Gaseous elemental mercury concentration in atmosphere at urban and remote sites in China

An investigation of gaseous elemental mercury concentration in atmosphere was conducted at Beijing and Guangzhou urban, Yangtze Delta regional sites and China Global Atmosphere Watch Baseline Observatory （CGAWBO） in Mt. Waliguan of remote continental area of China. High temporal resolved data were obtained using automated mercury analyzer RA-915^＋. Results showed that the overall hourly mean Hg^0 concentrations in Mt. Waliguan were 1.7±1.1 ng/m3 in summer and 0.6±0.08 ng/m^3 in winter. The concentration in Yangtze Delta regional site was 5.4±4.1 ng/m^3, which was much higher than those in Waliguan continental background area and also higher than that found in North America and Europe rural areas. In Beijing urban area the overall hourly mean Hg^0 concentrations were 8.3±3.6 ng/m^3 in winter, 6.5±5.2 ng/m^3 in spring, 4.9±3.3 ng/m^3 in summer, and 6.7±3.5 ng/m^3 in autumn, respectively, and the concentration was 13.5±7.1 ng/m^3 in Guangzhou site. The mean concentration reached the lowest value at 14：00 and the highest at 02：00 or 20：00 in all monitoring campaigns in Beijing and Guangzhou urban areas, which contrasted with the results measured in Yangtze Delta regional site and Mr. Waliguan. The features of concentration and diurnal variation of Hg^0 in Beijing and Guangzhou implied the importance of local anthropogenic sources in contributing to the high Hg^0 concentration in urban areas of China. Contrary seasonal variation patterns of Hg^0 concentration were found between urban and remote sites. In Beijing the highest Hg^0 concentration was in winter and the lowest in summer, while in Mt. Waliguan the Hg^0 concentration in summer was higher than that in winter. These indicated that different processes and factors controlled Hg^0 concentration in urban, regional and remote areas.

Analysis of solid sorbents for control and removal processes for elemental mercury from gas streams:a review

Due to the restriction such as the Minamata Convention as well as the IED of the European Commission,mercury removal from flue gases of coal-fired power plants(CPP)is an increasingly important environmental issue.This makes this topic very crucial for both the energy industry and scientists.This paper shows how mercury arises from natural resources,i.e.,coals,through their combustion processes in CPP and considers the issue of mercury content in flue gases and solid-state coal combustion by-products.The main part of this paper presents a review of the solid sorbents available for elemental mercury control and removal processes,tested on a laboratory scale.The described solutions have a potential for wider usage in exhaust gas treatment processes in the energy production sector.These solutions represent the latest developments in the field of elemental mercury removal from gases.The authors present an overview of the wide range of solid sorbents and their modifications intended to increase affinity for Hg^(0).Among the presented sorbents are the wellknown activated carbon solutions but also novel modifications to these and other innovative sorbent proposals based on,e.g.,zeolites,biochars,other carbon-based materials,metal-organic frameworks.The paper presents a wide range of characteristics of the described sorbents,as well as the conditions for the Hg^(0) removal experiments summarizing the compendium of novel solid sorbent solutions dedicated to the removal of elemental mercury from gases.

Regulated adsorption sites using atomically single cluster over biochar for efficient elemental mercury uptake

Carbon-based materials have been widely used in gaseous pollutant removal because of their sufficient surface functional groups;however,its removal efficiency for elemental mercury(Hg^(0))is low.In this study,we fabricated biomass using a chelated coupled pyrolysis strategy and further constructed the regulated adsorption sites for gaseous Hg^(0) uptake.A series of Mnδ-N_(2)O_(2)/BC with different manganese cluster sizes demonstrated that manganese clusters anchored on biochar acted as highly active and durable adsorbents for Hg^(0) immobilization,which increased the adsorption efficiency of Hg^(0) by up to 50%.Shrimp-and crab-based biochar adsorbents exhibited excellent Hg^(0) removal because of their chitosan-like structure.In particular,small Mn clusters and oxygen species around the defect led to a boost in the Hg^(0) adsorption by carbon.The results of density functional theory calculation revealed that the presence of oxygen in the carbon skeleton can tune the electrons of small-sized Mn clusters,thereby promoting the affinity of mercury atoms.The newly developed Mnδ-N_(2)O_(2)/BC_(shrimp) had an adsorption capacity of 7.98-11.52 mg g^(−1) over a broad temperature range(50-200℃)and showed a high tolerance to different industrial flue gases(H_(2)O,NO,HCl,and SO_(2)).These results provide novel green and low-carbon disposal methods for biomass resource utilization and industrial Hg^(0) emission control.

Catalytic oxidation of gas-phase elemental mercury by nano-Fe_2 O_3

Heterogeneous oxidation of gas-phase Hg 0 by nano-Fe 2 O 3 was investigated on a fixed bed reactor, and the effects of oxygen concentration, bed temperature, water vapour concentration and particle size have been discussed. The results showed that Hg 0 could be oxidized by active oxygen atom on the surface of nano-Fe 2 O 3 as well as lattice oxygen in nano-Fe 2 O 3 . Among the factors that affect Hg 0 oxidation by nano-Fe 2 O 3 , bed temperature plays an important role. More than 40% of total mercury was oxidized at 300°C, however, the test temperature at 400°C could cause sintering of nano-catalyst, which led to a lower efficiency of Hg 0 oxidation. The increase of oxygen concentration could promote mercury oxidation and led to higher Hg 0 oxidation efficiency. No obvious mercury oxidation was detected in the pure N 2 atmosphere, which indicates that oxygen is required in the gas stream for mercury oxidation. The presence of water vapour showed different effects on mercury oxidation depending on its concentration. The lower content of water vapour could promote mercury oxidation, while the higher content of water vapour inhibits mercury oxidation.

Absorption characteristics of elemental mercury in mercury chloride solutions

Elemental mercury （Hg^0） in flue gases can be efficiently captured by mercury chloride （HgCl2） solution. However, the absorption behaviors and the influencing effects are still poorly understood. The mechanism of Hg^0 absorption by HgCl2 and the factors that control the removal were studied in this paper. It was found that when the mole ratio of Cl^- to HgCl2 is 10：1, the Hg^0 removal efficiency is the highest. Among the main mercury chloride species, HgCl3^- is the most efficient ion for Hg^0 removal in the HgCl2 absorption system when moderate concentrations of chloride ions exist. The Hg^0 absorption reactions in the aqueous phase were investigated computationaIIy using Moller-Plesset perturbation theory. The calculated Gibbs free energies and energy barriers are in excellent agreement with the results obtained from experiments. In the presence of SO3^2- and SO2, Hg^2＋ reduction occurred and Hg^0 removal efficiency decreased. The reduced Hg^0 removal can be controlled through increased chloride concentration to some degree. Low pH value in HgCla solution enhanced the Hg^0 removal efficiency, and the effect was more significant in dilute HgCl2 solutions. The presence of SO4^2- and NO3^- did not affect Hg^0 removal by HgCl2.

Removal of elemental mercury with Mn/Mo/Ru/Al2O3 membrane catalytic system

In this work, a catalytic membrane using Mn/ Mo/Ru/A12O3 as the catalyst was employed to remove elemental mercury （Hg^0） from flue gas at low temperature. Compared with traditional catalytic oxidation （TCO） mode, Mn/A12O3 membrane catalytic system had much higher removal efficiency of Hg^0. After the incorporation of Mo and Ru, the production of C12 from the Deacon reaction and the retainability for oxidants over Mn/A12O3 membrane were greatly enhanced. As a result, the oxidization of Hg^0 over Mn/A12O3 membrane was obviously promoted due to incorporation of Mo and Ru. In the presence of 8 ppmv HC1, the removal efficiency of Hg^0 by Mn/Mo/Ru/A12O3 membrane reached 95% at 423 K. The influence of NO and SO2 on Hg^0 removal were insignificant even if 200 ppmv NO and 1000 ppmv SO2 were used. Moreover, compared with the TCO mode, the Mn/Mo/Ru/A12O3 membrane catalytic system could remarkably reduce the demanded amount of oxidants for Hg^0 removal. Therefore, the Mn/Mo/Ru/A12O3 membrane catalytic system may be a promising technology for the control of Hg~ emission.

Removal of elemental mercury by KI-impregnated clay

This study described the use of clay impreg- nated by KI in gas phase elemental mercury （Hg°） removal in flue gas. The effects of KI loading, temperature, 02, SO2 and H20 on Hg°removal were investigated using a fixed bed reactor. The Hg° removal efficiency of KI-clay with 3% KI loading could maintain at a high level （approxi- mately 80 %） after 3 h. The KI-clay demonstrated to be a potential adsorbent for Hg° removal when compared with activated carbon based adsorbent. 02 was found to be an important factor in improving the Hg° removal. 02 was demonstrated to assist the transfer of KI to I2 on the surface of KI-clay, which could react with Hg° directly. NO and SO2 could slightly improve Hg° removal, while H20 inhibited it greatly. The results indicated that after adsorption, most of the mercury escaped from the surface again. Some of the mercury may have been oxidized as it left the surface. The results demonstrated that the chemical reaction primarily occurred between KI and mercury on the surface of the KI-clay.

Simultaneous removal of gaseous CO and elemental mercury over Cu-Co modified activated coke at low temperature

Cu-Co multiple-oxides modified on HNO_3-pretreated activated coke(AC_(N))were optimized for the simultaneous removal of gaseous CO and elemental mercury(Hg^(0))at low temperature(<200℃).It was found that 2%CuOx-10%CoOx/AC_(N)catalyst calcined at 400℃resulted in the coexistence of complex oxides including CuO,Cu_2 O,Co_(3)O_(4,Co_(2)O_(3)and CoO phases,which might be good for the simultaneous catalytic oxidation of CO by Co-species and removal of Hg^(0)by Cu-species,benefiting from the synergistic catalysis during the electrointeraction between Go and Cu cations(CoO■Co_(3)O_(4)and Cu_(2)O■CuO).The catalysis removal of CO oxidation was obviously depended on the reaction temperature obtaining94.7%at 200℃,while no obvious promoting effect on the Hg^(0)removal(68.3%-78.7%).These materials were very substitute for the removal of CO and Hg^(0)from the flue gas with the conditions of 8-20 vol.%O_(2)and flue-gas temperature below 200℃.The removal of Hg^(0)followed the combination processes of adsorption and catalytic oxidation reaction via LangmuirHinshelwood mechanism,while the catalysis of CO abided by the Mars-van Krevelen mechanism with lattice oxygen species.

Hg^0 absorption in potassium persulfate solution

The aqueous phase oxidation of gaseous elemental mercury (Hg0) by potassium persulfate (KPS) catalyzed by Ag+ was investigated using a glass bubble column reactor. Concentration of gaseous mercury and potassium persulfate were measured by cold vapor atom absorption (CVAA) and ion chromatograph (IC), respectively. The effects of pH value, concentration of potassium persulfate and silver nitrate (SN), temperature, Hg0 concentration in the reactor inlet and tertiary butanol (TBA), free radical scavenger, on the removal efficiency of Hg0 were studied. The results showed that the removal efficiency of Hg0 increased with increasing concentration of potassium persulfate and silver nitrate, while temperature and TBA were negatively effective. Furthermore, the removal efficiency of Hg0 was much better in neutral solution than in both acidic and alkaline solution. But the influence of pH was almost eliminated by adding AgNO3. High Hg0 concentration has positive effect. The possible reaction mechanism of gaseous mercury was also discussed.

Co_(3)O_(4) with ordered pore structure derived from wood vessels for efficient Hg^(0) oxidation

Catalytic oxidation of Hgo to Hg~O is an efficient way to remove Hg^(0) from coal-fired flue gas.The catalyst with ordered pore structure can lower mass transfer resistance resulting in higher Hg^(0) oxidation efficiency.Therefore,in the present work,wood vessels were used as sacrificial template to obtain Co_(3)O_(4) with ordered pore structure.SEM and BET results show that,when the mass concentrations of Co(NO_(3))_(2)·6H_(2)O was 20%,the obtained catalyst(Co_(3)O_(4) [20%Co(NO_(3))_(2)])possesses better pore structure and higher surface area.It will expose more available surface active sites and lower the mass transfer resistance.Furthermore,XPS results prove that Co_(3)O_(4) [20%Co(NO_(3))_(2)]has the highest ratio of chemisorbed oxygen which plays an important role in Hg^(0) oxidation process.These results lead to a better Hg^(0) oxidation efficiency of Co_(3)O_(4) [20%Co(NO_(3))_(2)],which is about 90%in the temperature range of 200 to 350℃,Furthermore,Co_(3)O_(4) [20%Co(NO_(3))_(2)]has a stable catalytic activity,and its Hg^(0) oxidation efficiency maintains above 90%at 250℃even after 90 h test,A probable reaction mechanism is deduced by the XPS results of the fresh,used and regenerated catalyst of Co_(3)O_(4) [20%Co(NO3)2].Chemisorbed oxygen can react with Hg^(0) forming HgO with the reduction of Co^(3+)to Co^(2)+.And lattice oxygen and gaseous oxygen can supplement the consumption of chemisorbed oxygen to oxidize Co^(2+)to Co^(3+).

Mercury oxidation and adsorption characteristics of potassium permanganate modified lignite semi-coke

The adsorption characteristics of virgin and potassium permanganate modified lignite semi-coke （SC） for gaseous Hg were investigated in an attempt to produce more effective and lower price adsorbents for the control of elemental mercury emission. Brunauer-Emmett- Teller （BET） measurements, X-ray powder diffraction （XRD） and X-ray photoelectron spectroscopy （XPS） were used to analyze the surface physical and chemical properties of SC, Mn-SC and Mn-H-SC before and after mercury adsorption. The results indicated that potassium permanganate modification had significant influence on the properties of semi-coke, such as the specific surface area, pore structure and surface chemical functional groups. The mercury adsorption efficiency of modified semi-coke was lower than that of SC at low temperature, but much higher at high temperature. Amorphous Mn7＋, Mn6＋ and Mn4＋ on the surface of Mn-SC and Mn-H-SC were the active sites for oxidation and adsorption of gaseous Hg~, which oxidized the elemental mercury into Hg2＋ and captured it. Thermal treatment reduced the average oxidation degree of Mn2＋ on the surface of Mn-SC from 3.80 to 3.46. However, due to the formation of amorphous MnOx, the surface oxidation active sites for gaseous Hg0 increased, which gave Mn-H-SC higher mercury adsorption efficiency than that of Mn-SC at high temperature.

New insights into mercury removal mechanism on CeO2- based catalysts： A first-principles study

First-principles calculanons were performed to investigate the mechamsm of Hg0 adsorpnon and oxidation on CeO2（111）. Surface oxygen acnvated by the reducnon of Ce to Ce a vlta to Hg~ adsorption and oxidation processes. Hg0 was fully oxidized by the surface lattice oxygen on CeO2（111）, without using any other oxidizing agents. HCI could dissociate and react with the Hg adatom on CeO2（111） to form adsorbed Hg CI or CI-Hg-Cl groups, which promoted the desorption of oxidized Hg and prevented CeO2 catalyst deactivation. In contrast, O-H and H-O-H groups formed during HC1 adsorption consumed the active surface oxygen and prohibited Hg oxidation. The consumed surface oxygen was replenished by adding O2 into the flue gas. We proposed that oxidized Hg desorption and maintenance of sufficient active surface oxygen were the rate-determining steps of Hg0 removal on CeO2-based catalysts. We believe that our thorough understanding and new insights into the mechanism of the Hg0 removal process will help provide guidelines for developing novel CeO2-based catalysts and enhance the Hg removal efficiency.

Mercury enrichment in Brassica napus in response to elevated atmospheric mercury concentrations

Mercury enrichment in response to elevated atmospheric mercury concentrations in the organs of rape （Brassica napus） was investigated using an open top chamber fumigation experiment and a soil mercury enriched cultivation experiment. Results indicate that the mercury concentration in leaves and stems showed a significant variation under different concentrations of mercury in atmospheric and soil experiments while the concentration of mercury in roots, seeds and seed coats showed no significant variation under different atmospheric mercury concentrations. Using the function relation established by the experiment, results for atmospheric mercury sources in -rape field biomass showed that atmospheric sources accounted for at least 81.81% of mercury in rape leaves and 32.29% of mercury in the stems. Therefore, mercury in the aboveground biomass predominantly derives from the absorption of atmospheric mercury.

MoS_(2) quantum dots based MoS_(2)/HKUST-1 composites for the highly efficient catalytic oxidation of elementary mercury

Due to the ever-tightening regulation on mercury emission in recent decades,there is an urgent need to develop novel materials for the removal of elemental mercury at coal-fired power plants.In this study,a series of MoS_(2) quantum dots(QDs)-based MoS_(2)/HKUST-1 composite materials were prepared.It is found that MoS_(2)QDs were encapsulated by HKUST-1and enhanced the crystallinity and specific surface area of HKUST-1.The MoS_(2)/HKUST-1 showed excellent performance in catalytic oxidation of Hg~0as compared with pristine HKUST-1.It is found that surface layer of lattice oxygens is active and participates in Hg^(0) oxidation,while the consumption of surface oxygens then leads to the formation of oxygen vacancies on the surface.These vacancies are effective in the adsorption and dissociation of O_(2),which subsequently participates in the oxidation of Hg^(0).Moreover,the study on the influence of commonly seen gas components,such as SO_(2),NO,NH_(3) and H_(2)O,etc.,on Hg^(0) oxidation demonstrated that synergistic effects exist among these gas species.It is found that the presence of NO promotes the oxidation of Hg^(0) using oxygen as the oxidant.

100 years of high GEM concentration in the Central Italian Herbarium and Tropical Herbarium Studies Centre(Florence,Italy)

Up to 1980 s,the most used preservative for herbaria specimens was HgCl2,sublimating at ambient air conditions;ionic Hg then reduces to Hg0(gaseous elemental mercury,GEM)and diffuses throughout poor ventilated environments.High GEM levels may indeed persist for decades,representing a health hazard.In this study,we present new GEM data from the Central Italian Herbarium and Tropical Herbarium Studies Centre of the University of Florence(Italy).These herbaria host one of the largest collection of plants in the world.Here,HgCl2 was documented as plant preservative up to the 1920 s.GEM surveys were conducted in July 2013 and July and December 2017,to account for temporal and seasonal variations.Herbaria show GEM concentrations well above those of external locations,with peak levels within specimen storage cabinets,exceeding 50,000 ng/m3.GEM concentrations up to^7800 ng/m3 were observed where the most ancient collections are stored and no ventilation systems were active.On the contrary,lower GEM concentrations were observed at the first floor.Here,lower and more homogeneously distributed GEM concentrations were measured in 2017 than in 2013 since the air-conditioning system was updated in early2017.GEM concentrations were similar to other herbaria worldwide and lower than Italian permissible exposure limit of 20,000 ng/m3(8-hr working day).Our results indicate that after a century from the latest HgCl2 treatment GEM concentrations are still high,i.e.,the treatment itself is almost irreversible.Air conditioning and renewing is probably the less expensive and more effective method for GEM lowering.