Effect of amorphous silica and silica sand on removal of chromium(VI) by zero-valent iron

The effect of two surfaces (amorphous silica and silica sand) on the reduction of chromium(VI) by zero-valent iron (Fe(0)) was investigated using batch reactors. The amendment of both surfaces significantly increased the rate and extent of Cr(VI) removal. The rate enhancement by amended surfaces is presumed to result from scavenging of Fe(0)-Cr(VI) reaction products by the provided surfaces, which minimized surface deactivation of Fe(0). The rate enhancing effect was greater for silica compared to sand, and the difference is attributed to silica's higher surface area, greater affinity for reaction products and pH buffering effect. For a given mass of Fe(0), the reactivity and longevity of Fe(0) to treat Cr(VI) increased with increasing dose of silica. Elemental analyses of the reacted iron and silica revealed that chromium removed from the solution was associated with both surfaces, with its mass distribution being approximately 1:1 per mass of iron and silica. The overall result suggests reductive precipitation was a predominant Cr(VI) removal pathway, which involves initial reduction of Cr(VI) to Cr(III), followed by formation of Cr(III)/Fe(III) hydroxides precipitates.     

Reductive dechlorination and biodegradation of 2,4,6-trichlorophenol using sequential permeable reactive barriers: laboratory studies

The reductive dechlorination and biodegradation of 2,4,6-trichlorophenol (2,4,6-TCP) was investigated in a laboratory-scale sequential barrier system consisting of a chemical and biological reactive barrier. Palladium coated iron (Pd/Fe) was used as a reactive barrier medium for the chemical degradation of 2,4,6-TCP, and a sand column seeded with anaerobic microbes was used as a biobarrier following the chemical reactive barrier in this study. Only phenol was detected in the effluent from the Pd/Fe column reactor, indicating that the complete dechlorination of 2,4,6-TCP was achieved. The residence time of 30.2-21.2h was required for the complete dechlorination of 2,4,6-TCP of 100 mg l(-1) in the column reactor. The surface area-normalized rate constant (k(SA)) is 3.84 (+/-0.48)x10(-5)lm(-2)h(-1). The reaction rate in the column tests was one order of magnitude slower than that in the batch test. In the operation of the biobarrier, about 100 microM of phenol was completely removed with a residence time of 7-8d. Consequently, the dechlorination prior to biodegradation turns out to increase the overall treatability. Moreover, the sequential permeable reactive barriers, consisting of iron barrier and biobarrier, could be recommended for groundwater contaminated with toxic organic compounds such as chlorophenols.     

Source identification and characterization of the accumulating non-biodegradable organics in Korean reservoirs

An increase in the chemical oxygen demand (COD) has been noticed in most Korean reservoirs. Therefore, this research systematically investigated the causes of organic accumulation. Samples of soil affecting the quality of water of reservoirs were collected at various sources and analyzed for their organic characteristics. The COD to biochemical oxygen demand (BOD) ratio was used as the key parameter in the evaluation of non-biodegradable (NBD) organic accumulation in the reservoirs. Soil samples containing plant roots were agitated, with the supernatant showing COD/BOD ratios of less than 2.8, while those of the composted tree leaves were greater than 5.0, suggesting that humic substances produced in forest areas are a major cause of NBD organic accumulation in reservoirs. In addition, the organic fractionation of the leachate from leaching tests showed that of the various types of hydrophobic natural organic matter (NOM), the larger molecular weight humic acid makes a greater contribution than fulvic acid to the increase in the NBD COD in Korean reservoirs.     

Enhancement of turbulent scalar mixing and its application by a multihole nozzle in selective catalytic reduction of NOx

The mixing characteristics of a passive scalar in the turbulent flow of a selective catalytic reduction process were numerically and experimentally investigated, focusing especially on an injection nozzle with multiple holes for the reducing agent. The multihole injection nozzle studied has six holes that are perpendicular to the ambient flue gas flow and are located near the tip of the nozzle. Large eddy simulation was applied to the turbulent flow and mixing fields to elucidate the mixing mechanism of the proposed nozzle compared with the single-hole nozzle that is commonly used in the conventional selective catalytic reduction process. From the results, there exist broader regions of higher turbulent intensities for the multihole nozzle than for the conventional single-hole nozzle. These regions are well matched with the positions of high vorticity in the near upstream region of the jet flow issuing from the multiple holes of the nozzle. Consequently, the high turbulent intensities and vorticity magnitudes lead to intensified mixing between the flue gas and the reducing agent. Hence, the most suitable molar ratio between NOx and the reducing agent for the catalytic reaction can be easily obtained within a shorter physical mixing length as a result of the enhanced scalar mixing. Finally, the numerical results were applied to a trial design version of a multihole nozzle, and this nozzle was experimentally tested to confirm its mixing performance.     

Wastewater treatment plants (WWTPs) as a source of sediment contamination by toxic organic pollutants and fecal sterols in a semi-enclosed bay in Korea

Toxic organic contaminants and a macrobenthic community were assayed in sediments collected near a wastewater treatment plant (WWTP) outfall to assess the impact of WWTP discharges on an aquatic environment. Average concentrations of toxic organic contaminants in sediments from 20 locations were 96.7ng TEQ/kg dry matter for PCDD/Fs, 1.84ng TEQ/kg dry matter for dioxin-like PCBs, 29.1microg/kg dry matter for PBDEs, 411microg/kg dry matter for nonylphenols, 1021microg/kg dry matter for fecal sterols, and 928microg/kg dry matter for PAHs. Concentrations of all the organic contaminants and fecal sterols varied widely and there was a clear decrease in concentration gradients with increasing distances from the WWTP outfall. This result suggests that WWTP activities contribute to contamination by organic chemicals. A survey of benthic organisms showed the dominance of a few polychaete species, indicating a deterioration of the macrobenthic community by the WWTP discharge. Non-parametric multidimensional scaling (MDS) ordination and Spearman correlation analyses showed that organic contamination is associated with the benthic community structure. For polychaete species, the sensitive species for organic contaminants was Paraprionospio pinnata, while contaminant-tolerant species were Spiochaetopterus koreana and Capitella capitata. BIOENV analyses of all locations suggested PCDDs and PCDFs as the major contaminants influencing the structure of the macrobenthic community. The present study highlights that continuous WWTP discharges contribute to severe organic contamination and risks for the benthic community in an aquatic ecosystem.     

Photocatalytic bacterial inactivation by polyoxometalates

The photocatalytic inactivation (PCI) of Escherichia coli (Gram-negative) and Bacillus subtilis (Gram-positive) was performed using polyoxometalate (POM) as a homogeneous photocatalyst and compared with that of heterogeneous TiO₂ photocatalyst. Aqueous suspensions of the microorganisms (10⁷–10⁸ cfu ml⁻¹) and POM (or TiO₂) were irradiated with black light lamps. The POM-PCI was faster than (or comparable to) TiO₂-PCI under the experimental conditions employed in this study. The relative efficiency of POM-PCI was species-dependent. Among three POMs (H₃PW₁₂O₄₀, H₃PMo₁₂O₄₀, and H₄SiW₁₂O₄₀) tested in this study, the inactivation of E. coli was fastest with H₄SiW₁₂O₄₀ while that of B. subtilis was the most efficient with H₃PW₁₂O₄₀. Although the biocidal action of TiO₂ photocatalyst has been commonly ascribed to the role of photogenerated reactive oxygen species such as hydroxyl radicals and superoxides, the cell death mechanism with POM seems to be different from TiO₂-PCI. While TiO₂ caused the cell membrane disruption, POM did not induce the cell lysis. When methanol was added to the POM solution, not only the PCI of E. coli was enhanced (contrary to the case of TiO₂-PCI) but also the dark inactivation was observed. This was ascribed to the in situ production of formaldehyde from the oxidation of methanol. The interesting biocidal property of POM photocatalyst might be utilized as a potential disinfectant technology.     

Implementation of a windblown dust parameterization into MODELS-3/CMAQ: Application to episodic PM events in the US/Mexico border

Windblown dust is known to impede visibility, deteriorate air quality and modify the radiation budget. Arid and semiarid areas with unpaved and unvegetated land cover are particularly prone to windblown dust, which is often attributed to high particulate matter (PM) pollution in such areas. Yet, windblown dust is poorly represented in existing regulatory air quality models. In a study by the authors on modeling episodic high PM events along the US/Mexico border using the state-of-the-art CMAQ/MM5/SMOKE air quality modeling system [Choi, Y.-J., Hyde, P., Fernando, H.J.S., 2006. Modeling of episodic particulate matter events using a 3D air quality model with fine grid: applications to a pair of cities in the US/Mexico border. Atmospheric Environment 40, 5181–5201], some of the observed PM₁₀ NAAQS exceedances were inferred as due to windblown dust, but the modeling system was incapable of dealing with time-dependent episodic dust entrainment during high wind periods. In this paper, a time-dependent entrainment parameterization for windblown dust is implemented in the CMAQ/MM5/SMOKE modeling system with the hope of improving PM predictions. An approach for realizing windblown dust emission flux for each grid cell over the study domain on an hourly basis, which accounts for the influence of factors such as soil moisture content, atmospheric stability and wind speed, is presented in detail. Comparison of model predictions with observational data taken at a pair of US/Mexico border towns shows a clear improvement of model performance upon implementation of the dust emission flux parameterization.     

Performance of an electrochemical COD (chemical oxygen demand) sensor with an electrode-surface grinding unit

An electrochemical COD (chemical oxygen demand) sensor using an electrode-surface grinding unit was investigated. The electrolyzing (oxidizing) action of copper on an organic species was used as the basis of the COD measuring sensor. Using a simple three-electrode cell and a surface grinding unit, the organic species is activated by the catalytic action of copper and oxidized at a working electrode, poised at a positive potential. When synthetic wastewater was fed into the system, the measured Coulombic yields were found to be dependent on the COD of the synthetic wastewater. A linear correlation between the Coulombic yields and the COD of the synthetic wastewater was established (10-1000 mg L(-1)) when the electrode-surface grinding procedure was activated briefly at 8 h intervals. When various kinds of wastewater samples obtained from various sewage treatment plants were measured, linear correlations (r(2)> or = 0.92) between the measured EOD (electrochemical oxygen demand) value and COD of the samples were observed. At a practical wastewater treatment plant, the measurement system was successfully operated with high accuracy and good stability over 3 months. These experimental results show that the application of the measurement system would be a rapid and practical method for the determination of COD in water industries.     

Structural and photocatalytic properties of TiO2 films fabricated on silicon substrates by MOCVD method

Silicon(111) and Silicon(100) were employed for fabrication of TiO2 films by metal organic chemical vapor deposition( MOCVD).Titanium(Ⅳ) isopropoxide(Ti[O(C3H7)4]) was used as a precursor. The as-deposited TiO2 films were characterized with FE-SEM, XRD and AFM. The photocatalytic properties were investigated by decomposition of aqueous Orange Ⅱ. And UV-VlS photospectrometer was used for checking the absorption characteristics and photocatalytic degradation activity. The crystalline and structural properties of TiO2 film had crucial influences on the photodegradation efficiency. For MOCVD in-situ deposited films on Si substrates, the photoactivities varied following a shape of “M”: at Iower(350℃ ), middle(500℃ ) and higher(800℃ ) temperature of deposition, relative lower photodegradation activities were observed. At 400% and 700% of deposition, relative higher efficiencies of degradation were obtained, because one predominant crystallite orientation could be obtained as deposition at the temperature of two levels, especially a single anatase crystalline TiO2 film could be obtained at 700℃.     

Combined simulation of combustion and gas flow in a grate-type incinerator

Computational fluid dynamic (CFD) analysis of the thermal flow in the combustion chamber of a solid waste incinerator provides crucial insight into the incinerator's performance. However, the interrelation of the gas flow with the burning waste has not been adequately treated in many CFD models. A strategy for a combined simulation of the waste combustion and the gas flow in the furnace is introduced here. When coupled with CFD, a model of the waste combustion in the bed provides the inlet conditions for the gas flow field and receives the radiative heat flux onto the bed from the furnace wall and gaseous species. An unsteady one-dimensional bed model was used for the test simulation, in which the moving bed was treated as a packed bed of homogeneous fuel particles. The simulation results show the physical processes of the waste combustion and its interaction with the gas flow for various operational parameters.