Mercury leaching characteristics of waste treatment residues generated from various sources in Korea

In this study, mercury (Hg) leaching characteristics of the waste treatment residues (fly ash, bottom ash, sludge, and phosphor powder) generated from various sources (municipal, industrial, medical waste incinerators, sewage sludge incinerator, oil refinery, coal-fired power plant, steel manufacturing plant, fluorescent lamp recycler, and cement kiln) in Korea were investigated. First, both Hg content analysis and toxicity characteristic leaching procedure (TCLP) testing was conducted for 31 collected residue samples. The Hg content analysis showed that fly ash from waste incinerators contained more Hg than the other residue samples. However, the TCLP values of fly ash samples with similar Hg content varied widely based on the residue type. Fly ash samples with low and high Hg leaching ratios (R_L) were further analyzed to identify the major factors that influence the Hg leaching potential. Buffering capacity of the low-R_L fly ash was higher than that of the high-R_L fly ash. The Hg speciation results suggest that the low-R_L fly ashes consisted primarily of low-solubility Hg compounds (Hg₂Cl₂, Hg⁰ or HgS), whereas the high-R_L fly ashes contain more than 20% high-solubility Hg compounds (HgCl₂ or HgSO₄).     

Gaseous mercury oxidation behavior in homogeneous reaction with chlorine compounds

Homogeneous oxidation reactions of gaseous elemental mercury were experimentally tested to study the behavior of mercury compounds that contribute to toxic emissions in combustion flue gas. Chemical equilibrium calculations and reaction kinetics analysis were also carried out to help explain the experimental results. In particular, the chemical forms of oxidized mercury and their reaction paths were verified in detail. Among the experimental results, molecular chlorine was confirmed to have a higher oxidizing ability toward elemental mercury than hydrogen chloride does. From the chemical equilibrium calculation, the final product of mercury compounds oxidized by chlorine was confirmed to be mercury chloride (HgCl₂). Numerical analyses of reaction kinetics were mostly consistent with the experimental results and the chemical equilibrium calculations. The ratio of mercury oxidization by chlorine increases with temperature from 473 K to 873 K, although it decreases at temperatures higher than 1000 K. Sensitivity analysis revealed the dominant reaction path of the mercury oxidation by chlorine. First, elemental mercury reacts with Cl radicals to form HgCl. Then, the HgCl reacts with Cl₂ to produce HgCl₂.     

Fate and behavior of selected heavy metals with mercury mass distribution in a fluidized bed sewage sludge incinerator

In this paper, emission and distribution behavior of six heavy metals (As, Cd, Cr, Ni, Pb, and Hg), particulate matter and mass distribution of mercury within the different streams of a fluidized bed sewage sludge incinerator are presented. At the inlet of air pollution control devices (APCDs); Cd, Cr, Ni and Pb were mainly enriched in coarse particles; comparatively As content was higher in fine particles (<PM_2.5). The concentration of heavy metals in total particulate matter and PM_2.5, at the inlet of APCDs, were in the order of Cr > Ni > Pb > As > Cd. Mercury was almost always distributed in flue gas. Metals, other than mercury, were efficiently removed in APCDs and their concentrations in bottom ash, with fly ash being higher, whereas for that in wastewater, then waste sand was lesser. Overall mercury removal efficiency of APCDs was 98.6 %. More than 83.3 % of mercury was speciated into oxidized form at the inlet of APCDs, attributed by higher chlorine content in sludge. Mercury was mainly distributed in wastewater (78.4 %), wastewater from a spray dry reactor (16.8 %), fly ash in a hopper (3.4 %) and flue gas (1.4 %). This result is one of the first for data to be obtained; more experiments are required to control emission from such sources.     

Nucleophilic substitution of poly(vinyl chloride) with iminoacetic acid and n-dodecanethiol

The modification of poly(vinyl chloride) was carried out with iminodiacetic acid (IDA, C₄H₇NO₄) and iminodiacetic acid dimethylester (IDADM, C₆H₁₁NO₄), as well as with n-dodecanethiol (DT, C₁₂H₂₆S) in the presence of K₂CO₃. The reaction was carried out at different temperatures below 100 °C with dimethyl formamide (DMF) and cyclohexanone as solvents. IDA did not show any reactivity, probably due to the dipolar character of the molecule. IDADM caused the elimination of HCl, while only substitution ratios of about 3 % were observed. However, the modification of PVC with DT resulted in a substitution rate of 18 % without elimination. DT-PVC showed excellent thermal properties, comparable with those of the unmodified polymer.     

Mercury reduction studies to facilitate the thermal decontamination of phosphor powder residues from spent fluorescent lamps

This work investigates the thermal release of mercury from phosphor powder of spent fluorescent lamps. The treatment conditions and the ability of various reducing agents (primarily sodium borohydride) to lower the overall heating temperature required to improve the release of Hg have been evaluated. Hg species in samples were monitored in a thermal desorption atomic absorption spectrometer system, and total mercury was analyzed in a cold vapor atomic absorption spectrometer. Sodium borohydride was the best reducing agent among the ones studied. However, citric acid presented a high capacity to weaken mercury bonds with the matrix. When the sample was crushed with sodium borohydride for 40min in a mass ratio of 10:1 (sample:reducing agent) and submitted to thermal treatment at 300 degrees C for 2h, the concentration of mercury in a phosphor powder sample with 103mgkg(-1) of mercury reached 6.6mgkg(-1).     

Mercury Capture on Fly Ash and Sorbents: The Effects of Coal Properties and Combustion Conditions

The US fleet of coal-fired power plants, with generating capacity of just over 300 GW, is known to be a major source of domestic mercury (Hg) emissions. To address this, in March 2005, the Environmental Protection Agency (EPA) promulgated the Clean Air Mercury Rule (CAMR) to reduce emissions of mercury from these plants. It is generally believed that most of the initial (Phase I) mercury reductions will come as a co-benefit of existing controls used to remove particulate matter (PM), SO₂, and NO _X . Deeper reductions in emissions (as required in Phase II of CAMR) may require the installation of mercury-specific control technology. Duct injection of activated carbon sorbents is the mercury-specific control technology that has been most widely studied and has been demonstrated over a wide range of coal types and combustion conditions. The effectiveness of the mercury control options (both “co-benefit control” and “mercury-specific control”) is significantly impacted by site-specific characteristics such as the combustion conditions, the configuration of existing air pollution controls, and the type of coal burned. This paper identifies the role of coal properties and combustion conditions in the capture of mercury by fly ash and injected sorbents.     

Removal of mercury from flue gas using sewage sludge-based adsorbents

Mercury from coal-fired utility boilers, as the largest atmospheric mercury emission source, imposes serious environmental risks and health concerns. In order to explore the possibility of reducing costs of activated carbon injection, we investigated the most promising mercury control technology, Hg⁰ removal using ZnCl₂-impregnated adsorbents derived from sewage sludge. The results demonstrated that sludge-based adsorbents (SBAs) had fairly high mercury adsorption capacity over a wide range of temperatures (80–170 °C). Oxidizing atmosphere could improve the adsorption of Hg⁰ and weaken the inhibition of SO₂ on mercury adsorption to some extent. NO exhibited no obvious impact on mercury removal performance. In addition, to clarify whether oxygen- or chlorine-containing functional groups attributed to good mercury adsorption capacity of SBAs, the oxygen-containing functional groups were removed using Boehm’s method, and a temperature-programmed decomposition desorption experiment was conducted. The results suggest that chlorine-containing functional groups played a significant role in the removal process of mercury from flue gas using SBAs.     

Characteristics of NO2 Pollution in the City of Gothenburg, South-West Sweden—Relation to NO x and O3 Levels, Photochemistry and Monitoring Location

Concentrations of NO₂, NO, and O₃ from a rooftop monitoring station in Gothenburg, Sweden (2002–2006) were analysed to characterise NO₂ pollution. [NO₂] was shown to correlate strongly and non-linearly with [NO _x ] (NO _x ?=?NO?+?NO₂), in line with observations in other cities. The [NO₂] to [NO _x ] fraction fell initially with increasing [NO _x ]. At [NO _x ] levels >200 ppb, the decline in [NO₂]/[NO _x ] with increasing [NO _x ] levelled out and [NO₂]/[NO _x ] converged towards approximately 0.15–0.16, independent of [NO _x ]. Data from a traffic route site showed the same pattern. This value of [NO₂]/[NO _x ] at high [NO _x ] can be interpreted as the NO₂ fraction of the NO _x emissions from vehicle exhaust. Situations with high NO _x pollution and minimum [NO₂]/[NO _x ] were always associated with [O₃] close to zero. Plotting [Ox] (Ox?=?NO₂?+?O₃) vs. [NO _x ] provided a strong linear correlation for situations dominated by local pollution ([NO]/[NO₂]>1). The slope of the regression, a measure of the primary NO₂ fraction in NO _x emissions, was 0.13 during the day and 0.14 during the night. With stronger winds, the rooftop monitoring station became more similar, in terms of NO₂ pollution, to a city street site and a traffic route site, although [NO₂] was almost always higher at the street/traffic route locations. The EU standard for the annual average of [NO₂] (40 μg m^?3) was exceeded, while the hourly standard (200 μg m^?3, not to be exceeded more than 18 times per year by 2010) was not exceeded at any of the sites.     

Indoor Air Quality Assessment of Elementary Schools in Curitiba, Brazil

The promotion of good indoor air quality in schools is of particular public concern for two main reasons: (1) school-age children spend at least 30% of their time inside classrooms and (2) indoor air quality in urban areas is substantially influenced by the outdoor pollutants, exposing tenants to potentially toxic substances. Two schools in Curitiba, Brazil, were selected to characterize the gaseous compounds indoor and outdoor of the classrooms. The concentrations of benzene, toluene, ethylbenzene, and the isomers xylenes (BTEX); NO₂; SO₂; O₃; acetic acid (HAc); and formic acid (HFor) were assessed using passive diffusion tubes. BTEX were analyzed by gas chromatography–ion trap mass spectrometry and other collected gasses by ion chromatography. The concentration of NO₂ varied between 9.5 and 23?µg m^?3, whereas SO₂ showed an interval from 0.1 to 4.8?µg m^?3. Within the schools, BTEX concentrations were predominant. Formic and acetic acids inside the classrooms revealed intermediate concentrations of 1.5?µg m^?3 and 1.2?µg m^?3, respectively.     

Pyrrolidinium Imides: Promising Ionic Liquids for Direct Capture of Elemental Mercury from Flue Gas

A new approach to vapor phase elemental mercury capture has been explored; this approach exploits an ionic liquid coating layer to oxidize elemental mercury for subsequent immobilization by chelating ligands. The room temperature ionic liquid 1-butyl-1-methyl pyrrolidinium bis(trifluoromethane sulfonyl)imide (P₁₄) was selected for study based on its oxidation potential window, thermal stability, and low vapor pressure. Tests were also completed in which KMnO₄ was added to P₁₄ to form a new ionic liquid, P₁₄–KMnO₄, with a higher oxidation potential. In room-temperature bulk liquid phase capture experiments, 59% of the elemental mercury in the inlet gas was captured using P₁₄ alone; mercury capture using P₁₄–KMnO₄ was quantitative. P₁₄ and P₁₄–KMnO₄ coatings were successfully applied to mesoporous silica substrates and to silica substrates functionalized with mercury chelating ligands. The coating layers were found to be thermally stable up to 300°C. Fixed-bed tests of nonfunctionalized silica coated with P₁₄ showed an elemental mercury uptake of 2.7 mg/g adsorbent at 160°C; at the same temperature, functionalized silica coated with P₁₄–KMnO₄ showed an elemental mercury capacity of at least 7.2 mg/g adsorbent, several times higher than that of activated carbon. The empty bed gas residence time in these tests was 0.04 s. A chelating adsorbent incorporating P₁₄ in the coating layer, may be capable of simultaneous removal of elemental and oxidized mercury from coal combustion flue gases.     

Bio-oil production by fast pyrolysis of cellulose/polyethylene mixtures in the presence of metal chloride

Cellulose/polyethylene mixture (3:1 w/w) and Tetra Pak wastes with and without metal chloride (ZnCl₂, AlCl₃, CuCl₂, FeCl₃) addition were subjected to a fast pyrolysis process at 350–500 °C and heating rate 100 °C/s to evaluate the possibility of liquid product formation with a high yield. The addition of zinc, aluminum, iron and copper chlorides has influenced the range of samples decomposition as well as the chemical composition of resulting pyrolytic oils. It was found that formation of levoglucosan, the main product of cellulose thermal decomposition, and phenol and its derivatives decreased in a presence of metal chlorides. Non-catalytic fast pyrolysis of polyethylene leads to the formation of solid long chain hydrocarbons, whereas the addition of metal chlorides promotes the formation of more liquid hydrocarbons.     

Preparation and characterization of mesoporous γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> recovered from aluminum cans waste and its use in the dehydration of methanol to dimethyl ether

The present study includes synthesis of two γ-Al₂O₃ samples from waste aluminum cans using a simple precipitation method. Precipitation was carried out using two different precipitating agents (i.e. NaOH and NH₄OH). The two prepared alumina samples were characterized by means of X-ray diffraction (XRD) and N₂ adsorption–desorption techniques. Surface acidity of γ-Al₂O₃ samples was measured by adsorption of two different probe molecules (i.e. pyridine and dimethyl pyridine) followed by desorption measurements using thermogravimetry (TG) and differential scanning calorimetry (DSC) techniques. Catalytic activity of the two prepared alumina samples towards the dehydration of methanol (to dimethyl ether) was studied in a fixed bed reactor at 300 °C. For comparison reasons, commercial γ-Al₂O₃ sample was, also, tested for the same catalytic reaction under the same conditions. Results showed that the alumina sample prepared using NaOH as a precipitating agent exhibited a better catalytic activity and stability compared with that prepared using NH₄OH and showed a similar activity as the commercial γ-Al₂O₃ sample.     

Fluxes and Loading of Heavy Metals, Benzo[a]pyrene and Oil Products in Vilnius City

The concentrations of heavy metals Pb, Cd, Cu, Zn and Hg, benzo[a]pyrene and oil products (C₁₅–C₂₈) in bulk (wet and dry) atmospheric deposition in Vilnius city in 2005–2006 were analysed. The highest flux to the ground surface of the city residential area, reaching 1,680 mg m^?2 year^?1, was determined for oil products, which in atmospheric bulk deposition was estimated to be mainly in the form of solid sediments. Among heavy metals, the highest flux was determined for Zn (113.5 mg m^?2 year^?1), while the lowest flux was determined for Hg (0.06 mg m^?2 year^?1). The flux of investigated pollutants ranges from a few times, or for some pollutants, up to one order of magnitude higher at the urban sampling site in comparison to residential or background sites. Some hundred tons of oil products, approximately 52 tons of zinc and a considerably lower amount of mercury, benzo[a]pyrene and cadmium deposit yearly to the ground and water surface of Vilnius city. Metallic constructions related to transport and buildings, automobile exhausts, spills of fuel and lubricants are suggested to be the factors which result in the accumulation of high amounts of heavy metals, oil products and other pollutants on the ground surface of the city.     

Study of nitrogen oxide absorption in the calcium sulfite slurry

Experiments were conducted using a bubbling reactor to investigate nitrogen oxide absorption in the calcium sulfite slurry. The effects of CaSO₃ concentration, NO₂/NO mole ratio and O₂ concentrations on NO₂ and SO₂ absorption efficiencies were investigated. Five types of additives, including MgSO₄, Na₂SO₄, FeSO₄, MgSO₄/Na₂SO₄ and FeSO₄/Na₂SO₄, had been evaluated for enhancing NO₂ absorption in CaSO₃ slurry. Results showed that CaSO₃ concentration had significant impact on NO₂ and SO₂ absorption efficiencies, and the highest absorption efficiencies of SO₂ and NO₂ could reach about 99.5 and 75.0 %, respectively. Furthermore, the NO₂ absorption was closely related to the NO₂/NO mole ratio, and the existence of NO₂ in flue gas may promote NO absorption. The presence of O₂ in simulated flue gas was disadvantage for NO _x removal because it can oxidize sulfite to sulfate. It was worth pointing out that FeSO₄/Na₂SO₄ was the best additive among those investigated additives, as the NO₂ removal efficiency was significantly increased from 74.8 to 95.0 %. IC and in situ FTIR results suggest that the main products were NO₃ ^? and NO₂ ^? in liquid phase and N₂O, N₂O₅ and HNO₃ in gas phase during the CaSO₃ absorption process.     

Sources and Variability of Indoor and Outdoor Gaseous Aerosol Precursors (O3, NOx and VOCs)

Measurements of indoor and outdoor aerosol concentrations and their gaseous precursors (O₃, NO and NO₂) as well as volatile organic compounds (VOCs) concentrations were performed at two houses in the Oslo metropolitan area. The variability of the concentration of gaseous compounds was studied in respect to their sources in the indoor and outdoor environments. Domestic heating during the winter and photochemical production during the summer were the main sources for outdoor NOx and O₃. In the indoor environment infiltration of outdoor air, candle burning, smoking and indoor chemical reactions were the main sources affecting their concentrations. The concentrations of VOCs outdoors were enhanced during the summer due to biogenic emissions whereas in the indoor environment their values were affected mostly by emissions from materials used during the recent refurbishing of the houses (>0.4 mg/m³).     

Characteristics of mercury desorption from sorbents at elevated temperatures

This study investigated the dynamic desorption characteristics of mercury during the thermal treatment of mercury-loaded sorbents at elevated temperatures under fixed-bed operations. Experiments were carried out in a 25.4 mm ID quartz bed enclosed in an electric furnace. Elemental mercury and mercuric chloride were tested with activated carbon and bauxite. The experimental results indicated that mercury desoption from sorbents was strongly affected by the desorption temperature and the mercury–sorbent pair. Elemental mercury was observed to desorb faster than mercuric chloride and activated carbon appeared to have higher desorption limits than bauxite at low temperatures. A kinetic model considering the mechanisms of surface equilibrium, pore diffusion and external mass transfer was proposed to simulate the observed desorption profiles. The model was found to describe reasonably well the experimental results.     

Air–Soil Exchange of NO,NO2 and O3 in Forests

The exchange of NO, NO₂ and O₃ at the soil surface wasmeasured with automatic dynamic chambers in a spruce forest and in abeech forest during periods of several months.NO was emitted from the soil at a rate of0–8 ng N m^-2 s^-1(spruce) and 0–15 ng Nm^-2 s^-1(beech), but there was no simple relationship between the flux andeither soil temperature or soil moisture. NO₂ and O₃ weredeposited at the soil surface. Deposition velocities forNO₂were on average 0.3 mm s^-1 (spruce) and 0.1 mms^-1(beech), and the deposition velocities of O₃ were on average 1.6 mm s^-1 (spruce) and 1.4 mm s^-1 (beech). The depositionvelocity of O₃ is fairly constant whereas the deposition velocityof NO₂ varies greatly, but the reasons remain to be investigated.     

Fabrication of Biodegradable Superabsorbent Using RSM Design for Controlled Release of KNO<Subscript>3</Subscript>

Present study envisaged the sequential experimental design approach for the development of biodegradable Gelatin-Tapoica/polyacrylamide superabsorbent. Percentage water uptake efficacy of candidate sample was optimized using Response Surface Methodology (RSM) design under microwave irradiation. Different process variables such as potassium persulphate and ammonium persulphate (KPS:APS) ratio, pH, reaction time concentration of acrylamide and N,N-methylene-bis-acrylamide (MBA) were investigated as a function of percentage swelling using sequential experimental design. Maximum liquid efficacy of 1550% was obtained at KPS:APS?=?1.0:0.5; acrylamide?=?7.67?×?10^?1 mol L^?1; MBA?=?1.76?×?10^?2 mol L^?1; pH 10 and time?=?110 s. The 3D crosslinked network formed was characterized using Fourier Transformation Infrared spectroscopy (FTIR), X-ray diffraction (XRD), Scanning Electron Microscopic (SEM) techniques and thermal stability was ensured by Thermal gravimetric Analysis/Differential Thermal Analysis/Differential Thermal Gravimetric (TGA/DTA/DTG) studies. Superabsorbent synthesized could increase the moisture content in different type of soils and was found to enhance the water-holding capability of the soil upto 60 days in clayey, 40 days in sandy and 51 days in mixture of two soils under controlled conditions. Further, candidate polymer was investigated for the in-vitro controlled release of the KNO₃ with diffusion exponent ‘n’ was found to be 0.4326 indicating Fickian type diffusion. Also, initial diffusion coefficient (D_I?=?3.49?×?10^?5 m² h^?1) was found to be greater than the lateral diffusion coefficient (D_L?=?3.76?×?10^?6 m² h^?1) indicated rapid release of KNO₃ during initial hours with slow release afterwards. The ecofriendly nature of the synthesized polymer was also tested by conducting biodegradation studies and it was found to degrade upto 94% and 88.1% within 70 days with degradation rate of 1.34 and 1.26% per day using composting method and vermicomposting method respectively. So, the synthesized candidate polymer was found to be boon for agriculture-horticulture sector with wide applicability.     

Mercury cleanup: The commercial application of a new mercury removal/recovery technology

Efficient, economical treatment of mercury-contaminated soils and industrial wastes requires a treatment process that reduces mercury content to near background levels (<1 ppm) and recovers the removed mercury in pure recyclable form without producing liquid, solid, or gaseous secondary wastes. This article reviews the results achieved using a medium-temperature thermal desorption process developed and commercialized by Mercury Recovery Services, Inc. (MRS) that has successfully achieved these goals.     

Production of hydrogen by steam gasification of dehydrochlorinated poly(vinyl chloride) or activated carbon in the presence of various alkali compounds

Steam gasification of dehydrochlorinated poly(vinyl chloride) (PVC) or activated carbon was carried out in the presence of various alkali compounds at 3.0 MPa and 560°C–660°C in a batch reactor or in a semi-batch reactor with a flow of nitrogen and steam. Hydrogen and sodium carbonate were the main products, and methane and carbon dioxide were the minor products. Yields of hydrogen were high in the presence of sodium hydroxide and potassium hydroxide. The acceleration effect of the alkali compounds on the gasification reaction was as follows: KOH > NaOH > Ca(OH)₂ > Na₂CO₃. The rate of gasification increased with increasing partial steam pressure and NaOH/C molar ratio. However, the rate became saturated at a molar ratio of NaOH/C greater than 2.0.