Degradation of atrazine by modified stepwise-Fenton's processes

The removal of atrazine (ATZ) by stepwise Fenton's processes (stepwise-FP) was studied and the system models were developed through the examination of reaction kinetics. The study compared the performance of the removal of ATZ by conventional FP with stepwise-FP, where the total dose of H(2)O(2) was split and inputted into the system at different times and/or quantities. The performance of stepwise-FP was found to be better than that of conventional FP. This was probably due to the minimization of the peak concentration of H(2)O(2) in the solution, which reduced the probability that valuable H(2)O(2) and hydroxyl radicals would be consumed in forming weaker radicals. The reaction kinetics of the decay of ATZ in stepwise-FP was found to be a two-stage process; and in each stage, fast decay followed by stagnant decay was observed. Two characterized constants (the initial decay rate and the oxidative capacity) were introduced and were found to be useful in quantifying the stepwise-FP. The models for predicting stepwise-FP with respect to different dosing times and/or asymmetrical doses were developed, and were found to be very useful for evaluating the system performance and/or for process design.     

Biosorption of reactive black 5 by Corynebacterium glutamicum biomass immobilized in alginate and polysulfone matrices

Corynebacterium glutamicum, a lysine fermentation industry waste, showed promise for the removal of Reactive black 5 (RB5). Due to practical difficulties in solid-liquid separation, the free biomass was immobilized in two polymer matrices: calcium alginate and polysulfone. Initially, the optimization of biomass loading in polymeric beads and bead dosage were examined. Of the different combinations examined, 4% (with bead dosage of 2 g per 40 ml) and 14% (with bead dosage of 1 g per 40 ml) in the case of alginate and polysulfone beads, respectively, were identified as the optimal conditions. According to the Langmuir model, at pH 1, the maximum RB5 uptakes of 352, 282 and 291 mg g(-1) were observed for free, alginate and polysulfone-immobilized biomass, respectively. According to the Weber-Morris model, intraparticle diffusion was found to be the potential rate limiting step for the immobilized beads. Regeneration experiments, with 0.01 M NaOH and Na(2)CO(3) as eluents, revealed that polysulfone beads exhibited invariable RB5 uptake capacity and very high mechanical stability even at the end of twentieth cycle, confirming the technical feasibility of the biosorption process for industrial applications.     

Effects of temperature and dissolved oxygen on Se(IV) removal and Se(0) precipitation by Shewanella sp. HN-41

Facultative anaerobic Shewanella sp. strain HN-41 was able to utilize selenite (Se(IV)) as a sole electron acceptor for respiration in anaerobic condition, resulting in reduction of Se(IV) and then precipitation of elemental Se nano-sized spherical particles, which were identified using energy-dispersive X-ray spectroscopy and X-ray absorption near-edge structure spectroscopy. When the effects on Se(IV) reduction to elemental Se were studied by varying incubation temperatures and dissolved oxygen contents, Se(IV) reduction occurred more actively with higher removal rate of Se(IV) in aqueous phase and well-shaped spherical Se(0) nanoparticles were formed from the incubations under N(2) (100%) or N(2):O(2) (80%:20%) at 30 degrees C with average diameter values of 181+/-40 nm and 164+/-24 nm, respectively, while relatively less amounts of irregular-shaped Se(0) nanoparticles were produced with negligible amount of Se(IV) reduction and removal under 100% of O(2). The Se particle size distributions based on scanning electron microscopy also showed a general tendency towards decreased Se particle size as oxygen content increased, whereas the particle size seemed uncorrelated to the change in the incubation temperature. These results also suggest that the size-controlled biological Se(0) nanospheres production may be achieved simply by changing the culture conditions.     

Transport and Adhesion of Escherichia coli JM109 in Soil Aquifer Treatment (SAT): One-Dimensional Column Study

Bacteria transport and adhesion experiments under water-saturated and partially saturated conditions were examined over a wide range of ionic strength, from 1 to 100 mM KCl, CaCl₂, and MgCl₂, and at water contents of 0.15 and 0.22 in sand columns packed with three different sands, baked, sterilized, and raw sands in order to investigate the effects of ionic strength, water content, and porous media type on the microbial adhesion in soil aquifer treatment (SAT). Well-characterized Escherichia coli JM109 were used as model bacterial cells in this study. Column study results showed that bacterial deposition rates increased with increasing ionic strength and decreasing water content, and were higher in raw sand columns than those in other sand columns. The Derjaguin–Landau–Verwey–Overbeek (DLVO) theory was applied to experimental results in order to consider the interaction energies between the bacterial cells and collector grains; results revealed that a considerable amount of bacterial cells was weakly deposited onto the solid surfaces in secondary minimum.     

Estimation Of Selenium Concentration In Shallow Groundwater In Alluvial Fan Area In Tsukui, Central Japan

Total selenium (Se) and water-soluble Se in soil, and Se in a shallow groundwater were hydrogeochemically researched in an alluvial fan area in Tsukui, Central Japan. The water-soluble Se was estimated at average level of 2.6 ± 1.2μg Se kg⁻¹ dry soil (± SD, n = 25), showing less than 1% of the total Se (349–508μg Se kg⁻¹ dry soil) in soil. The monthly Se concentration in groundwater was average 2.2μg,L⁻¹, ranging 1.6–2.4μg,L⁻¹ during 2001–2003. The Se in groundwater significantly decreased with increasing groundwater level after rainfall. This result indicated that Se-bearing water percolated with relatively low Se concentration through the soil layer. According to our prediction model of linear regression curve on the observation data, Se concentration in the groundwater was estimated to be increasing with the very low rate of 4.35 × 10⁻³μg Se L⁻¹,yr⁻¹. The hydrogeochemical research and the result of the prediction model showed that any explosive increase of Se will hardly occur in this groundwater without an anthropogenic Se contamination.     

Desorption Kinetics of Benzene in a Sandy Soil in the Presence of Powdered Activated Carbon

Desorption kinetics of benzene was investigated with a modified biphasic desorption model in a sandy soil with five different powdered activated carbon (PAC) contents (0, 1, 2, 5, 10% w/w) as sorbents. Sorption experiments followed by series dilution desorption were conducted for each sorbent. Desorption of benzene was successively performed at two stages using deionized water and hexane. Modeling was performed on both desorption isotherm and desorption rate for water-induced desorption to elucidate the presence of sorption–desorption hysteresis and biphasic desorption and if present to quantify the desorption-resistant fraction (q _irr) and labile fraction (F) of desorption site responsible for rapid process. Desorption isotherms revealed that sorption–desorption exhibited a severe hysteresis with a significant fraction of benzene being irreversibly adsorbed onto both pure sand and PAC, and that desorption-resistant fraction (q _irr) increased with PAC content. Desorption kinetic modeling showed that desorption of benzene was biphasic with much higher (4–40 times) rate constant for rapid process (k ₁) than that for slow process (k ₂), and that the difference in the rate constant increased with PAC content. The labile fraction (F) of desorption site showed a decreasing tendency with PAC. The experimental results would provide valuable information on remediation methods for soils and groundwater contaminated with BTEX.     

PCDD/F and dioxin-like PCB in Hong Kong air in relation to their regional transport in the Pearl River Delta region

PCDD/F and dioxin-like PCB were measured in 142 air samples of Hong Kong. The annual average PCDD/F and dioxin-like PCB concentrations obtained for Hong Kong air at Tap Mun (PCDD/F: 1724+/-1984; dioxin-like PCB: 1572+/-1170 fg m(-3)), Yuen Long (PCDD/F: 2927+/-2695; dioxin-like PCB: 4331+/-1962 fg m(-3)) and Tsuen Wan (PCDD/F: 1875+/-1502; dioxin-like PCB: 2972+/-1510 fg m(-3)) from January 2004 to March 2005 were comparable to other urban centers around the world and were within the Japanese and USA ambient air quality guidelines. A clear seasonal pattern was observed for PCDD/F, generally with a 50-60 times higher air concentration in winter when background northerly wind was weaker and land-sea breeze prevailed, resulting in regional transport; and a lower concentration in summer, due to the inflow of clean oceanic southeasterly wind from the South China Sea. A higher WHO-TEQ value of dioxin-like PCB (mainly attributed to the relatively higher WHO-TEQ value of PCB 126) in Yuen Long during winter, compared with other months, could also be related to the regional transport by the winter monsoon wind and the low mixing height in winter. Spatially, air concentrations of PCDD/F and dioxin-like PCB demonstrated a west-to-east gradient (with Yuen Long>Tsuen Wan>Tap Mun). It is suggested that PCDD/F and dioxin-like PCB were transported into the western airshed of Hong Kong from the Pearl River Delta by land-sea breeze circulation and confined to the northwestern part, due to the blocking effect of the northwestern airshed in Hong Kong.     

Effect of mixing on NO removal in the selective noncatalytic reduction reaction process

The effect of mixing of NH₃ and NO on the selective noncatalytic reduction (SNCR) reaction was investigated using a bench-scale reactor. Three different experimental conditions were compared for the removal of NO in the bulk gas with NH₃, a reducing agent, by means of mixing and contacting. The temperature that gave the highest NO removal efficiency was about 800°C when NH₃ was injected with air or NH₃ was premixed and air was injected. It is suggested that control of mixing of the reducing agent and the injection conditions could be a good way to increase NO removal efficiency as well as to lower the reaction temperature. When NH₃ was injected with air, the NO removal efficiency increased with increasing injected air flow if the initial NO concentration was low, whereas for high NO concentrations, the NO removal efficiency slightly increased up to an injected air flow rate of 100 ml/min. A proposed mixed-flow model can be used as a prediction tool for the NO removal efficiency covering various conditions of the real SNCR process.     

Long-Term Impacts of Land-Use Change on Non-Point Source Pollutant Loads for the St. Louis Metropolitan Area, USA

A land-use-change simulation model (LEAM) and a non-point-source (NPS) water quality model (L-THIA) were closely coupled as LEAMwq in order to determine the long-term implications of various degree of urbanization on NPS total nitrogen (TN), total suspended particles (TSP), and total phosphorus (TP) loads. A future land-use projection in the St. Louis metropolitan area from 2005 to 2030 using three economic growth scenarios (base, low, and high) and a long-term precipitation dataset were used to predict the mean annual surface runoff and mean annual NPS pollutant loads in the region. Results show mean annual TN increases of 0.21%, 0.13%, and 0.14% by 2030 compared to 2000 under the base, high, and low scenarios, respectively. TSP and TP showed similar trends with different magnitudes. Corresponding changes in annual mean surface runoff were shown to be lower than expected, which might be attributed to the small-scale conversion pattern of land uses. In the most dramatic change (high growth) scenario, the runoff would increase across time but at varying rates, and temporal pollutant loads would result in a more complicated pattern than in the other scenarios. This is attributed to the complex interactions between event mean concentrations of pollutants and the magnitude of changes in land-use acreages. By integrating L-THIA with LEAM, LEAMwq was found to be a useful planning tool to illustrate in a quick and simple manner how future water quality is connected to decision-making on future land-use change.     

Nitrate reduction by fluoride green rust modified with copper

Nitrate reduction by the fluoride form of green rust modified with copper (GR-F(Cu)) was investigated using a batch reactor system. The extent of nitrate reduction was measured by measuring the increase in concentration of ammonia, which is the final product of nitrate reduction by GR. This approach was required, because nitrate could be removed from solution by ion exchange without reduction. The rate of ammonium production was investigated over the range of pH 7.8-11. The fastest reaction was achieved at pH 9 when GR was present at a concentration of 0.083M as Fe(II) and 1mM of Cu(II) was added. The rate at pH 9 was enhanced by a factor of 2.5 compared to that at pH 7.8 by comparing the time elapsed to transform all nitrate to ammonium. Kinetics of nitrate reduction by GR-F at pH 7.8 were affected by the concentration of Cu(II) added. The rate constants for ammonium production increased from 0.012 to 1.52h(-1) as Cu(II) additions increased from 0 to 2.5mM, but the reaction rate at 5mM was slightly decreased to 1.25h(-1). The mechanism of enhanced rates of nitrate reduction by addition of Cu(II) could not be fully determined in this study. However, XRD results showed that magnetite was produced in the reaction of Cu(II) and GR-F and SEM shows the production of nano-size particles which were not fully identified in this study. In addition, the concentration of Fe(II) in GR was observed to linearly decrease with concentration of Cu(II) added.