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.

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.

Potential bioavailability of mercury in humus-coated clay minerals

It is well-known that both clay and organic matter in soils play a key role in mercury biogeochemistry, while their combined effect is less studied. In this study, kaolinite,vermiculite, and montmorillonite were coated or not with humus, and spiked with inorganic mercury（IHg） or methylmercury（Me Hg）. The potential bioavailability of mercury to plants or deposit-feeders was assessed by CaCl2 or bovine serum albumin（BSA） extraction. For uncoated clay, IHg or Me Hg extraction was generally lower in montmorillonite, due to its greater number of functional groups. Humus coating increased partitioning of IHg（0.5%–13.7%） and Me Hg（0.8%–52.9%） in clay, because clay-sorbed humus provided more strong binding sites for mercury. Furthermore, humus coating led to a decrease in IHg（3.0%–59.8% for CaCl2 and 2.1%–5.0% for BSA） and Me Hg（8.9%–74.6% for CaCl2 and 0.5%–8.2% for BSA）extraction, due to strong binding between mercury and clay-sorbed humus. Among various humus-coated clay particles, mercury extraction by CaCl2（mainly through cation exchange）was lowest in humus-coated vermiculite, explained by the strong binding between humus and vermiculite. The inhibitory effect of humus on mercury bioavailability was also evidenced by the negative relationship between mercury extraction by CaCl2 and mercury in the organo-complexed fraction. In contrast, extraction of mercury by BSA（principally through complexation） was lowest in humus-coated montmorillonite. This was because BSA itself could be extensively sorbed onto montmorillonite. Results suggested that humus-coated clay could substantially decrease the potential bioavailability of mercury in soils, which should be considered when assessing risk in mercury-contaminated soils.