Effect of transition metal doping under reducing calcination atmosphere on photocatalytic property of TiO2 immobilized on SiO2 beads

TiO₂ immobilized on SiO₂ (TiO₂/SiO₂) have been prepared by sol-gel method and various ions of transition metals (Cr³⁺, Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺) were doped on the photocatalyst using wet impregnation method under reducing calcination atmosphere. The photocatalytic activity of metal doped TiO₂/SiO₂ towards phenol degradation under black light irradiation were investigated and compared with undoped TiO₂/SiO₂. The results showed that the photoresponse of Cu²⁺ and Zn²⁺ doped TiO₂/SiO₂ were larger than undoped TiO₂/SiO₂, indicating that the photogenerated carriers were separated more efficiently in Cu²⁺ and Zn²⁺ doped TiO₂/SiO₂. The reactivity was in the order of Cu²⁺ > Zn²⁺ > Ni²⁺ > Cr³⁺ > Co²⁺. The different photoreactivity was ascribed to combine effect of the different ionic radii and photocorrison tendency of the dopants. The sample was also characterized by surface analytical methods such as X-ray diffraction, scanning electron micrograph/electron dispersive X-ray analyzer and UV-Vis absorption spectrum.     

Iron and lead ion adsorption by microbial flocculants in synthetic wastewater and their related carbonate formation

Although microbial treatments of heavy metal ions in wastewater have been studied, the removal of these metals through incorporation into carbonate minerals has rarely been reported. To investigate the removal of Fe^3＋ and Pb^2＋, two representative metals in wastewater, through the precipitation of carbonate minerals by a microbial flocculant （MBF） produced by Bacillus mucilaginosus. MBF was added to synthetic wastewater containing different Fe^3＋ and Pb^2＋ concentrations, and the extent of flocculation was analyzed. CO2 was bubbled into the mixture of MBF and Fe^3＋/Pb^2＋ to initiate the reaction. The solid substrates were analyzed via X-ray diffraction, transmission electron microscopy and energy dispersive spectroscopy. The results showed that the removal efficiency decreased and the MBF adsorption capacity for metals increased with increasing heavy metal concentration. In the system containing MBF, metals （Fe^3＋ and Pb^2＋）, and CO2, the concentrated metals adsorbed onto the MBF combined with the dissolved CO2, resulting in oversaturation of metal carbonate minerals to form iron carbonate and lead carbonates. These results may be used in designing a method in which microbes can be utilized to combine CO2 with wastewater heavy metals to form carbonates, with the aim of mitigating environmental problems.     

小球藻培养条件优化及油脂积累特征

为探索小球藻光生物反应器培养和油脂积累的最佳条件,就pH和不同浓度的NO3-N、Mg2+、Fe3+和Zn2+等环境因素对小球藻生长的影响进行了探讨,同时应用尼罗红染色荧光法对各环境因子条件下小球藻细胞内油脂积累状况进行了动态监测;继而应用正交实验对显著影响小球藻生长和油脂积累的培养条件进行了组合优化。结果表明:高浓度的NO3-N、Mg2+、Fe3+可促进小球藻的生长,而Zn2+则抑制其生长,pH对其生长及油脂积累影响不明显;在一定范围内,氮限制和高浓度的金属离子可以有效地促进小球藻油脂的积累;小球藻最优培养条件组合为:Fe3+浓度为12μmol/L,Zn2+浓度为7.2μmol/L,NO3-N浓度为0.3 mmol/L。     

聚合铝铁对A2/O系统 EPS及生物絮凝性能的影响

通过向实验室构建的A2/O模型好氧池末端投加聚合铝铁(PAFC)来强化系统的生物除磷,使得出水总磷达到《城市污水处理厂污染物排放标准GB 18918-2002》中的一级A标准,并重点分析投加的PAFC对A2/O系统中活性污泥胞外聚合物(EPS)和活性污泥生物絮凝性能的影响.结果表明,随着PAFC投药量的增加,A2/O系统活性污泥EPS总量变化不大,但EPS组分中蛋白/多糖含量的比值逐渐降低,由投药前的3.30降低至投药后的2.30;EPS中金属离子含量逐渐增加,在厌氧-缺氧-好氧的运行周期内,各处理单元污泥的EPS中金属铝离子含量增加.投加PAFC后,活性污泥颗粒变大,二沉池出水的Zeta电位明显降低,由投药前-15.83 mV降低至-21.20 mV,污泥产量增加.因此,适量投加PAFC后,生物絮凝性能得到改善,出水中悬浊颗粒减少,出水水质变好.     

Removal of copper ions from aqueous solution by calcium alginate immobilized kaolin

Kaolin has been widely used as an adsorbent to remove heavy metal ions from aqueous solutions. However, the lower heavy metal adsorption capacity of kaolin limits its practical application. A novel environmental friendly material, calcium alginate immobilized kaolin (kaolin/CA), was prepared using a sol-gel method. The e ects of contact time, pH, adsorbent dose, and temperature on Cu2+ adsorption by kaolin/CA were investigated. The Langmuir isotherm was used to describe the experimental adsorption, the maximum Cu2+ adsorption capacity of the kaolin/CA reached up to 53.63 mg/g. The thermodynamic studies showed that the adsorption reaction was a spontaneous and endothermic process.     

Effects of metal cations on sorption-desorption of p-nitrophenol onto wheat ash

The mutual e ects of metal cations (Cu2+, Pb2+, Zn2+, and Cd2+) and p-nitrophenol (NP) on their adsorption desorption behavior onto wheat ash were studied. Results suggested that Cu2+, Pb2+, and Zn2+ diminished the adsorption and increased the desorption of NP remarkably, while Cd2+ had no such e ect. In contrast, NP diminished the adsorption of Cu2+, Pb2+, and Zn2+ onto ash, however, this suppression e ect depended on the initial concentrations of metal cations. NP had no e ect on Cd2+ adsorption on ash. Fourier transform infrared (FT-IR) and X-ray absorption spectroscopic (XAS) studies suggested the following mechanisms responsible for the metal suppression e ect on NP adsorption: (1) large hydrated Cu2+, Pb2+, and Zn2+ shells occupied the surface of ash and prevent nonspecific adsorption of NP onto ash surface; (2) Cu2+, Pb2+, and Zn2+ may block the micropores of ash, resulting in decreased adsorption of NP; (3) complexation of Cu2+, Pb2+, and Zn2+ was likely via carboxyl, hydroxylic and phenolic groups of wheat ash and these same groups may also react with NP during adsorption. As a “soft acid”, Cd2+ is less e cient in the complexation of oxygencontaining acid groups than Cu2+, Pb2+, and Zn2+. Thus, Cd2+ had no e ect on the adsorption of NP on wheat ash.     

Removal of heavy metal ions from aqueous solution using red loess as an adsorbent

The adsorption behaviors of heavy metals onto novel low-cost adsorbent, red loess, were investigated. Red loess was characterized by X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectra. The results indicated that red loess mainly consisted of silicate, ferric and aluminum oxides. Solution pH, adsorbent dosage, initial metal concentration, contact time and temperature significantly influenced the efficiency of heavy metals removal. The adsorption reached equilibrium at 4 hr, and the experimental equilibrium data were fitted to Langmuir monolayer adsorption model. The adsorption of Cu(II) and Zn(II) onto red loess was endothermic, while the adsorption of Pb(II) was exothermic. The maximum adsorption capacities of red loess for Pb(II), Cu(II) and Zn(II) were estimated to be 113.6, 34.2 and 17.5 mg/g, respectively at 25°C and pH 6. The maximum removal efficiencies were 100% for Pb(II) at pH 7, 100% for Cu(II) at pH 8, and 80% for Zn(II) at pH 8. The used adsorbents were readily regenerated using dilute HC1 solution, indicating that red loess has a high reusability. All the above results demonstrated that red loess could be used as a possible alternative low-cost adsorbent for the removal of heavy metals from aqueous solution.     

重金属离子快速检测技术研究与应用进展

在突发环境污染事件和区域生态风险筛查中迫切需要环境样品中重金属离子的快速检测技术手段。环境样品中重金属离子的快速检测技术有电化学方法和生物学方法。电化学检测方法主要是阳极溶出伏安法(AnodicStripping Voltammetry,ASV),可以同时检测多种重金属离子,有标准化认证的产品,但是检测成本相对较高。随着纳米粒子技术(Nanoparticles,NPs)和石英微天平分析技术(Quartz Crystal Microbalance,QCM)的引入,ASV法的检测成本将不断降低;生物检测方法包括免疫检测(Immunoassay,IA)和功能DNA(Functional DNA)检测技术。重金属离子的免疫检测技术样品通量大,检测成本低,已经广泛用于食品行业,其中汞离子的免疫检测方法已经成为环境样品标准检测方法之一。免疫检测传感器技术将拓展重金属离子的快速检测的应用空间。功能DNA传感器检测的研究为重金属离子的快速检测提供了新的技术手段,但是这些仅限于实验室研究,还没有达到实际应用的水平。     

Reaction mechanism and metal ion transformation in photocatalytic ozonation of phenol and oxalic acid with Ag+/TiO2

Photocatalytic ozonation of phenol and oxalic acid （OA） was conducted with a Ag^＋/TiO2 catalyst and different pathways were found for the degradation of different compounds. Ag^＋ greatly promoted the photocatalytic degradation of contaminants due to its role as an electron scavenger. It also accelerated the removal rate of OA in ozonation and the simultaneous process for its complex reaction with oxalate. Phenol could be degraded both in direct ozonation and photolysis, but the TOC removal rates were much higher in the simultaneous processes due to the oxidation of hydroxyl radicals resulting from synergetic effects. The sequence of photo-illumination and ozone exposure in the combined process showed quite different effects in phenol degradation and TOC removal. The synergetic effects in different combined processes were found to be highly related to the properties of the target pollutants. The color change of the solution and TEM result confirmed that Ag＋ was easily reduced and deposited on the surface of Tit2 under photo-illumination, and dissolved again into solution in the presence of ozone. This simple cycle of enrichment and distribution of Ag^＋ can greatly benefit the design of advanced oxidation processes, in which the sequences of ozone and photo-illumination can be varied according to the needs for catalyst recycling and the different properties of pollutants.     

柱状污泥基活性炭制备方法及其除污染效能研究

以城市污水厂剩余污泥为原料,用氯化锌活化法研究一种柱状污泥基活性炭(CSAC)的制备方法及其工艺条件优化,并选择粉末污泥基活性炭(PSAC)和一种商品煤质碳(MAC)作为对照,考察了CSAC对重金属离子Cu(Ⅱ)和Pb(Ⅱ)及有机污染物硝基苯的吸附去除效能.结果表明,CSAC的比表面积及微孔容积分别是306.9 m2·g-1和0.109 cm3·g-1,仅为MAC的36.7%和23.6%,但其对Cu(Ⅱ)和Pb(Ⅱ)的平衡吸附量却远远高于MAC,说明CSAC表面存在的高含量酸性官能团在吸附去除重金属过程中起到了重要的作用.由于制备原料相同及制备工艺相似,CSAC与PSAC的理化性质基本相同,两种炭的表面酸性官能团含量较高,对Cu(Ⅱ)和Pb(Ⅱ)均具有较好的吸附去除效果,优于MAC,只是CSAC的比表面积和微孔容积略低于PSAC;在对硝基苯的吸附实验中,CSAC及PSAC的吸附效率均远远低于MAC,说明在对有机物硝基苯的吸附中,活性炭的比表面积等物理性质起到了较大的作用.同时,所制备的CSAC的稳定度大于95%,易于分离回收,不会造成二次污染,适合废水中重金属离子的吸附去除.