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 desulftLrization （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 （Hg^2＋） and more elemental mercury （Hg^0） 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.

Transformation of mercury speciation through the SCR system in power plants

Coal-fired utility boilers are now identified as the largest source of mercury in the United States. There is speculation that the installation of selective catalytic reduction （SCR） system for reduction of NOx can also prompt the oxidation and removal of mercury. In this paper, tests at six full-scale power plants with similar type of the SCR systems are conducted to investigate the effect of the SCR on the transformation of mercury speciation. The results show that the SCR system can achieve more than 70%-80% oxidation of elemental mercury and enhance the mercury removal ability in these units. The oxidation of elemental mercury in the SCR system strongly depends on the coal properties and the operation conditions of the SCR systems. The content of chloride in the coal is the key factor for the oxidization process and the maximum oxidation of elemental mercury is found when chloride content changes from 400 to 600 ppm. The sulfur content is no significant impact on oxidation of elemental mercury.

Mercury speciation and removal across full-scale wet FGD systems at coal-fired power plants

The Ontario Hydro Method （OHM） recommended by the United States Environmental Protection Agency （EPA） was used to determine mercury speciation in the combustion flue gas across wet FGD systems. Four coal-fired units with wet FGD systems were chosen to evaluate mercury speciation and mercury removal efficiencies through these wet FGD systems. Chlorine content in coal had been suggested as a main factor that affects mercury speciation in flue gas. It is shown that the higher the chlorine concentration in coal is, the higher the percentage of oxidized mercury （Hg2＋） is removed in wet FGD systems, which can increase overall mercury removal efficiencies through wet FGD systems. The selective catalyst reduction （SCR） system has a function of oxidizing ele- mental mercury （Hg0） to oxidized mercury. A higher percentage of oxidized mercury in the total vapor mercury at the FGD inlet is observed when SCR is in service. Therefore, higher overall mercury removal efficiencies through wet FGD are attained. Because of different wet FGD operating conditions, there are different mercury removal efficiencies in different units. Elemental mercury reemission took place when a fraction of oxidized mercury absorbed in the slurry is reduced to elemental mercury, and Hg2＋ is reemitted from stack, which results in decreases in mercury removal efficiencies through wet FGD systems.

Mercury Speciation of Flue Gas Desulphurization By-Products in Coal-Fired Power Plants in China

The aim of this study was to develop and examine the morphology and distribution of mercury (Hg) in flue gas desulfurization (FGD) by-product. Mercury in the coal of coal-fired power plants is concentrated in the by-products of desulfurization process, and it is widely used as an additive in cement, building materials and other industries. Due to the different stability of various forms of mercury in the environment, subsequent use of products containing desulfurization by-product additives will continue to be released into the environment, endangering human health. Therefore, it is very necessary to study the form and distribution of mercury in the by-products of desulfurization in coal-fired power plants to provide a theoretical basis for subsequent harmless treatment. For content and morphology of mercury analysis, 1 sample of dry FGD ash and 6 samples of wet FGD gypsum were analyzed. The total 7 samples were extracted using a modification of sequential chemical extractions (SCE) method, which was employed for the partitioning Hg into four fractions: water soluble, acid soluble, H2O2 soluble, and residual. The Hg analysis was done with United States Environmental Protection Agency (USEPA) method 7471B. Comparing with the wet FGD gypsums of coal-fired boilers, the total Hg content in the dry FGD by-product was as high as 1.22 mg/kg, while the total Hg content in the FGD gypsum is 0.23 - 0.74 mg/kg, which was 2 times over the wet FGD gypsum. The concentration of water soluble Hg in the dry FGD by-product was the highest amount (0.72 mg/kg), accounting for 59.02% of the total mercury. While residual Hg content was 0.16 mg/kg, only about 13.11% of the total mercury. Mercury content in FGD gypsum was expressed in the form of ρ (residual Hg) > ρ (H2O2 soluble Hg) > ρ (water soluble Hg) > ρ (acid soluble Hg). The morphology and distribution of mercury in FGD by-products is supposed to be analyzed before utilization, and the impact of mercury on the environment should be considered.

Environmental impact factors and mercury speciation in the sediment along Fujian and eastern Guangdong coasts

Concentrations of total mercury （THg） and methyl mercury （MeHg） were determined for 32 surface sed- iments collected along the coastal line of Fujian Province and eastern Guangdong Province. The spatial distributions of THg and MeHg and their environmental impact factors were investigated. The average con- centrations of THg and MeHg in the sediments were 31.5 ng/g and 0.096 ng/g, respectively. Both sediment THg and MeHg concentrations showed relatively high value in the Minjiang Estuary and the coastal areas of Quanzhou and Putian. The concentrations overall decreased as the distance to the shoreline increased. The correlations among environmental impact factors and THg, MeHg were analyzed. The sediment THg concentration was highly correlated to the concentrations of organic matter, copper, total nitrogen （TN） and total phosphorus （TP）, and significantly correlated to pH value of the bottom seawater and concentration of sediment sulfide. The sediment MeHg concentration was highly correlated to the concentrations of organic matter and copper, and significant correlated to the concentrations of sulfide, TN, TP and pH value of the bottom seawater.

Mercury speciation, bioavailability and risk assessment on soil–rice systems from a watershed impacted by abandoned Hg mine-waste tailings

Mercury(Hg) is a global pollutant and can be accumulated in the food chain, posing exposure risks to humans. In this study, rice plants and corresponding rhizosphere soil samples were collected from a watershed of the Wawu River Basin that is heavily impacted by historic Hg mining and retorting activities. Total mercury(THg)and methylmercury(MeHg) in rice grains, as well as other tissues and soil samples, were measured. Five soil Hg fractions, as well as soil parameters, were also determined.The results show that the average concentrations of THg and MeHg in rice grains were 14 ± 7.0 lg kg^(-1) and7.2 ± 4.0 lg kg^(-1). Soil organic-bound(Hg-o) and strong complex-bound(Hg-s) were the main Hg fractions,accounting for 44% of the total. To estimate the Hg–ligand interaction in the soils, soil-N/Hg(R = 0.451, p \ 0.05),-S/Hg(R = 0.372, p \ 0.1), and-OM/Hg ratio(R = 0.320,p \ 0.5) with MeHg_(soil) were observed with significant positive correlations, indicating that the formation of Hg–OM, Hg–N–OM or Hg–S–OM complexes could prevent Hg(II) from methylation in soils. The significant positive correlations of the-N/Hg ratio,-S/Hg ratio and-OM/Hg ratio with MeHg in rice tissues suggested that Hg methylation and MeHg demethylation occurred throughout the rice paddy ecosystem. The estimated MeHg daily intake(EDI) was 0.075 ± 0.041 lg kg^(-1) bw d^(-1) and was lower than the RfD level of 0.1 lg kg^(-1) bw d^(-1) recommended by the US EPA. However, approximately 29% of the hazardous index(HI) of MeHg in grain exceeded 1, posing a potential threat to local populations, particularly pregnant women and children.

Migration and speciation transformation mechanisms of mercury in undercurrent zones of the Tongguan gold mining area, Shaanxi Loess Plateau and impact on the environment

In order to study the migration and transformation mechanism of Hg content and occurrence form in subsurface flow zone of gold mining area in Loess Plateau and its influence on water environment,the field in-situ infiltration test and laboratory test were carried out in three typical sections of river-side loess,alluvial and proluvial strata in Tongguan gold mining area of Shaanxi Province,and the following results were obtained:(1)The source of Hg in subsurface flow zone is mainly caused by mineral processing activities;(2)the subsurface flow zone in the study area is in alkaline environment,and the residual state,iron and manganese oxidation state,strong organic state and humic acid state of mercury in loess are equally divided in dry and oxidizing environment;mercury in river alluvial or diluvial strata is mainly concentrated in silt,tailings and clayey silt soil layer,and mercury has certain stability,and the form of mercury in loess is easier to transform than the other two media;(3)under the flooding condition,most of mercury is trapped in the silt layer in the undercurrent zone where the sand and silt layers alternate with each other and the river water and groundwater are disjointed,and the migration capacity of mercury is far less than that of loess layer and alluvial layer with close hydraulic connection;(4)infiltration at the flood level accelerates the migration of pollutants to the ground;(5)the soil in the undercurrent zone is overloaded and has seriously exceeded the standard.Although the groundwater monitoring results are safe this time,relevant enterprises or departments should continue to pay attention to improving the gold extraction process,especially vigorously rectify the small workshops for illegal gold extraction and the substandard discharge of the three wastes,and intensify efforts to solve the geological environmental problems of mines left over from history.At present,the occurrence form of mercury in the undercurrent zone is relatively stable,but the water and soil layers have been polluted.The risk of disjointed groundwater pollution can not be ignored while giving priority to the treatment of loess and river alluvial landform areas with close hydraulic links.The research results will provide a scientific basis for water conservancy departments to groundwater prevention and control in water-deficient areas of the Loess Plateau.

Mercury speciation and spatial distribution in surface waters of the Yarlung Zangbo River,Tibet

The Yarlung Zangbo River is the highest river in the world.It flows from west to east through the southern part of Tibet.The mercury(Hg)speciation and distribution in surface waters and soils near the bank of the Yarlung Zangbo River and its two tributaries,the Lhasa and Niyang Rivers,were investigated in June 2007.Simultaneously,major water quality parameters were also measured at the same stations.Total Hg(THg)and total methylmercury(TMeHg)concentrations in surface waters of the Yarlung Zangbo River ranged from 1.46 to 4.99 ng/L and from 0.06 to 0.29 ng/L,respectively,representing the background levels in river systems of the Tibetan Plateau.Particulate Hg(PHg)accounted for 69%of the THg,and the two Hg species had a significant relationship(r=0.990,P<0.01).Approximately 61%of the spatial distribution of THg was controlled by the concentrations of total suspended particles(TSP).Reactive Hg(RHg)concentrations ranged from 0.10 to 0.36 ng/L,and this fraction may play a weak role in terms of the transport and fate of Hg in surface waters.Dissolved methylmercury(DMeHg)constituted 71%of the TMeHg and was significantly correlated with TMeHg(r=0.746,P<0.01).The spatial distribution of TMeHg is not strongly affected by environmental factors such as THg,RHg,temperature,pH,dissolved organic carbon(DOC),and TSP.In addition,the inflow of both the Lhasa and Niyang Rivers probably influences the concentrations of THg in surface waters of the mainstream, but such an effect is not obvious for TMeHg.

The Chemical Speciation and Behavior of Mercury and Selenium in the Insoluble Fraction of Striped Dolphin Liver

Most of the mercury and selenium exist in the insoluble fraction of dolphin liver. After the insoluble fraction was digested by alkaline protease in the presence of 1%SDS, approximately 50% of Hg and Se consisted in the supernatant and the others in the residue. Gel filtration chromatography of the hydrolysate showed that 96% of Hg and 87% of Se were combined with the high molecular weight proteins stably, which cannot be substituted by the complex reagents. Mercury and selenium in the residue were confirmed as HgSe crystal.

Distribution and speciation of mercury in the Hongfeng Reservoir,Guizhou Province, China

The water, pore water, sediment, and fish samples were collected from the Hongfeng Reservoir in No- vember 2003 and February 2004 in accordance with trace metal protocols. The average concentrations of total mer- cury (THg), dissolved mercury (DHg), reactive mercury, dissolved gaseous mercury, total methylmercury, and dis- solved methylmercury in the water columns were 8.00, 5.70, 0.63, 0.05, 0.16, and 0.07 ng/L, respectively. THg and DHg in the water columns, THg in pore water and THg in lake sediments of the Hongfeng Reservoir showed the level of mercury in the Hongfeng Reservoir was higher than in other natural waters in the world due to the loading of a lot of waste water with relatively high concentrations of mercury, whereas methylmercury concentrations in fish (wet weight) varied from 1.73–51.00 ng/g, much lower than in most remote lakes and reservoirs reported in northern Europe and North America. Methylmercury distributions in pore water and sediments showed methylation oc- curred mainly in the upper several centimeters of sediment cores in the Hongfeng Reservoir. The concentrations of dissolved organic carbon, total suspended particles, total Hg, and methylmercury were higher at Houwu than those at Daba in November 2003. It is suggested that other pollutants such as N and P from fishing farm and other waste water at Houwu,which resulted in deterioration of water quality, affected the concentrations and distributions of mercury species in the reservoir.

In-situ measurement and distribution of flue gas mercury for a utility PC boiler system

The in-situ instrumentation technique for measuring mercury and itsspeciation downstream a utility 100 MW pulverized coal (PC) fired boiler system was developed andconducted by the use of the Ontario hydro method (OHM) consistent with American standard test methodtogether with the semi-continuous emissions monitoring (SCEM) system as well as a mobile laboratoryfor mercury monitoring. The mercury and its speciation concentrations including participate mercuryat three locations of before air preheater, before electrostatic precipitator (ESP) and after ESPwere measured using the OHM and SCEM methods under normal operation conditions of the boiler systemas a result of firing a bituminous coal. The vapor-phase total mercury Hg(VT) concentration declinedwith the decrease of flue gas temperature because of mercury species transformation from oxidizedmercury to particulate mercury as the flue gas moved downstream from the air preheater to the ESPand after the ESP. A good agreement for Hg°, Hg^(2+) and Hg( VT) was obtained between the twomethods in the ash-free area. But in the dense particle-laden flue gas area, there appeared to be abig bias for mercury speciation owing to dust cake formed in the filter of OHM sampling probe. Theparticulateaffinity to the flue gas mercury and the impacts of sampling condition to accuracy ofmeasure were discussed.

Neural network approach to predicting mercury emission from utility boiler

The feasibility of using an ANN method to predict the mercury emission and speciation in the flue gas of a power station under un-tested combustion/operational conditions is evaluated. Based on existing field testing datasets for the emissions of three utility boilers, a 3-layer back-propagation network is applied to predict the mercury speciation at the stack. The whole prediction procedure includes： collection of data, structuring an artificial neural network （ANN） model, training process and error evaluation. A total of 59 parameters of coal and ash analyses and power plant operating conditions are treated as input variables, and the actual mercury emissions and their speciation data are used to supervise the training process and verify the performance of prediction modeling. The precision of model prediction （ root- mean-square error is 0. 8 μg/Nm3 for elemental mercury and 0. 9 μg/Nm3 for total mercury） is acceptable since the spikes of semi- mercury continuous emission monitor （SCEM） with wet conversion modules are taken into consideration.

The Challenge and Its Solution When Determining Biogeochemically Reactive Inorganic Mercury(RHg):Getting the Analytical Method Right

Biogeochemially reactive inorganic mercury (RHg) is an important fraction of Hg. Researchers have attempted to measure RHg when characterizing Hg-impacted sites, conducting research and development of remediation practices, or evaluating remediation efficiency. In these uses, RHg will be the best choice for analysis in ways that total methyl, and other species of Hg cannot duplicate. The fraction has been inadequately measured using the Sn2+ reduction method and operationally defined as “Sn2+ reducible Hg2+”, but the resulting data did not reflect well the nature of the fraction and caused researchers to lose interest, thus limiting the use of RHg in past years. In this work, the problems of using the Sn2+ reduction method were discovered to be generating irreproducible and negatively biased results. Negative bias from 20% to 99% was found in different types of waters. To obtain reliable results, an ethylation-based GC-CVAFS method was used to determine RHg. The performance of the method was evaluated by comparing it to the Sn2+ reduction method. Biogeochemically meaningful results have been obtained in the application of the method to determine RHg in mercury mine-impacted waters from the Idrijca River in Slovenia.

Mercury Emission From Coal-fired Power Plants in China

燃煤是最大的人为汞排放源之一，燃煤电厂的汞排放控制问题也越来越为人们所关注。该文将目前公布的中国电厂的汞排放数据进行筛选汇总，得到18个电厂的汞排放数据，通过对比和分析，总结出了符合我国燃煤电厂特点的一般性汞排放规律。结果表明：与美国煤种相比，我国的燃煤具有低氯、高灰的特性，这不利于汞的排放控制；循环流化床燃烧可能会因燃尽率的不同而较煤粉炉燃烧易获得较高的Hgp；空气污染控制设备的使用能够有效地减少汞排放，选择性催化还原＋静电除尘器／布袋除尘器＋石灰石-石膏湿法脱硫（SCR＋ESP／FF＋WFGD）组合的平均脱汞率可达71．48％；SCR的大规模应用可能会将汞大量转移到飞灰和脱硫石膏中，带来二次污染的问题。

Farmland mercury contamination in the vicinity of an organic chemical factory in Guizhou,China

This study assesses the level of contamination of Hg in farmland soils along the irrigating channel down-stream from Guizhou Organic Chemical Factory (GOCF),where metallic mercury is used as a catalyst to produce acetic acid. The total input of mercury into the environment,as announced by GOCF,is 140 t in the past 30 years (1971-2000). Sampling sites were chosen based on the distance from the source of pollution—the chemical factory. A total of 39 samples were collected from the study area and analyzed for total mercury concentrations and methyl mercury concentrations. The characteristics of vertical and horizontal distributions of total mercury and methyl mer-cury in the study area (farmland) are described in this paper. Much attention was paid to the transformation of inor-ganic Hg into organic mercury species in soils as well. The results showed that the farmland has been heavily con-taminated by Hg. Land cultivation activity,land utilization style and distance from the pollution source could be the dominant factors controlling the distribution of THg and MeHg. It is observed that active transformation of inorganic Hg into organic mercury species (MeHg) usually takes place in paddy soils.

Characteristics and distributions of atmospheric mercury emitted from anthropogenic sources in Guiyang, southwestern Chin

Continuous measurements of speciated atmo- spheric mercury （Hg）, including gaseous elemental mer- cury （GEM）, particulate mercury （PHg）, and reactive gaseous mercury （RGM） were conducted in Guizhou Pro- vince, southwestern China. Guiyang Power Plant （GPP）, Guiyang Wujiang Cement Plant, Guizhou Aluminum Plant （GAP）, and Guiyang Forest Park （GFP） in Guiyang were selected as study sites. Automatic Atmospheric Mercury Speciation Analyzers （Tekran 2537A） were used for GEM analysis. PHg and RGM were simultaneously collected by a manual sampling system, including elutriator, coupler/ impactor, KCl-coated annular denuder, and a filter holder. Results show that different emission sources dominate different species of Hg. The highest average GEM value was 22.2 ±28.3 ng·m-3 and the lowest 6.1 ± 3.9 ng·m-3, from samples collected at GPP and GAP, respectively. The maximum average PHg was 1984.9 pg·m-3 and the mini- mum average 55.9 pg·m-3, also from GPP and GAP, respectively. Similarly, the highest average RGM of 68.8 pg·m-3 was measured at GPP, and the lowest level of 20.5 pg·m-3 was found at GAP. We conclude that coal combustion sources are still playing a key role in GEM; traffic contributes significantly to PHg; and domestic pol- lution dominates RGM.

Spatial Differences and Influencing Factors of Dissolved Gaseous Mercury in the Yellow Sea and Bohai Sea in Spring

From 28 March to 17 April, 2018, different forms of mercury(Hg) in the Yellow Sea and Bohai Sea were measured to study the influencing factors on the distribution and transformation of Hg in spring using a shared cruise. The mean concentration of dissolved gaseous mercury(DGM) in the surface water of the Yellow and Bohai Seas was(44.3 ± 43.9) pg/L, which was close to that in mid-latitude oceans and deep seas. The ratio of DGM to THg(total mercury) was lower than in the oceans and in the Yellow and Bohai Seas in summer or fall. DGM concentrations in surface water were highest in the central part of the South Yellow Sea and were higher than those in the Bohai Sea, and their spatial distributions were consistent with RHg(reactive mercury). DGM and RHg correlated positively with water temperature in surface seawater(r = 0.506, P < 0.01;r = 0.278, P < 0.05). The concentrations of both DGM and RHg in surface water were controlled by solar radiation and water temperature. Foggy weather did not benefit the production of DGM and RHg. DGM in the bottom seawater was mainly affected by Dissolved Oxygen and water temperature(r =-0.366, P < 0.01;r = 0.331, P < 0.01), produced mainly by anaerobic reactions of the bottom seawater and sediment microorganisms. The bottom DGM concentrations in the Yellow and Bohai Seas were the highest, and DGM produced in bottom seawater and sediment plays a more important role than the surface water in spring. The concentrations of DGM and RHg in the surface and bottom water in the South Yellow Sea were all higher than those in the middle layer. Vertical variations in the North Yellow Sea and the Bohai Sea were small. The production and distribution of DGM and RHg were influenced by differences of latitude and by the Yellow Sea warm current in spring.

Mercury pollution in the Chongqing part of the Three Gorges Reservoir area and its remediation and prevention

Mercury pollution in the Three Gorges Reservoir area of P.R.China merits special attention.We investigated into the current situation in the Chongqing part of the Reservoir area,identified the pollution sources and proposed some suggestions for the remediation and prevention of mercury pollution in this area.Atmospheric mercury in Chongqing was mainly from coal burning and releases of mercury-containing products such as various types of lights and fever thermometers.Urban drainage in Chongqing and Changshou,and runoffs from the high mercury background area in the lower reaches of the Wujiang River contributed most of the mercury in the water of the Yangtze River.A majority of the blame should be laid on mercury and gold mining in the Wujiang valley.We suggested foresting sloping lands to relieve soil erosion and prevent mercury-bearing soil from running into rivers,educational activities to discourage use of mercury-containing products and improved infrastructure to collect mercury-containing wastes for reducing mercury releases,more facilities for treating wastewater and solid waste to accommodate increased requirements of discharge,and growing selected perennial plants in mercury-contaminated land to absorb the mercury in soil.We also suggested concerted operation of a dedicated water-quality monitoring system,reinforced legislation and an effective administrative mechanism to ensure lasting efforts are invested in curbing mercury releases and restoring mercury contaminated land and water in the Reservoir area.

Experimental research on mercury emission from one-dimensional combustion test facility

The research of mercury release from coal combustion and mercury speci-ation in flue gas was conducted in a one-dimensional combustion test facility. The ex-perimental results indicated that combustion temperature was the primary factor in af-fecting mercury vaporization and release. Experimental measurements showed high mercury levels in the particulate phase. Hg(S) is enriched in fly ash and dispersed in bottom ash. Hg(B) content decreases and the Hg(F) content increases with higher fur-nace temperature. At 1 100℃, the levels of Hg2+(g) are 17%~48% for limited chemical kinetics .The mercury equilibrium in the flue-gas is frozen below some temperature.