Assessing the effects of surface-bound humic acid on the phototoxicity of anatase and rutile TiO2 nanoparticles in vitro

In this study,the cytotoxicity of two different crystal phases of TiO₂ nanoparticles,with surface modification by humic acid（HA）,to Escherichia coli,was assessed.The physicochemical properties of TiO₂ nanoparticles were thoroughly characterized.Three different initial concentrations,namely 50,100,and 200 ppm,of HA were used for synthesis of HA coated TiO₂ nanoparticles（denoted as A/RHA50,A/RHA100,and A/RHA200,respectively）.Results indicate that rutile（LC50（concentration that causes 50%mortality compared the control group）=6.5）was more toxic than anatase（LC₅0=278.8）under simulated sunlight（SSL）irradiation,possibly due to an extremely narrow band gap.It is noted that HA coating increased the toxicity of anatase,but decreased that of rutile.Additionally,AHA50 and RHA50had the biggest differences compared to uncoated anatase and rutile with LC₅0of 201.9 and21.6,respectively.We then investigated the formation of reactive oxygen species（ROS）by TiO₂ nanoparticles in terms of hydroxyl radicals（OH）and superoxide anions（O₂^-）.Data suggested that O₂^- was the main ROS that accounted for the higher toxicity of rutile upon SSL irradiation.We also observed that HA coating decreased the generation of OH and O₂^- on rutile,but increased O₂^- formation on anatase.Results from TEM analysis also indicated that HA coated rutile tended to be attached to the surface of E.coli more than anatase.     

Photocatalytic degradation of volatile organic compounds at the gas-solid interface of a TiO2 photocatalyst

In the present work, photocatalytic degradation of volatile organic compounds including gas-phase trichloroethylene (TCE), acetone, methanol and toluene over illuminated TiO2 was closely examined in a batch photoreactor as a function of water vapor, molecular oxygen and reaction temperature. Water vapor enhanced the photocatalytic degradation rate of toluene, but was inhibitive for acetone, and, there was an optimum water vapor concentration in the TCE and methanol removal. In a nitrogen atmosphere, it showed lower photocatalytic degradation rate than in air and pure oxygen. Thus, it could be concluded that oxygen is an essential component in photocatalytic reactions by trapping photogenerated electrons on the semiconductor surface and by decreasing the recombination of electrons and holes. As for the influence of reaction temperature, it was found that photocatalytic degradation was more effective at a moderate temperature than at an elevated temperature for each compound.     

Kinetics of reductive denitrification by nanoscale zero-valent iron

Zero-valent iron powder (Fe0) has been determined to be potentially useful for the removal of nitrate in the water environment. This research is aimed at subjecting the kinetics of denitrification by nanoscale Fe0 to an analysis of factors affecting the chemical denitrification of nitrate. Nanoscale iron particles with a diameter in the range of 1-100 nm, which are characterized by the large BET specific surface area to mass ratio (31.4 m2/g), removed mostly 50, 100, 200, and 400 mg/l of nitrate within a period of 30 min with little intermediates. Compared with microscale (75-150 microm) Fe0, end product is not ammonia but N2 gas. Kinetics analysis from batch studies revealed that the denitrification reaction with nanoscale Fe0 appeared to be a pseudo first-order with respect to substrate and the observed reaction rate constant (k(obs)) varied with iron content at a relatively low degree of application. The effects of mixing intensity (rpm) on the denitrification rate suggest that the denitrification appears to be coupled with oxidative dissolution of iron through a largely mass transport-limited surface reaction (<40 rpm).     

Remediation of arsenic-contaminated soils and washing effluents

Laboratory experiments were conducted to determine the distribution of various arsenic species in tailings and soils. Other specific goal of the tests were to evaluate the extraction efficiency of arsenic using alkaline or acid washing, to determine optimum operational parameters of alkaline washing, and to evaluate the arsenic precipitation of washing effluents by pH adjustment or ferric chloride addition. Alkaline washing using sodium hydroxide was found to be favorable in removing arsenic from tailings or soils having a higher portion of arsenic in the operationally defined crystalline mineral fraction of crystalline oxide and amorphous aluminosilicates. This is due to the ligand displacement reaction of hydroxyl ions with arsenic species and high pH conditions that can prevent readsorption of arsenic because predominant negatively charged crystalline oxides do not attract the negatively charged oxyanions. For tailings, sodium hydroxide had 10-20 times higher extraction efficiencies than hydrochloric- or citric acid. The optimum concentration of sodium hydroxide for soil washing was determined to be 200 mM for all samples, while the optimum ratios were 10:1 and 5:1 for tailings and field/river sedimentary soils, respectively. The washing effluent of river soil was effectively treated by adjusting pH to 5-6 with hydrochloric acid, resulting in arsenic concentrations of <50 microgl(-1). In the case of field soil effluent, an addition of ferric chloride with a minimum mass ratio of 11 (Fe/As) was needed to reduce the arsenic below 50 microgl(-1).     

Ozone disintegration of excess biomass and application to nitrogen removal.

A pilot-scale facility integrated with an ozonation unit was built to investigate the feasibility of using ozone-disintegration byproducts of wasted biomass as a carbon source for denitrification. Ozonation of biomass resulted in mass reduction by mineralization as well as by ozone-disintegrated biosolids recycling. Approximately 50% of wasted solids were recovered as available organic matter (ozonolysate), which included nonsettleable microparticles and soluble fractions. Microparticles were observed in abundance at relatively low levels of ozone doses, while soluble fractions became dominant at higher levels of ozone doses in ozone-disintegrated organics. Batch denitrification experiments showed that the ozonolysate could be used as a carbon source with a maximum denitrification rate of 3.66 mg nitrogen (N)/g volatile suspended solids (VSS) x h. Ozonolysate was also proven to enhance total nitrogen removal efficiency in the pilot-scale treatment facility. An optimal chemical oxygen demand (COD)-to-nitrogen ratio for complete denitrification was estimated as 5.13 g COD/g N. The nitrogen-removal performance of the modified intermittently decanted extended aeration process dependent on an external carbon supply could be described as a function of solids retention time.     

Effect of photosensitizer riboflavin on the fate of 2,4,6-trinitrotoluene in a freshwater environment

The effect of riboflavin (1 microM) on the fate of TNT (20 mg/l) in a natural water environment was studied. The relative contribution of photolysis, microbial assemblages and freshwater matrix to TNT degradation was examined. The rates, extent and products of TNT and riboflavin transformation were compared under different experimental conditions. It was found that riboflavin significantly enhanced the degradation of TNT in natural water environment. Thus it is a potentially useful photosensitizing agent for the treatment of TNT-contaminated surface water. Furthermore, in the presence of riboflavin, two new intermediates with max. absorption wavelength of 230 nm were found, demonstrating that transformation of TNT in the presence of riboflavin undergoes different pathways.     

Effect of cold-temperature shock on nitrification.

Nitrification is known as the most temperature-sensitive step among the biological processes in wastewater treatment. The purpose of this study was to investigate the effect of temperature on nitrification, in the case of a sharp decrease of temperature, and to compare this effect with that of a gradual temperature decrease. It was found that a sudden temperature decrease affected nitrification much more than predicted. The immediate decrease of temperature by 10 degrees C led to a 20% larger decrease of specific nitrification rate than predicted by the temperature correction factor of 1.072. The change of nitrification rate resulting from a gradual temperature decrease was modeled correctly with the current default temperature correction factor of 1.072. It was concluded that the correction factor actually can be applied to a gradual temperature-change situation; however, in the case of a sudden temperature decrease, measures need to be taken to avoid nitrifier washout.     

Epipelagic mesozooplankton succession and community structure over a marine ouffall area in the northeastern South China Sea

This study analyses distribution and abundance patterns of mesozooplankton communities at 13 stations in the coastal waters over a marine outfall area in the northeastern South China Sea. Cruises were conducted in March, June and September 2002, and plankton samples were collected with a 333 microm North Pacific net. The Mesozooplankton was dominated by calanoid Copepods, Cladocera, Chaetognatha and Pteropoda. Stations located near the entrance of the harbor provided a relatively higher abundance of Noctilucales and Radiolarians. In total, 20 zooplankton groups were identified in which, Calanoida, Cladocera, Chaetognatha, Pteropoda, Poecilostomatoida and Appendicularia comprised 92.77% of the total zooplankton abundance. Copepoda dominated in all three cruises, comprising 65.32% of the total mesozooplankton abundance. Samples collected in June recorded higher mesozooplankton abundance than March and September samples. Onshore stations recorded higher BOD values, higher abundance of Noctilucales and Radiolarians and a relativelylower abundance of the overall mesozooplankton. Total mesozooplankton abundance did not correlate significantly with temperature, pH, or dissolved oxygen, but correlated negatively with BOD.     

Large-eddy simulation of turbulent flow and dispersion over a complex urban street canyon

Turbulent flow and dispersion characteristics over a complex urban street canyon are investigated by large-eddy simulation using a modified version of the Fire Dynamics Simulator. Two kinds of subgrid scale (SGS) models, the constant coefficient Smagorinsky model and the Vreman model, are assessed. Turbulent statistics, particularly turbulent stresses and wake patterns, are compared between the two SGS models for three different wind directions. We found that while the role of the SGS model is small on average, the local or instantaneous contribution to total stress near the surface or edge of the buildings is not negligible. By yielding a smaller eddy viscosity near solid surfaces, the Vreman model appears to be more appropriate for the simulation of a flow in a complex urban street canyon. Depending on wind direction, wind fields, turbulence statistics, and dispersion patterns show very different characteristics. Particularly, tall buildings near the street canyon predominantly generate turbulence, leading to homogenization of the mean flow inside the street canyon. Furthermore, the release position of pollutants sensitively determines subsequent dispersion characteristics.     

Water-soluble characteristics of chlorine in char derived from municipal solid wastes

Chlorine in char derived from municipal solid waste (MSW) was characterized and quantified based on its water solubility: easily water-soluble, hardly water-soluble, and non-water-soluble chlorine. For that, a four-cycle process of water-washing, heating or carbonation were carried out. In order to confirm the characteristics of non-water-soluble chlorine, additional thermal treatment and an alkali-acid washing process were applied to washed char. It was found that a large particle size of char (0.5-1.0 mm) significantly contributed to the amount of non-water-soluble chlorine. Pulverization and HNO3-HF digestion were performed to identify a factor to interfere chlorine release from char with a large particle size. Pulverization was proven ineffective for release of non-water-soluble chlorine, whereas approximately 32% of non-water-soluble chlorine was extracted by HNO3-HF digestion. Therefore, the presence of non-water-soluble chlorine is likely to originate from its chemical property rather than simply from its physical one.