Modelling the environmental degradation of water contaminants. Kinetics and mechanism of the riboflavin-sensitised-photooxidation of phenolic compounds

The aerobic visible-light-photosensitised irradiation of methanolic solutions of either of the phenolic-type contaminants model compounds (ArOH) p-phenylphenol (PP), p-nitrophenol (NP) and phenol (Ph), and for two additional phenolic derivatives, namely p-chlorophenol (ClP) and p-methoxyphenol (MeOP), used in some experiments, was carried out. Employing the natural pigment riboflavin (Rf) as a sensitiser, the degradation of both the ArOH and the very sensitiser was observed. A complex mechanism, common for all the ArOH studied, operates. It involves superoxide radical anion (O₂^√−) and singlet molecular oxygen (O₂(¹Δ_g)) reactions. Maintaining Rf in sensitising concentrations levels (≈0.02 mM), the mechanism is highly dependent on the concentration of the ArOH. Kinetic experiments of oxygen and substrate consumption, static fluorescence, laser flash photolysis and time-resolved phosophorescence detection of O₂(¹Δ_g) demonstrate that at ArOH concentrations in the order of 10 mM, no chemical transformation occurs due to the complete quenching of Rf singlet excited state. When ArOH is present in concentrations in the order of mM or lower, O₂^√− is generated from the corresponding Rf radical anion, which is produced by electron transfer reaction from the ArOH to triplet excited Rf. The determined reaction rate constants for this step show a fairly good correlation with the electron-donor capabilities for Ph, PP, NP, ClP and MeOP. In this context, the main oxidative species is O₂^√−, since O₂(¹Δ_g) is quenched in an exclusive physical fashion by the ArOH. The production of O₂^√− regenerates Rf impeding the total degradation of the sensitiser. This kinetic scheme could partially model the fate of ArOH in aquatic media containing natural photosensitisers, under environmental conditions.     

Gas/particle partitioning of atmospheric PCDD/Fs in a satellite town in Eastern China

Gas/particle partitioning of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in ambient air was investigated in a satellite town in Eastern China from April 2007 to January 2008 comprehending large temperature variations (from 3 to 34 °C, daily average). Molecular weight, molecular structure and ambient temperatures are the three major factors that govern the gas/particle partitioning of atmospheric PCDD/Fs throughout the year. Generally, good agreements were obtained (except for winter) between measured particulate fractions and theoretical estimates of both the Junge–Pankow adsorption model and Harner Bidleman absorption model using different sets of subcooled liquid vapor pressure and octanol–air partition coefficient (K_oa), respectively. Models utilizing estimates, derived from gas chromatographic retention indices (GC-RIs), are more accurate than that of entropy-based. Moreover, during winter, the K_oa-based model using the GC-RIs approach performs better on lower chlorinated PCDD/Fs than that of -based. Furthermore, possible sources of mismatch between measured and predicted values in winter (3–7 °C) were discussed. Gas adsorption artifact was demonstrated to be of minor importance for the phenomena observed. On the other hand, large deviations of slopes (m_r) and intercepts (b_r) in logK_p vs. plots from theoretical values are observed in the literature data and these are found to be linearly correlated with ambient temperatures (P<0.001) in this study. This indicates that the non-equilibrium partitioning of PCDD/Fs in winter may be significantly influenced by the colder temperatures that may have slowed down the exchange between gaseous and particulate fractions.     

膨胀珍珠岩负载TiO2光催化脱色性能的研究

以钛酸四丁酯为原料 ,膨胀珍珠岩为载体 ,用溶胶 -凝胶法制备可漂浮于水面的负载型TiO2 。利用该负载型TiO2 对罗丹明B(RB)进行光催化脱色实验 ,结果表明 ,浸渍 3次的负载型TiO2 光催化活性最高 ,催化剂最佳用量为 5 0 0mg/10 0mLRB ,经 5h光照 ,对 10 0mL浓度为 1mg/L和 2 .5mg/LRB脱色率分别为 76 .6 7%和 4 7.2 7% ;该催化剂使用寿命长 ,2 5h后催化剂脱色性能没有减弱 ,可重复使用 ;经 8h光照 ,染料废水脱色效果好。     

Comparative studies of the Fe–UV, H2O2–UV, TiO2–UV/vis systems for the decolorization of a textile dye X-3B in water

The degradation of a common textile dye, Reactive-brilliant red X-3B, by several advanced oxidation technologies was studied in an air-saturated aqueous solution. The dye was resistant to the UV illumination (wavelength λ  320 nm), but was decolorized when one of Fe³⁺, H₂O₂ and TiO₂ components was present. The decolorization rate was observed to be quite different for each system, and the relative order evaluated under comparable conditions followed the order of Fe²⁺–H₂O₂–UV  Fe²⁺–H₂O₂ > Fe³⁺–H₂O₂–UV > Fe³⁺–H₂O₂ > Fe³⁺–TiO₂–UV > TiO₂–UV > Fe³⁺–UV > TiO₂–visible light (λ  450 nm) > H₂O₂–UV > Fe²⁺–UV. The mechanism for each process is discussed, and linked together for understanding the observed differences in reactivity.     

Study of oil-water partitioning of a chemical dispersant using an acute bioassay with marine crustaceans

The toxicity of seawater dispersions of a chemical dispersant to two marine crustaceans was investigated in the presence and absence of various quantities of a non-toxic mineral oil. From the results and a physical-chemical partitioning analysis, a limiting value of the oil-water partition coefficient of the toxic compounds is deduced suggesting that essentially all of the toxic compounds in the dispersant will partition into solution in water following dispersant application to an oil spill. This conclusion simplifies interpretation and prediction of the toxic effects of a dispersed oil spill.The combined bioassay-partitioning procedure may have applications to the study of the toxicity of other complex mixtures such as industrial effluents.     

层状氢氧化镁铝对偶氮染料酸性黑10B的脱色性能研究

分别用层状氢氧化镁铝(LDH)和焙烧层状氢氧化镁铝(CLDH)作为吸附剂吸附脱除水溶液中偶氮染料酸性黑10B.考察了脱色时间、pH值、吸附剂的投加量、温度、染料初始浓度和焙烧温度等因素对脱色率的影响.结果表明,LDH及CLDH对酸性黑10B染料具有良好的脱除效果,室温下,10g/L LDH和1g/L的CLDH对浓度为100mg/L的染料的脱色率分别达95.93%和99.97%.pH值是影响吸附能力的关键因素,吸附剂对溶液pH值有一定缓冲作用.LDH及CLDH对酸性黑10B吸附结果符合Langmuir吸附等温式.饱和吸附后的LDH及CLDH用高温热解法再生,吸附性能良好,随再生次数增多,脱色率下降.     

改性阴极生物电芬顿系统降解罗丹明B

分别采用十八烷基三甲基氯化铵（OATC）和磷酸改性电极并负载铁涂覆在碳布表面,制得Fe/OC-OATC电极和Fe/PC电极用于构建生物电芬顿系统,提高电芬顿技术中H₂O₂的原位生产能力,达到高效降解印染废水的目的.通过极化曲线、功率密度曲线以及循环伏安曲线对2种复合电极的电化学性质进行分析,结果表明,Fe/OC-OATC的电流密度、最大功率密度以及氧还原能力等均优于Fe/PC,最大功率密度为4.89W/m³,相应的电流密度可达22.9A/m³.然后探究了2种复合电极构建的生物电芬顿系统对罗丹明B的降解效果,结果显示,Fe/OC-OATC体系﹥ Fe/PC体系,Fe/OC-OATC体系对罗丹明B的去除率最高达96.4%.最后根据动力学分析和反应机理的研究,分析了2种系统对罗丹明B的降解机理.     

三维有机LDH的制备及其对有机物的普适性吸附

以表面活性剂十二烷基硫酸钠(SDS)为软模板剂,制得有机三维花状层状双金属氢氧化物(3D-SLDH).采用X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线能谱仪(EDS)和N₂吸附-脱附等表征手段对3D-SLDH的结构进行表征,确定最佳合成尿素浓度,并通过静态吸附实验考察了3D-SLDH对金橙Ⅱ(AO7)、罗丹明(RhB)以及萘(NAP)的吸附性能.结果表明,室温下,3D-SLDH对AO7、RhB和NAP的吸附容量分别为454.9,46.8和43.7mg/g,表明其对有机物的吸附具有普适性.3D-SLDH对AO7、RhB和NAP吸附过程均符合准二级动力学模型,对AO7和RhB的吸附等温线符合Langmuir模型,而对NAP的等温吸附行为符合partition-adsorption模型.升温有利于3D-SLDH对AO7和RhB的去除,不利于对NAP的去除.此外,结合反应前后固样XRD,FT-IR和XPS分析,可知3D-SLDH对AO7的去除机制主要是层间离子交换作用,对RhB的去除机制主要是疏水及表面吸附作用,而对NAP的去除机制主要为分配作用.     

Efficient degradation of Rhodamine B by magnetically recoverable Fe3O4-modified ternary CoFeCu-layered double hydroxides via activating peroxymonosulfate

Environment-friendly nano-catalysts capable of activating peroxymonosulfate (PMS) have received increasing attention recently. Nevertheless, traditional nano-catalysts are generally well dispersed and difficult to be separated from reaction system, so it is particularly important to develop nano-catalysts with both good catalytic activity and excellent recycling efficiency. In this work, magnetically recoverable Fe₃O₄-modified ternary CoFeCu-layered double hydroxides (Fe₃O₄/CoFeCu-LDHs) was prepared by a simple co-precipitation method and initially applied to activate PMS for the degradation of Rhodamine B (RhB). X-ray diffraction (XRD), fourier transform infrared spectrometer (FT-IR), scanning electron microscope (SEM), transmission electron microscopy (TEM), Brunauer-Emmett-Teller method (BET), and vibrating sample magnetometer (VSM) were applied to characterize morphology, structure, specific surface area and magnetism. In addition, the effects of several key parameters were evaluated. The Fe₃O₄/CoFeCu-LDHs exhibited high catalytic activity, and RhB degradation efficiency could reach 100% within 20 min by adding 0.2 g/L of catalyst and 1 mmol/L of PMS into 50 mg/L of RhB solution under a wide pH condition (3.0-7.0). Notably, the Fe₃O₄/CoFeCu-LDHs showed good super-paramagnetism and excellent stability, which could be effectively and quickly recovered under magnetic condition, and the degradation efficiency after ten cycles could still maintain 98.95%. Both radicals quenching tests and electron spin resonance (ESR) identified both HO? and SO₄^?? were involved and SO₄^?? played a dominant role on the RhB degradation. Finally, the chemical states of the sample's surface elements were measured by X-ray photoelectron spectroscopy (XPS), and the possible activation mechanism in Fe₃O₄/CoFeCu-LDHs/PMS system was proposed according to comprehensive analysis.     

Bi-FeC2O4复合催化剂活化过硫酸盐降解罗丹明B

采用溶剂热法将Bi单质附着于草酸亚铁（FeO_x）上,制备了系列Bi-FeOx复合催化剂并用于活化过硫酸盐.通过X射线衍射仪（XRD）、傅里叶变换红外光谱仪（FT-IR）、扫描电子显微镜（SEM）、X射线光电子能谱仪（XPS）等表征方法对复合催化剂的结构、形貌和元素价态进行表征.以罗丹明B（RhB）为降解对象,研究了Bi-FeOx/过硫酸盐/可见光体系中Bi单质含量、催化剂投加量、pH及过硫酸盐浓度等因素对RhB的降解影响.在最佳条件下,反应5 min后,RhB的降解率高达99.8%.Bi的引入,使得复合催化剂增强了对可见光的吸收,提高了光生电子的传输效率,从而加速了对RhB的降解.