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.

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.

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.

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.

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.

Dithizone-functionalized C18 online solid-phase extraction-HPLC-ICP-MS for speciation of ultra-trace organic and inorganic mercury in cereals and environmental samples

A simple and efficient dithizone-functionalized solid-phase extraction(SPE)procedure,online coupled with high-performance liquid chromatography(HPLC)-inductively coupled plasma mass spectrometry,was developed for the first time for enrichment and determination of ultra-trace mercury(Hg)species(inorganic divalent Hg(Hg(Ⅱ)),methylmercury(CH_(3)Hg(Ⅱ))and ethylmercury(C_(2)H_(5)Hg(Ⅱ))in cereals and environmental samples.In the proposed method,functionalization of the commercial C_(18) column with dithizone,enrichment,and elution of the above Hg species can be completed online with the developed SPE device.A simple solution of 2-mercaptoethanol(1%(V/V))could be used as an eluent for both the SPE and HPLC separation of Hg species,significantly simplifying the method and instrumen-tation.The online SPE method was optimized by varying dithizone dose,2-mercaptoethanol concentration,and sample volume.In addition,the effect of pH,coexisting interfering ions,and salt effect on the enrichment was also discussed.Under the optimized conditions,the detection limits of Hg species for 5 mL water sample were 0.15 ng/L for Hg(Ⅱ),0.07 ng/L for CH_(3)Hg(Ⅱ),and 0.04 ng/L for C_(2)H_(5)Hg(Ⅱ)with recoveries in the range of 85%-100%.The developed dithizone-functionalized C_(18) SPE column can be reused after a single function-alization,which significantly simplifies the enrichment step.Moreover,the stability of Hg species enriched on the SPE column demonstrated its suitability for field sampling of Hg species for later laboratory analysis.This environment-friendly method offers a robust tool to detect ultra-trace Hg species in cereals and environmental samples.

Application of KCl-denuder for measuring gas-phase mercuric species(Hg^(2+))in atmosphere

KCl denuder technique was meployed in the measurement of Hg(II) species in atmosphere firstly. Intensive lab tests indicate that Hg 0 can pass through KCl denuder freely, while Hg 2+ can be trapped in it very efficiently. The efficiencies for adsorbing inorganic Hg 2+ averaged between 95% to 100% with a gross mean of 98%, and those for absorption of organic Hg 2+ were around 94%. Mass balance calculation shows that mercury trapped in denuder can be quantitatively extracted by 1 mol/L HCl (super grade) and analysed by the method of SnCl 2 reduction CVAFS determination, thus, demonstrated the feasibility of KCl denuder in measurement of Hg(II) in atmosphere. Preliminary application at two sites Gteborg, Sweden and one site in Ireland, found 0 04—0 15 ng/m 3 of Hg(II) species, contributing to 2%—10% of the total mercury.

Insights into mercury in glacier snow and its incorporation into meltwater runoff based on observations in the southern Tibetan Plateau

The Tibetan Plateau（TP） is recognized as ＂Water Tower of Asia＂. Yet our understanding of mechanisms influencing incorporation of mercury（Hg） into freshwater in mountain glaciers on the TP remains quite limited. Extensive sampling of environmental matrices（e.g., snow/ice）were conducted on the East Rongbuk glacier on Mt. Everest and Zhadang glacier on Mt.Nyainqentanglha for Hg speciation analysis. Speciated Hg behaved quite different during snowmelt： a preferential early release of DHg（dissolved Hg） was observed at the onset of snowmelt, whereas PHg（particulate-bound Hg） and THg（total Hg） become relatively enriched in snow and released later. Small fraction of Hg in snow was lost during a snowmelt day（18.9%–34.7%） with a large proportion（58.1%–87.3%） contributed by PHg decrease, indicating that the deposited Hg is most likely retained in glacier snow/ice. Furthermore, THg were positively correlated with PHg and crustal major ions（e.g., Ca2＋, Mg2＋） during snowmelt, indicating that Hg is mainly migrated with particulates. The main pathway of Hg loss during snowmelt was most probably associated with release of PHg with meltwater, which was greatly influenced by ablation intensity of snow/ice. This should be paid particular concern as Hg preserved in mountain glaciers will mostly enter aquatic ecosystem as climate warms, impacting on downstream ecosystems adversely. Obvious decrease of THg during the downstream transport from glacier was observed with a large proportion contributed by PHg decrease. The main removal mechanism of Hg was associated with sedimentation of PHg during the transport process.

Impact of Flue Gas Species and Temperature on Mercury Oxidation

Systematic experimental research has been conducted in a fixed-bed reactor system to determine the impact of coal-fired flue gas species and temperature on mercury oxidation. This work focuses on the temperatures range of 200℃ to 800℃ to demonstrate that temperature is a critical factor for the effect of the gas components on the mercury oxidation process. Among the investigated gases, hydrogen chloride is es- sential for oxidizing the elemental mercury. Nitrogen oxide was also found to have a positive correlation with the mercury oxidation when hydrogen chloride was present. Sulfur dioxide can either promote or inhibit the oxidation depending on the conditions; however, when nitrogen oxide is also present, sulfur dioxide has a negative impact. Ammonia exhibits an strong inhibitory effect. Several plausible mercury oxidation pathways are suggested in this paper.

Fate of mercury in flue gas desulfurization gypsum determined by Temperature Programmed Decomposition and Sequential Chemical Extraction

A considerable amount of Hg is retained in flue gas desulfurization（FGD） gypsum from Wet Flue Gas Desulfurization（WFGD） systems. For this reason, it is important to determine the species of Hg in FGD gypsum not only to understand the mechanism of Hg removal by WFGD systems but also to determine the final fate of Hg when FGD gypsum is disposed. In this study, Temperature Programmed Decomposition（TPD） and Sequential Chemical Extraction（SCE） were applied to FGD gypsum to identify the Hg species in it. The FGD gypsum samples were collected from seven coal-fired power plants in China, with Hg concentrations ranging from 0.19 to 3.27 μg/g. A series of pure Hg compounds were used as reference materials in TPD experiments and the results revealed that the decomposition temperatures of different Hg compounds increase in the order of Hg_2Cl_2〈 HgCl_2〈 black HgS 〈 Hg_2SO_4〈 red HgS 〈 HgO 〈 HgSO_4. The Hg compounds existing in FGD gypsums identified by TPD included HgCl_2, Hg_2Cl_2, Hg_2SO_4, black HgS and red HgS, of which mercury sulfides were the primary compounds. The results of SCE indicated that Hg was mainly distributed in the strongly complexed phase. The low Hg content in FGD gypsum increases the ambiguity of assigning extraction fractions to certain Hg species by SCE. The fact that the primary compounds in FGD gypsum are HgS phases leads the leaching of Hg in the natural environment to be quite low, but a considerable amount of Hg may be released during the industrial heating process.