Sorption and desorption behavior of benzidine in different solvent-sediment systems

The sorption and desorption behavior of benzidine in eight solvent-sediment systems were studied using a batch method. The solvents tested included deionized water (DI), calcium chloride solution (CaCl2), sodium hydroxide solution (NaOH), acetonitrile (ACN), a mixture of acetonitrile and ammonium acetate solution (ACN-NH4OAc), methanol (MeOH), ammonium acetate solution (NH4OAc) and hydrochloric acid solution (HCl). Three sets of sorption isotherm experiments were conducted separately in these eight solvents with seven days, three weeks, and two months of contact times, respectively. The results demonstrated nonlinear benzidine sorption phenomena in all eight solvents with higher sorption affinities for sediment sites in the aqueous solvents than in the organic solvents. The results from the desorption experiments revealed that the benzidine desorption efficiencies in the solvents decreased in an order, which was approximately the reverse order of its sorption affinity. Results also suggested that hydrophobic partitioning and covalent binding processes dominated in the desorption experiments, while cation exchange process had little effect on desorption of benzidine. A three-stage model was subsequently applied to simulate the desorption data in the selected solvents of ACN, ACN-NH4OAc and NaOH, respectively. The rapidly desorbing initial fractions were about 0.13-0.20, 0.15-0.26, and 0.18-0.25 for ACN, ACN-NH4OAc and NaOH, respectively. Finally, the sorbed concentrations of benzidine in slowly and very slowly desorbing domains in the selected solvents were correlated with the maximum sorption capacities obtained from the Langmuir sorption isotherm model. The maximum sorption capacities of benzidine were found to be comparable to the amount of benzidine residing in the slowly and very slowly desorbing domains.     

Using FeGAC/H2O2 process for landfill leachate treatment

Due to the growing concern of highly contaminated landfill leachate problems in Taiwan, an innovative advanced catalytic oxidation (FeGAC/H(2)O(2)) process was developed and employed in this research to treat the landfill leachate from central Taiwan. Experimental results indicated that the FeGAC/H(2)O(2) process could effectively remove organic compounds from landfill leachate. The presence of iron oxide coated granular activated carbon (FeGAC) greatly improved the oxidative ability of H(2)O(2) for the removal of humic acids, fulvic acids and non-humic substance from leachate. For instance, at pH 6, the removal efficiencies of FeGAC/H(2)O(2) and H(2)O(2) processes were 70% and 8%, respectively. FeGAC/H(2)O(2) combined both advantages of FeGAC and H(2)O(2) where FeGAC had good organics adsorption ability and could effectively catalyse the hydrogen peroxide oxidation reaction for organics removal.     

Evaluation of nitrification inhibitor 3,4-dimethyl pyrazole phosphate on nitrogen leaching in undisturbed soil columns

The application of nitrogen fertilizers leads to various ecological problems such as nitrate leaching. The use of nitrification inhibitors (NI) as nitrate leaching retardants is a proposal that has been suggested for inclusion in regulations in many countries. In this study, the efficacy of the new NI, 3,4-dimethyl pyrazole phosphate (DMPP), was tested under simulated high-risk leaching situations in two types of undisturbed soil columns. The results showed that the accumulative leaching losses of soil nitrate under treatment of urea with 1.0% DMPP, from columns of silt loam soil and heavy clay soil, were 66.8% and 69.5% lower than those soil columns tested with regular urea application within the 60 days observation, respectively. However, the losses of ammonium leaching were reversely increased 9.7% and 6.7% under the former treatment than the latter one. Application of regular urea with 1.0% DMPP addition can reduce about 59.3%-63.1% of total losses of inorganic nitrogen via leaching. The application of DMPP to urea had stimulated the inhibition effects of DMPP on the ammonium nitrification process in the soil up to 60 days. It is proposed that the DMPP could be used as an effective NI to control inorganic N leaching losses, minimizing the risk of nitrate pollution in shallow groundwater.     

Influence of metal ion on sorption of p-nitrophenol onto sediment in the presence of cetylpyridinium chloride

Heavy metals and surfactants have a significant effect on the sorption of organic contaminants. In this study, batch equilibrium experiments were carried out to investigate the influence of Pb(NO(3))(2) on the sorption of p-nitrophenol (PNP) onto sediments in the presence of cationic surfactant cetylpyridinium chloride (CPC). Results indicated that in the complex system containing PNP, Pb(NO(3))(2) and CPC, the sorption of PNP decreased with increasing concentration of Pb(NO(3))(2) due primarily to competing for adsorption sites. Likewise, partitioning of PNP in adsorbed surfactant layers and micelles decreased with increasing level of Pb(NO(3))(2). Moreover, the influence of different metal ions (Pb(2+), Cd(2+), Zn(2+)) was examined and results indicated that the presence of heavy metals inhibited the sorption of PNP in the order: Pb(2+)>Cd(2+)>Zn(2+). The competitive effect of the heavy metals was in agreement with the hydration energy and hydrated radius. The results are believed to provide a useful insight into describing the transport and fate of PNP in natural environments.     

Pressurized CO2/zero valent iron system for nitrate removal

A fluidized zero valent iron (ZVI) reactor pressurized by CO(2) gas for controlling pH was employed for nitrate reduction. The proposed CO(2) pressurized system potentially has advantages of using less CO(2) gas and reaching equilibrium pH faster than CO(2)-bubbled system. However, due to weak acid nature of carbonic acid, system pH gradually increased with increasing oxidation of ZVI and reduction of nitrate. As pH increased with progress of reaction, nitrate removal rate decreased continuously. The results indicate that nitrate removal efficiency increases with increasing initial ZVI dosage but reaches plateau at ZVI doses of higher than 8.25gl(-1), and initial nitrate concentration up to 100mg l(-1) as N has minimal impact on the removal efficiency. Unlike the fluidized system with pH control by strong acid reported in our pervious study, near 100% of nitrogen recovery was observed in the current process, indicating that nitrate reduction by ZVI with different pH controlled mechanisms will have different reaction routes.     

The study on the dechlorination of OCDD with Pd/C catalyst in ethanol-water solution under mild conditions

Dechlorination of octachlorodibenzo-p-dioxin (OCDD) was carried out in ethanol-water (v/v=1:1) solution of NaOH in the presence of Pd/C catalysts with the use of H(2). The substrate was dechlorinated with Pd/C under mild conditions (atmospheric pressure and <100 degrees C) to give a chlorine-free product, dibenzo-p-dioxin (DD), in high yields. After reaction of 3h at 50 degrees C, 95.9% OCDD was degraded to low dechlorinated congeners and the yield of DD was 77.4%. We have also studied the dechlorination selectivity of chlorine atoms on the different substituted positions and postulated the dechlorination pathway of OCDD. For OCDD, the 2-position has higher reactivity than 1-position, but the difference is very small. From the distribution statistics of the intermediates during the reaction, we postulate that the steric effect plays an important role during the reaction and affect the dechlorination pathway of OCDD.     

Influence of the DMPP (3,4-dimethyl pyrazole phosphate) on nitrogen transformation and leaching in multi-layer soil columns

The application of nitrogen fertilizers leads to various ecological problems such as nitrate leaching. The use of nitrification inhibitors as nitrate leaching retardants is a proposal that has been suggested for inclusion in regulations in many countries. In this study, using a multi-layer soil column device, the influence of new nitrification inhibitor DMPP (3,4-dimethyl pyrazole phosphate) was studied for understanding the nitrogen vertical transformation and lowering the nitrate leaching at different soil profile depths. The results indicated that, within 60 d of experiment, the regular urea added 1.0% DMPP can effectively inhibit the ammonium oxidation in the soil, and improve the ammonium concentration in soil solution over the 20cm depths of soil profile, while decline the concentrations of nitrate and nitrite. No obvious difference was found on ammonium concentrations in soil solution collected from deep profile under 20cm depths between regular urea and the urea added 1.0% DMPP. There was also no significant difference for the nitrate, ammonium and nitrite concentrations in the soil solution under 40cm depths of soil profile with the increasing nitrogen application level, among the treatments of urea added 1.0% DMPP within 60 d. It is proposed that DMPP could be used as an effective nitrification inhibitor in some region to control ammonium oxidation and decline the ion-nitrogen leaching, minimizing the shallow groundwater pollution risk and being beneficial for the ecological environment.     

Mechanism of decolorization and degradation of CI Direct Red 23 by ozonation combined with sonolysis

The decolorization and degradation of CI Direct Red 23, which is suspected to be carcinogenic, were investigated using ozonation combined with sonolysis. The results showed that the combination of ozonation and sonolysis was a highly effective way to remove color from waste water. The operational parameters, namely concentration of the dye, pH, ozone dose and ultrasonic density, were investigated during the process. The decolorization of the dye followed pseudo-first-order kinetics. Increasing the initial concentration of Direct Red 23 led to a decreasing rate constant. The optimum pH for the reaction was 8.0, and both lower and higher pH decreased the removal rate. The effect of the ozone dose on the dye decolorization was much greater than that of the sonolysis density. Intermediates such as naphthalene-2-sulfonic acid, 1-naphthol, urea and acetamide were detected by gas chromatography coupled with mass spectrometry in the absence of pH buffer, while nitrate and sulfate ions and formic, acetic and oxalic acids were detected by ion chromatography. A tentative degradation pathway was proposed without any further quantitative analyses. During the degradation, all nitrogen atoms and phenyl groups of Direct Red 23 were degraded into urea, nitrate ion, nitrogen and formic, acetic and oxalic acids, etc.     

In situ studies on the distribution patterns and dynamics of microcystins in a biomanipulation fish--bighead carp (Aristichthys nobilis)

The distribution and dynamics of microcystins in various organs of the phytoplanktivorous bighead carp were studied monthly in Lake Taihu, which is dominated by toxic cyanobacteria. There was a good agreement between LC-MS and HPLC-UV determinations. Average recoveries of spiked fish samples were 63% for MC-RR and 71% for MC-LR. The highest MC contents in intestine, liver, kidney and spleen were 85.67, 2.83, 1.70 and 1.57 microg g-1 DW, respectively. MCs were much higher in mid-gut walls (1.22 microg g-1 DW) than in hind- and fore-gut walls (0.31 and 0.18 microg g-1 DW, respectively), suggesting the importance of mid-gut wall as major site for MC absorption. A cysteine conjugate of MC-LR was detected frequently in kidney. Among the muscle samples analyzed, 25% were above the provisional tolerable daily intake level by WHO. Bighead is strongly resistant to microcystins and can be used as biomanipulation fish to counteract cyanotoxin contamination in eutrophic waters.     

Photoelectrocatalytic degradation of pentachlorophenol in aqueous solution using a TiO2 nanotube film electrode

Titanium dioxide (TiO2) nanotube film electrodes are fabricated by the anodic oxidation method. Scanning electron microscopy (SEM) showed that these tubes were well aligned and organized into high-density uniform arrays. XRD analysis showed the TiO2 nanotubes to be in the anatase crystal form. The TiO2 nanotube film electrode exhibited increased photoelectrocatalytic (PEC) capability compared to a traditional TiO2 film electrode fabricated using the anodizing method for pentachlorophenol (PCP) degradation in aqueous solution. The bias potential, pH value, and electrolyte concentration were shown to be important factors influencing the degradation of PCP by the PEC method using the TiO2 nanotube film electrode as the working electrode.