ sorption onto humic and fulvic acids (which are more abundant than thiols). Potential benefits of the model for risk management and remediation of contaminated sites are discussed.     

湿式烟气脱硫系统同时脱汞研究

研究表明，湿法烟气脱硫装置(WFGD)可去除烟气中绝大部分Hg²⁺，但对单质汞的吸收效果不明显，因此研究提高湿法烟气脱硫系统中单质汞的氧化率的方法对控制汞的排放具有重要意义。综述了WFGD及在此系统中各种添加剂的脱汞性能，认为在添加剂中，气态的臭氧、液态的次氯酸和氯化钠稀溶液、 黄磷乳浊液、氢硫化钠溶液及EDTA的汞去除效果较好，且不会被SO₂大量消耗，可在WFGD系统实现同时脱硫脱汞；而气态的氯气，液态的K₂S₂O₈溶液虽然也有较好的汞去除效果，但因易被SO₂或亚硫酸盐溶液消耗，当在WFGD系统中用其氧化单质汞时，需要对脱硫塔进行分层或其他改造，使烟气中的SO₂被吸收后再控制汞，提高经济性。