超声与磁粉强化含单宁废水生物处理研究

单宁是一种典型的有毒难降解污染物，在制革、造纸、制药、印染等行业废水中广泛存在，对水环境造成污染并且影响废水生物处理效果。本研究针对含单宁废水生物处理效率低、较高浓度时微生物受抑制且污泥容易膨胀等问题，采用超声和磁粉来强化含单宁废水生物处理，研究超声和磁粉对微生物活性、污染物去除及污泥沉降性能的影响，并对其作用机理进行了分析和探讨。 研究结果表明，活性污泥系统中单宁酸容积负荷可以达到1.8kgCOD/(m3·d)，单宁酸和COD去除率分别达到85.2%和79.6%，但如果负荷进一步增大则微生物活性迅速降低。系统在pH 5~8、温度20~35℃、DO>1 mg/L的条件下具有较好的单宁酸降解效果和处理稳定性。单宁降解动力学参数为：μmax =0.208h-1；Ks=226mg/L；Ki=522mg/L；kd=0.0092h-1；Y =0.594。 磁粉对系统处理效果和污泥沉降性能有一定的促进作用，且效果要优于外磁场。适宜的磁粉粒径和投加量分别为0.05~0.15mm和1.0g/L，COD去除率比对照系统提高6.4%，SVI降低28.6%，污泥絮体结构紧密。磁粉强化主要是通过其对污泥菌胶团的凝聚、吸附作用以及对微生物活性的强化作用实现。 在适当强度（0.4W/cm2）和辐照时间（20min）的超声作用下污泥絮体和细胞膜通透性增大，酶分泌也增多，系统的COD去除率比对照提高了8.8%，单宁酶酶活提高了11%。但超声也使污泥絮体结构松散，沉降性能下降，SVI比对照系统升高9.3%。 由于污泥流失加剧导致污泥浓度相对较低，声磁联合强化系统相对于磁粉强化系统其处理效果并没有提高。但相对于单纯活性污泥系统，声磁联合作用下系统处理效果、污泥沉降性能以及系统运行稳定性都得到明显改善。本研究为难降解废水的生物处理提供了一个新的思路。 Tannins are typical refractory and toxic pollutants that commonly exist in wastewater from dye, medicine, paper and leather industries and cause many problems associated with environmental pollution and biological treatment of wastewater. Biological treatment efficiency of tannin-containing wastewater is usually low owing to its biological toxicity and low biodegradability, microbes are usually inhibited under high tannin concentration and sludge bulking frequently occurs. In this study, ultrasound and magnetic powder were used to improve the biological treatment performance of simulated tannic acid-containing wastewater. The effects of ultrasonic irradiation and magnetic powder on microbial activity, tannic acid degradation rate and sludge sedimentation were investigated. The augmentation mechanisms were analyzed and discussed. The experimental results showed that the microbes were prominently inhibited under high tannic acid concentration, but moderate degradation efficiency can be maintained under a tannic acid load of up to 1.8kgCOD/(m3·d), with the tannic acid degradation and COD removal percentage of 85.2% and 79.6% respectively. The highest degradation rates and treatment stability were achieved at pH range of 5~8, temperature range of 20~35℃ and DO concentration of above 1mg/L. The kinetic parameters were estimated, including: μmax =0.208h-1；Ks=226mg/L；Ki=522mg/L；kd=0.0092h-1；Y =0.594. The microbial activity, tannic acid degradation rate and sludge sedimentation were improved by adding Fe3O4 magnetic powder, and the augmentation performance was better than external magnetic field. The appropriate particle size and dosage of magnetic powder were found to be 0.05~0.15mm and 1.0g/L, respectively, under which the COD removal percentage was improved by 6.4% and SVI value decreased by 28.6%, and compact floc structure was observed. This was mainly caused by the flocculation and adsorption effects of magnetic powder against sludge floc and the stimulation of microbial activity under appropriate magnetic field. Under appropriate ultrasonic irradiation (ultrasonic intensity 0.4W/cm2, ultrasonic irradiation time 20min), the permeability of floc and cell membrane are improved, transfer of substrate and oxygen were reinforced; meanwhile, more enzyme were produced by microbes under the slight damage caused by ultrasound. However, the floc structure became loose under ultrasonic irradiation, leading to relatively poor sedimentation, with the SVI value 9.3% higher than the control system. Although the magnetic powder-ultrasonic irradiation combined augmentation system showed no improvement in treatment performance compared with sole magnetic augmentation system owing to its relatively low sludge concentration, it guaranteed the stable operation of system, meanwhile the tannic acid degradation and sludge sedimentation were significantly improved compared with sole activated sludge system. This study gives a new idea for biological treatment of refractory wastewater.

Kinetic study on the photo-catalytic degradation of pyridine in TiO2 suspension systems

It has been generally agreed that pyridine can be effectively mineralized in aerated TiO2 slurries using near-UV irradiation. The knowledge on the kinetics of the system possesses both practical and theoretical values. The present study, on the base of Langmuir-Hinshewood mechanism, illustrates a pseudo first-order kinetic model of the degradation with the limiting rate constant of 3.004 mg l(-1) min(-1) and equilibrium adsorption constant 2.763 x 10(-2) l mg(-1), respectively. The degradation efficiency in alkali is a little higher than that in acid with a minimum at about pH = 5, which is explained by the formation of acid-pyridine in acidic surrounding together with the amphoteric nature of the TiO2 surface. The promotion of H2O2 on the photo-degradation ties in its supplying proper amount of (OH)-O-. radicals for the inducement stage before surface redox reactions. (C) 2004 Elsevier B.V. All rights reserved.

Ultrafast dynamics of dye molecules in solution as a function of temperature

Femtosecond time-resolved studies using fluorescence depletion spectroscopy were performed on Rhodamine 700 in acetone solution and on Oxazine 750 in acetone and formamide solutions at different temperatures. The experimental curves that include both fast and slow processes have been fitted using a biexponential function. Time constants of the fast process, which corresponds to the intramolecular vibrational redistribution (IVR) of solute molecules, range from 300 to 420 fs and increase linearly as the temperature of the environment decreases. The difference of the average vibrational energy of solute molecules in the ground state at different temperatures is a possible reason that induces this IVR time-constant temperature dependence. However, the time constants of the slow process, which corresponds to the energy transfer from vibrational hot solute molecules to the surroundings occurred on a time scale of 1-50 ps, changed dramatically at lower temperature, nonlinearly increasing with the decrease of temperature. Because of the C-H...O hydrogen-bond between acetone molecules, it is more reasonable that acetone molecules start to be associated, which can influence the energy transfer between dye molecules and acetone molecules efficiently, even at temperatures far over the freezing point.

Ultrafast vibrational and thermal relaxation of dye molecules in solutions

Intra- and intermolecular relaxations of dye molecules are studied after the excitation to the high-lying excited states by a femtosecond laser pulse, using femtosecond time-resolved stimulated emission pumping fluorescence depletion spectroscopy (FS TR SEP FD). The biexponential decays indicate a rapid intramolecular vibrational redistribution (IVR) depopulation followed by a slower process, which was contributed by the energy transfer to the solvents and the solvation of the excited solutes. The time constants of IVR in both oxazine 750 and rhodamine 700 are at the 290-360 fs range, which are insensitive to the characters of solvents. The solvation of the excited solutes and the cooling of the hot solute molecules by collisional energy transfer to the surrounding takes place in the several picoseconds that strongly depend on the properties of solvents. The difference of Lewis basicity and states density of solvents is a possible reason to explain this solvent dependence. The more basic the solvent is, which means the more interaction between the solute and the neighboring solvent shell, the more rapid the intermolecular vibrational excess energy transfer from the solute to the surroundings and the solvation of the solutes are. The higher the states density of the solvent is, the more favorable the energy transfer between the solute and solvent molecules is.

Degradation mechanism of polystyrene sulfonic acid membrane and application of its composite membranes in fuel cells

The lifetime behavior of a H-2/O-2 proton exchange membrane (PEM) fuel cell with polystyrene sulfonic acid (PSSA) membrane have been investigated in order to give an insight into the degradation mechanism of the PSSA membrane. The distribution of sulfur concentration in the cross section of the PSSA membrane was measured by energy dispersive analysis of X-ray, and the chemical composition of the PSSA membrane was characterized by infrared spectroscopy before and after the lifetime experiment. The degradation mechanism of the PSSA membrane is postulated as: the oxygen reduction at the cathode proceeds through some peroxide intermediates during the fuel cell operation, and these intermediates have strong oxidative ability and may chemically attack the tertiary hydrogen at the a carbon of the PSSA; the degradation of the PSSA membrane mainly takes place at the cathode side of the cell, and the loss of the aromatic rings and the SO3- groups simultaneously occurs from the PSSA membrane. A new kind of the PSSA-Nafion composite membrane, where the Nafion membrane is bonded with the PSSA membrane and located at the cathode of the cell, was designed to prevent oxidation degradation of the PSSA membrane in fuel cells. The performances of fuel cells with PSSA-Nafion101 and PSSA-recast Nafion composite membranes are demonstrated to be stable after 835 h and 240 h, respectively.

Degradation products formed during UV-irradiation of humic waters

Natural humic lake water and aqueous solutions of humic substances were treated with ultraviolet (UV) radiation (λ = 254 nm). The effects on the dissolved organic carbon content (DOC) and the absorbance at 254 nm (Abs254) and 460 nm (Abs460) were monitored and the identity and concentrations of gas chromatographable organic degradation products were determined. The DOC content and the (Abs254) of the humic solutions decreased continuously with increasing UV-dose. Several aromatic and aliphatic degradation products were identified and roughly quantified The concentrations of aromatic hydroxy carboxylic acids and hydroxy aldehydes increased when relatively low UV-doses were used, but declined following further irradiation. The concentrations of aliphatic dibasic acids increased over the full range of UV-doses

Degradation of aquatic humic material by ultraviolet light

Natural humic water was treated with ultraviolet (UV) light and UV + hydrogen peroxide . The effects on the dissolved organic carbon content (DOC), the UV-absorbance at 254 nm (UV-abs.), the molecular size distribution, pH, and mutagenic activity were monitored, and the identity and concentrations of the most abundant gas chromatographable organic degradation products were determined. The DOC content and the UV-abs. of the water decreased substantially during treatment with. The decreases were dependent on the time of irradiation (UV dose) as well as on the H2O2 dose applied. The humus macromolecules were degraded to smaller fragments during irradiation. At higher UV doses, however, part of the dissolved organic matter (DOM) was found to precipitate, probably as a result of polymerization. Oxalic acid, acetic acid, malonic acid, and n-butanoic acid were the most abundant degradation products detected. These acids were found to account for up to 20% and 80% of the DOM in UV- and waters, respectively. No mutagenic activity was generated by the UV irradiation or the treatment. It is further concluded that the substantial mutagenic activity formed during chlorination of humic waters cannot be decreased by using UV irradiation as a pretreatment step.