Mercury-Organic Matter Interactions in Soils and Sediments: Angel or Devil?

Many studies have suggested that organic matter (OM) substantially reduces the bioavailability and risks of mercury (Hg) in soils and sediments; however, recent reports have supported that OM greatly accelerates Hg methylation and increases the risks of Hg exposure. This study aims to summarize the interactions between Hg and OM in soils and sediments and improve our understanding of the effects of OM on Hg methylation. The results show that OM characteristics, promotion of the activity of Hg-methylating microbial communities, and the microbial availability of Hg accounted for the acceleration of Hg methylation which increases the risk of Hg exposure. These three key aspects were driven by multiple factors, including the types and content of OM, Hg speciation, desorption and dissolution kinetics and environmental conditions.

Hierarchical Ag-SiO2@Fe3O4 magnetic composites for elemental mercury removal from non-ferrous metal smelting flue gas.

Hierarchical Ag-SiO2@Fe3O4 magnetic composites were selected for elemental mercury (Hg0) removal from non-ferrous metal smelting flue gas in this study. Results showed that the hierarchical Ag-SiO2@Fe3O4 magnetic composites had favorable Hg0 removal ability at low temperature. Moreover, the adsorption capacity of hierarchical magnetic composite is much larger than that of pure Fe3O4 and SiO2@Fe3O4. The Hg0 removal efficiency reached the highest value as approximately 92% under the reaction temperature of 150°C, while the removal efficiency sharply reduced in the absence of O2. The characterization results indicated that Ag nanoparticles grew on the surface of SiO2@Fe3O4 support. The large surface area of SiO2 supplied efficient reaction room for Hg and Ag atoms. Ag-Hg amalgam is generated on the surface of the composites. In addition, this magnetic material could be easily separated from fly ashes when adopted for treating real flue gas, and the spent materials could be regenerated using a simple thermal-desorption method.

Integrated removal of NO and mercury from coal combustion flue gas using manganese oxides supported on TiO2.

A catalyst composed of manganese oxides supported on titania (MnOx/TiO2) synthesized by a sol-gel method was selected to remove nitric oxide and mercury jointly at a relatively low temperature in simulated flue gas from coal-fired power plants. The physico-chemical characteristics of catalysts were investigated by X-ray fluorescence (XRF), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) analyses, etc. The effects of Mn loading, reaction temperature and individual flue gas components on denitration and Hg0 removal were examined. The results indicated that the optimal Mn/Ti molar ratio was 0.8 and the best working temperature was 240°C for NO conversion. O2 and a proper ratio of [NH3]/[NO] are essential for the denitration reaction. Both NO conversion and Hg0 removal efficiency could reach more than 80% when NO and Hg0 were removed simultaneously using Mn0.8Ti at 240°C. Hg0 removal efficiency slightly declined as the Mn content increased in the catalysts. The reaction temperature had no significant effect on Hg0 removal efficiency. O2 and HCl had a promotional effect on Hg0 removal. SO2 and NH3 were observed to weaken Hg0 removal because of competitive adsorption. NO first facilitated Hg0 removal and then had an inhibiting effect as NO concentration increased without O2, and it exhibited weak inhibition of Hg0 removal efficiency in the presence of O2. The oxidation of Hg0 on MnOx/TiO2 follows the Mars-Maessen and Langmuir-Hinshelwood mechanisms.

Selenium as an antidote in the treatment of mercury intoxication.

Selenium (Se) is an essential trace element for humans. It is found in the enzyme glutathione peroxidase. This enzyme protects the organism against certain types of damage. Some data suggest that Se plays a role in the body's metabolism of mercury (Hg). Selenium has in some studies been found to reduce the toxicity of Hg salts. Selenium and Hg bind in the body to each other. It is not totally clear what impact the amount of Se has in the human body on the metabolism and toxicity of prolonged Hg exposure.

Effective solidification/stabilisation of mercury-contaminated wastes using zeolites and chemically bonded phosphate ceramics.

In this study, two kinds of zeolites materials (natural zeolite and thiol-functionalised zeolite) were added to the chemically bonded phosphate ceramic processes to treat mercury-contaminated wastes. Strong promotion effects of zeolites (natural zeolite and thiol-functionalised zeolite) on the stability of mercury in the wastes were obtained and these technologies showed promising advantages toward the traditional Portland cement process, i.e. using Portland cement as a solidification agent and natural or thiol-functionalised zeolite as a stabilisation agent. Not only is a high stabilisation efficiency (lowered the Toxicity Characteristic Leaching Procedure Hg by above 10%) obtained, but also a lower dosage of solidification (for thiol-functionalised zeolite as stabilisation agent, 0.5 g g(-1) and 0.7 g g(-1) for chemically bonded phosphate ceramic and Portland cement, respectively) and stabilisation agents (for natural zeolite as stabilisation agent, 0.35 g g(-1) and 0.4 g g(-1) for chemically bonded phosphate ceramic and Portland cement, respectively) were used compared with the Portland cement process. Treated by thiol-functionalised zeolite and chemically bonded phosphate ceramic under optimum parameters, the waste containing 1500 mg Hg kg(-1) passed the Toxicity Characteristic Leaching Procedure test. Moreover, stabilisation/solidification technology using natural zeolite and chemically bonded phosphate ceramic also passed the Toxicity Characteristic Leaching Procedure test (the mercury waste containing 625 mg Hg kg(-1)). Moreover, the presence of chloride and phosphate did not have a negative effect on the chemically bonded phosphate ceramic/thiol-functionalised zeolite treatment process; thus, showing potential for future application in treatment of 'difficult-to-manage' mercury-contaminated wastes or landfill disposal with high phosphate and chloride content.

Economic analysis of atmospheric mercury emission control for coal-fired power plants in China.

Coal combustion and mercury pollution are closely linked, and this relationship is particularly relevant in China, the world's largest coal consumer. This paper begins with a summary of recent China-specific studies on mercury removal by air pollution control technologies and then provides an economic analysis of mercury abatement from these emission control technologies at coal-fired power plants in China. This includes a cost-effectiveness analysis at the enterprise and sector level in China using 2010 as a baseline and projecting out to 2020 and 2030. Of the control technologies evaluated, the most cost-effective is a fabric filter installed upstream of the wet flue gas desulfurization system (FF+WFGD). Halogen injection (HI) is also a cost-effective mercury-specific control strategy, although it has not yet reached commercial maturity. The sector-level analysis shows that 193 tons of mercury was removed in 2010 in China's coal-fired power sector, with annualized mercury emission control costs of 2.7 billion Chinese Yuan. Under a projected 2030 Emission Control (EC) scenario with stringent mercury limits compared to Business As Usual (BAU) scenario, the increase of selective catalytic reduction systems (SCR) and the use of HI could contribute to 39 tons of mercury removal at a cost of 3.8 billion CNY. The economic analysis presented in this paper offers insights on air pollution control technologies and practices for enhancing atmospheric mercury control that can aid decision-making in policy design and private-sector investments.

Hg0 removal from flue gas over different zeolites modified by FeCl3.

The elemental mercury removal abilities of three different zeolites (NaA, NaX, HZSM-5) impregnated with iron(III) chloride were studied on a lab-scale fixed-bed reactor. X-ray diffraction, nitrogen adsorption porosimetry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption (TPD) analyses were used to investigate the physicochemical properties. Results indicated that the pore structure and active chloride species on the surface of the samples are the key factors for physisorption and oxidation of Hg0, respectively. Relatively high surface area and micropore volume are beneficial to efficient mercury adsorption. The active Cl species generated on the surface of the samples were effective oxidants able to convert elemental mercury (Hg0) into oxidized mercury (Hg2+). The crystallization of NaCl due to the ion exchange effect during the impregnation of NaA and NaX reduced the number of active Cl species on the surface, and restricted the physisorption of Hg0. Therefore, the Hg0 removal efficiencies of the samples were inhibited. The TPD analysis revealed that the species of mercury on the surface of FeCl3-HZSM-5 was mainly in the form of mercuric chloride (HgCl2), while on FeCl3-NaX and FeCl3-NaA it was mainly mercuric oxide (HgO).

Regenerable cobalt oxide loaded magnetosphere catalyst from fly ash for mercury removal in coal combustion flue gas.

To remove Hg(0) in coal combustion flue gas and eliminate secondary mercury pollution of the spent catalyst, a new regenerable magnetic catalyst based on cobalt oxide loaded magnetospheres from fly ash (Co-MF) was developed. The catalyst, with an optimal loading of 5.8% cobalt species, attained approximately 95% Hg(0) removal efficiency at 150 °C under simulated flue gas atmosphere. O2 could enhance the Hg(0) removal activity of magnetospheres catalyst via the Mars-Maessen mechanism. SO2 displayed an inhibitive effect on Hg(0) removal capacity. NO with lower concentration could promote the Hg(0) removal efficiency. However, when increasing the NO concentration to 300 ppm, a slightly inhibitive effect of NO was observed. In the presence of 10 ppm of HCl, greater than 95.5% Hg(0) removal efficiency was attained, which was attributed to the formation of active chlorine species on the surface. H2O presented a seriously inhibitive effect on Hg(0) removal efficiency. Repeated oxidation-regeneration cycles demonstrated that the spent Co-MF catalyst could be regenerated effectively via thermally treated at 400 °C for 2 h.

Removal of vapor-phase elemental mercury from stack emissions with sulfur-impregnated activated carbon.

This systematic review of high-quality, relevant original research articles existing in the literature was conducted to comprehensively explore the efficiency of Hg11 capture from stack emissions by sulfur-impregnated vs. virgin ACs. Our systematic overview suggested that significantly higher amounts of Hg0 are absorbed by sulfurimpregnated ACs than by virgin ones ( 1.5-32 times higher, based on the applied operational conditions). The main reason for this is because Hg11 capture by virgin ACs follows a physisorption mechanism, whereas that by sulfur-impregnated ACs occurs from a combination of physisorption of Hg11 on carbon texture and chemical reaction between Hg0 and impregnated sulfur, with subsequent formation of HgS. Temperature increased the Hg0 adsorption capacity of virgin ACs, especially when temperatures exceeded 100 oc. For sulfur-impregnated ACs, increasing the temperature up to I 00 oc increased the Hg0 adsorption capacity by enhancing the chemisorption of Hg0 capture. A further increase in temperature enhanced the efficiency of ACs that were impregnated with Sat higher temperatures (600 °C, for instance). This mainly resulted from production of stronger bonding of sulfur to carbon at higher impregnation temperatures and also from a more even distribution of sulfur in the carbon matrix. The authors of different papers reported different results with respect to whether there is an effect of initial Hg11 concentration on AC adsorption capacity. The authors of two studies could find no such etl'ect. The predominant evidence, however, favors the view that increased Hg0 adsorption capacities exist at higher inlet Hg0 concentrations. Such behavior is attributed to faster kinetics of Hg0 capture and an enhanced higher driving force at higher initial Hg0 inlet concentrations. Results from reviewed studies also indicated that the optimum SIC ratio and sulfur content are 2/1 and I 0-20%, respectively. Surface area has a less significant impact on Hg11 adsorption capacity than does sulfur content. However, at equivalent sulfur content, AC surface area also becomes an important factor, in that Hg0 adsorption capacity is accentuated at higher surface areas. We conclude from having prepared this review that sulfur-impregnated ACs have significantly greater efficiencies than virgin ACs for capturing Hg0 from stack emissions. Therefore, using them is more cost effective than using raw ACs; using them can also partly resolve the problem of high costs posed by applying carbon sorbents. In addition, the sulfur deposited in the ACs impregnated at higher temperatures is more evenly distributed in the carbon micropores and binds more strongly to the carbon matrix. Hence, sulfur-impregnated ACs can retain higher Hg0 adsorption capacities under actual stack conditions, if the temperature is at least 140 oc. Finally, since the major mechanism for Hg'l removal by sulfur-impregnated ACs is through the chemical reaction between Hg0 and S. and subsequent formation via strong bonds of HgS, the Hg'i adsorbed on ACs is quite stable and is not easily released when discharged as waste to the environment.

Investigation on mercury reemission from limestone-gypsum wet flue gas desulfurization slurry.

Secondary atmospheric pollutions may result from wet flue gas desulfurization (WFGD) systems caused by the reduction of Hg(2+) to Hg(0) and lead to a damping of the cobenefit mercury removal efficiency by WFGD systems. The experiment on Hg(0) reemission from limestone-gypsum WFGD slurry was carried out by changing the operating conditions such as the pH, temperature, Cl(-) concentrations, and oxygen concentrations. The partitioning behavior of mercury in the solid and liquid byproducts was also discussed. The experimental results indicated that the Hg(0) reemission rate from WFGD slurry increased as the operational temperatures and pH values increased. The Hg(0) reemission rates decreased as the O2 concentration of flue gas and Cl(-) concentration of WFGD slurry increased. The concentrations of O2 in flue gas have an evident effect on the mercury retention in the solid byproducts. The temperature and Cl(-) concentration have a slight effect on the mercury partitioning in the byproducts. No evident relation was found between mercury retention in the solid byproducts and the pH. The present findings could be valuable for industrial application of characterizing and optimizing mercury control in wet FGD systems.

Gas-phase elemental mercury removal from flue gas by cobalt-modified fly ash at low temperatures.

Co modified fly ash (FA) prepared by the wet impregnation method was investigated for gas-phase elemental mercury capture under air at 80°C in this paper. X-ray fluorescence spectrometry, Brunauer-Emmett-Teller, scanning electron micrographs, X-ray diffraction, thermogravimetric (TG) analysis and X-ray photoelectron spectroscopy (XPS) were employed to characterize the samples. Experimental results showed that the optimal Co loading was 9 wt%, which gave a Hg(0) removal efficiency of 76% in a laboratory packed-bed reactor at low temperatures in the presence of O2. The high removal efficiency was mainly attributed to oxidation of Hg(0) by the enrichment of well-dispersed Co3O4on the surface of FA. However, higher Co loading resulted in the decrease of removal efficiency due to the decline of surface area and Co3O4agglomeration. TG and XPS characterization indicated that Hg(0) was oxidized by Co3O4and some of the oxidized mercury formed recombination mercury oxide with Co3O4, which could either exist stably at low temperature or be desorbed from the adsorbents at higher temperature. Finally, the possible adsorption mechanisms were proposed according to the observed phenomena.

A critical review on the heterogeneous catalytic oxidation of elemental mercury in flue gases.

Nowadays, an increasing attention has been paid to the technologies for removing mercury from flue gases. Up to date, no optimal technology that can be broadly applied exists, but the heterogeneous catalytic oxidation of mercury is considered as a promising approach. Based on a brief introduction of the pros and cons of traditional existing technologies, a critical review on the recent advances in heterogeneous catalytic oxidation of elemental mercury is provided. In this contribution, four types of Hg oxidation catalysts including noble metals, selective catalytic reduction (SCR) catalysts, transition metals, and fly ash have been summarized. Both the advantages and disadvantages of these catalysts are described in detail. The influence of various acidic gases including SO2, SO3, NH3, NOx, HCl, Cl2, etc. have been discussed as well. We expect this work will shed light on the development of heterogeneous catalytic oxidation of elemental mercury technology in flue gases, particularly the synthesis of novel and highly efficient Hg(0) oxidation catalysts.

Whole-lake nitrate addition for control of methylmercury in mercury-contaminated Onondaga Lake, NY.

Methylmercury (MeHg) strongly bioaccumulates in aquatic food webs resulting in exposure to humans and wildlife through consumption of fish. Production of MeHg is promoted by anaerobic conditions and the supply of inorganic Hg (Hg(2+)), sulfate (SO4(2-)), and labile organic carbon. The anaerobic sediments of stratified lakes are particularly active zones for methylation of Hg(2+) and can be an important source of MeHg to the water column during summer anoxia and fall turnover. Nitrate (NO3(-)) addition has recently been proposed as a novel approach for the control of MeHg accumulation in the hypolimnia of Hg-contaminated lakes. In 2011, a whole-lake NO3(-) addition pilot test was conducted in Hg-contaminated Onondaga Lake, NY with the objective of limiting release of MeHg from the pelagic sediments to the hypolimnion through maintenance of NO3(-)-N concentrations >1mgN/L. A liquid calcium-nitrate solution was added to the hypolimnion as a neutrally buoyant plume approximately three times per week during the summer stratification interval. Maximum hypolimnetic concentrations of MeHg and soluble reactive phosphorus (SRP) decreased 94% and 95% from 2009 levels, suggesting increased sorption to Fe and Mn oxyhydroxides in surficial sediments as the regulating mechanism. Increased MeHg concentrations in the upper waters during fall turnover, which had been a generally recurring pattern, did not occur in 2011, resulting in decreased exposure of aquatic organisms to MeHg. Over the 1992-2011 interval, the hypolimnetic NO3(-) supply explained 85% and 95% of the interannual variations in hypolimnetic accumulations of SRP and MeHg, respectively.

Removal of mercury bonded in residual glass from spent fluorescent lamps.

The current technologies available for recycling fluorescent lamps do not completely remove the phosphor powder attached to the surface of the glass. Consequently, the glass contains the mercury diffused through the glass matrix and the mercury deposited in the phosphor powder that has not been removed during treatment at the recycling plant. A low-cost process, with just one stage, which can be used to remove the layer of phosphor powder attached to the surface of the glass and its mercury was studied. Several stirring tests were performed with different extraction mixtures, different liquid-solid ratios, and different agitation times. The value of the initial mercury concentration of the residual glass was 2.37 ± 0.50 µg/g. The maximum extraction percentage was 68.38%, obtained by stirring for 24 h with a liquid-solid ratio of 10 and using an extraction solution with 5% of an acid mixture prepared with HCl and HNO(3) at a ratio of 3:1 by volume. On an industrial scale the contact time could be reduced to 8 h without significantly lowering the percentage of mercury extracted. In fact, 64% of the mercury was extracted.

Gaseous elemental mercury capture from flue gas using magnetic nanosized (Fe3-xMnx)1-δO4.

A series of nanosized (Fe3-xMnx)1-δO4 (x = 0, 0.2, 0.5, and 0.8) were synthesized for elemental mercury capture from the flue gas. Cation vacancies on (Fe3-xMnx)1-δO4 can provide the active sites for elemental mercury adsorption, and Mn(4+) cations on (Fe3-xMnx)1-δO4 may be the oxidizing agents for elemental mercury oxidization. With the increase of Mn content in the spinel structure, the percents of Mn(4+) cations and cation vacancies on the surface increased. As a result, elemental mercury capture by (Fe3-xMnx)1-δO4 was obviously promoted with the increase of Mn content. (Fe2.2Mn0.8)1-δO4 showed an excellent capacity for elemental mercury capture (>1.5 mg g(-1) at 100-300 °C) in the presence of SO2 and HCl. Furthermore, (Fe2.2Mn0.8)1-δO4 with the saturation magnetization of 45.6 emu g(-1) can be separated from the fly ash using magnetic separation, leaving the fly ash essentially free of sorbent and adsorbed Hg. Therefore, nanosized (Fe2.2Mn0.8)1-δO4 may be a promising sorbent for the control of elemental mercury emission.

Bioavailable mercury cycling in polar snowpacks.

Polar regions are subject to contamination by mercury (Hg) transported from lower latitudes, severely impacting human and animal health. Atmospheric Mercury Depletion Events (AMDEs) are an episodic process by which Hg is transferred from the atmospheric reservoir to arctic snowpacks. The fate of Hg deposited during these events is the subject of numerous studies, but its speciation remains unclear, especially in terms of environmentally relevant forms such as bioavailable mercury (BioHg). Here, using a bacterial mer-lux biosensor, we report the fraction of newly deposited Hg at the surface and at the bottom of the snowpack that is bioavailable. Snow samples were collected over a two-month arctic field campaign in 2008. In surface snow, BioHg is related to atmospheric Hg deposition and snow fall events were shown to contribute to higher proportions of BioHg than AMDEs. Based on our data, AMDEs represent a potential source of 20 t.y(-1) of BioHg, while wet and dry deposition pathways may provide 135-225 t.y(-1) of BioHg to Arctic surfaces.

Significance of RuO2 modified SCR catalyst for elemental mercury oxidation in coal-fired flue gas.

Catalytic conversion of elemental mercury (Hg(0)) to its oxidized form has been considered as an effective way to enhance mercury removal from coal-fired power plants. In order to make good use of the existing selective catalytic reduction of NO(x) (SCR) catalysts as a cobenefit of Hg(0) conversion at lower level HCl in flue gas, various catalysts supported on titanium dioxide (TiO(2)) and commercial SCR catalysts were investigated at various cases. Among the tested catalysts, ruthenium oxides (RuO(2)) not only showed rather high catalytic activity on Hg(0) oxidation by itself, but also appeared to be well cooperative with the commercial SCR catalyst for Hg(0) conversion. In addition, the modified SCR catalyst with RuO(2) displayed an excellent tolerance to SO(2) and ammonia without any distinct negative effects on NO(x) reduction and SO(2) conversion. The demanded HCl concentration for Hg(0) oxidation can be reduced dramatically, and Hg(0) oxidation efficiency over RuO(2) doped SCR catalyst was over 90% even at about 5 ppm HCl in the simulated gases. Ru modified SCR catalyst shows a promising prospect for the cobenefit of mercury emission control.

Conversion of elemental mercury with a novel membrane delivery catalytic oxidation system (MDCOs).

In order to overcome the shortcomings of the traditional catalytic oxidation (TCO) mode for the conversion of the trace level of elemental mercury (Hg(0)) in flue gas, we put forward a novel and unique assembly that integrated membrane delivery with catalytic oxidation systems (MDCOs), which combined the controlled delivery of oxidants with the catalytic oxidation of Hg(0). The results show that the demanded HCl for Hg(0) conversion in the MDCOs was less than 5% of that in the TCO mode, and over 90% of Hg(0) removal efficiency can be obtained in the MDCOs with less than 0.5 mg m(-3) of HCl escaped. Meanwhile, the inhibition of SO(2) to Hg(0) catalytic conversion in the MDCOs was also less significant than in the TCO. The MDCOs have high retainability for HCl, which is quite favorable to Hg(0) conversion and HCl utilization. The reaction mechanism on mercury conversion in the MDCOs is discussed. The MDCOs appear to be a promising method for emission control of elemental mercury.

Hair methylmercury: a new indication for therapeutic monitoring.

Maternal exposure to methylmercury can adversely affect fetal neurodevelopment. Long-term mercury exposure is best estimated by hair measurement of the metal. The authors analyzed the appropriateness of therapeutic monitoring of hair mercury in women of reproductive age using widely accepted criteria for therapeutic drug monitoring. The analysis reveals that such monitoring can help protect babies from long-term adverse effects, while ensuring appropriate maternal fish consumption.

Evaluation of mercury speciation and removal through air pollution control devices of a 190 MW boiler.

Air pollution control devices (APCDs) are installed at coal-fired power plants for air pollutant regulation. Selective catalytic reduction (SCR) and wet flue gas desulfurization (FGD) systems have the co-benefits of air pollutant and mercury removal. Configuration and operational conditions of APCDs and mercury speciation affect mercury removal efficiently at coal-fired utilities. The Ontario Hydro Method (OHM) recommended by the U.S. Environmental Protection Agency (EPA) was used to determine mercury speciation simultaneously at five sampling locations through SCR-ESP-FGD at a 190 MW unit. Chlorine in coal had been suggested as a factor affecting the mercury speciation in flue gas; and low-chlorine coal was purported to produce less oxidized mercury (Hg2+) and more elemental mercury (Hg0) at the SCR inlet compared to higher chlorine coal. SCR could oxidize elemental mercury into oxidized mercury when SCR was in service, and oxidation efficiency reached 71.0%. Therefore, oxidized mercury removal efficiency was enhanced through a wet FGD system. In the non-ozone season, about 89.5%-96.8% of oxidized mercury was controlled, but only 54.9%-68.8% of the total mercury was captured through wet FGD. Oxidized mercury removal efficiency was 95.9%-98.0%, and there was a big difference in the total mercury removal efficiencies from 78.0% to 90.2% in the ozone season. Mercury mass balance was evaluated to validate reliability of OHM testing data, and the ratio of mercury input in the coal to mercury output at the stack was from 0.84 to 1.08.