一级动力学反应方程参数估计中若干问题的讨论

在农药的环境行为研究中,常用一级动力学反应方程来模拟农药的降解或残留。本文论述了用线性回归分析法估计一级化学动力学方程参数时存在的初始浓度飘移和非本义最优化问题,讨论了与此相关联的试验设置、安全间隔期、分段模拟和试验数据处理等问题,提出了解决问题的初步设想。     

有机污染物生物降解途径控制反应的预测与优势菌选择模型的建立

本文把有机污染物生物降解途径的理论测和量化剖析相结合确定生物降解途径中的控制反应,给出控制反ＱＳＢＲ的概念模式。在此基础上上建立了Ｐｓｅｕｄｏｍｏｎａｓｓｐ．典型生物降解途径以应的ＱＳＢＲ模型,利用建立的模型指导１,２－１,４－二氯苯和１,２,４－三氯苯生物处理优势菌的选择。     

Hydroxyl radical concentration profile in photo-Fenton oxidation process: generation and consumption of hydroxyl radicals during the discoloration of azo-dye Orange II

Dynamic behaviors of hydroxyl (OH) radical generation and consumption in photo-Fenton oxidation process were investigated by measuring OH radical concentration during the discoloration of azo-dye Orange II. The effects of operating parameters for photo-Fenton discoloration, i.e. dosages of H₂O₂ and Fe, initial dye concentration, solution pH and UV irradiation, on the generation and consumption of OH radicals playing the main role in advanced oxidation processes were extensively studied. The scavenger probe or trapping technique in which coumarin is scavenger of OH radical was applied to estimate OH radical concentration in the photoreactor during the photo-Fenton discoloration process. The OH radical generation was enhanced with increasing the dosages of Fenton regents, H₂O₂ and Fe. At the initial stage of photo-Fenton discoloration of Orange II, the OH radical concentration rapidly increased (Phase-I) and the OH radical concentration decreased after reaching of OH radical concentration at maximum value (Phase-II). The decrease in OH radical concentration started when the complete discoloration of Orange II was nearly achieved and the H₂O₂ concentration became rather low. The dynamic behavior of OH radical concentration during the discoloration of Orange II was found to be strongly linked with the change in H₂O₂ concentration. The generation of OH radical was maximum at solution pH of 3.0 and decreased with an increase of solution pH. The OH radical generation rate in the Fenton Process was rather slower than that in the photo-Fenton process.     

Parathion degradation and its intermediate formation by Fenton process in neutral environment

The purpose of this study is to investigate parathion degradation by Fenton process in neutral environment. The initial parathion concentration for all the degradation experiments was 20 ppm. For hydrogen ion effect on Fenton degradation, the pH varied from 2 to 8 at the [H₂O₂] to [Fe²⁺] ratio of 2-2 mM, and the result showed pH 3 as the most effective environment for parathion degradation by Fenton process. Apparent degradation was also observed at pH 7. The subsequent analysis for parathion degradation was conducted at pH 7 because most environmental parathion exists in the neutral environment. Comparing the parathion degradation results at various Fenton dosages revealed that at Fe²⁺ concentrations of 0.5, 1.0 and 1.5 mM, the Fenton reagent ratio ([H₂O₂]/[Fe²⁺]) for best-removing performance were found as 4, 3, and 2, resulting in the removal efficiencies of 19%, 48% and 36%, respectively. Further increase in Fe²⁺ concentration did not cause any increase of the optimum Fenton reagent ratio for the best parathion removal. The result from LC-MS also indicated that hydroxyl radicals might attack the PS double bond, the single bonds connecting nitro-group, nitrophenol, or the single bond within ethyl groups of parathion molecules forming paraoxons, nitrophenols, nitrate/nitrite, thiophosphates, and other smaller molecules. Lastly, the parathion degradation by Fenton process at the presence of humic acids was investigated, and the results showed that the presence of 10 mg L⁻¹ of humic acids in the aqueous solution enhanced the parathion removal by Fenton process twice as much as that without the presence of humic acids.     

Interactive effects of cadmium and hypoxia on metabolic responses and bacterial loads of eastern oysters Crassostrea virginica Gmelin

Pollution by toxic metals including cadmium (Cd) and hypoxia are important stressors in estuaries and coastal waters which may interactively affect sessile benthic organisms, such as oysters. We studied metabolic responses to prolonged hypoxic acclimation (2 weeks at 5% O₂) in control and Cd-exposed (30 d at 50 μg L⁻¹ Cd) oysters Crassostrea virginica, and analyzed the effects of these stressors on abundance of Vibrio spp. in oysters. Hypoxia-acclimated oysters retained normal standard metabolic rates (SMR) at 5% O₂, in contrast to a decline of SMR observed during acute hypoxia. However, oysters spent more time actively ventilating in hypoxia than normoxia resulting in enhanced Cd uptake and 2.7-fold higher tissue Cd burdens in hypoxia. Cd exposure led to a significant decrease in tissue glycogen stores, increase in free glucose levels and elevated activity of glycolytic enzymes (hexokinase and aldolase) indicating a greater dependence on carbohydrate catabolism. A compensatory increase in activities of two key mitochondrial enzymes (citrate synthase and cytochrome c oxidase) was found during prolonged hypoxia in control oysters but suppressed in Cd-exposed ones. Cd exposure also resulted in a significant increase in abundance of Vibrio parahaemolyticus and Vibrio vulnificus levels during normoxia and hypoxia, respectively. Overall, Cd- and hypoxia-induced changes in metabolic profile, Cd accumulation and bacterial flora of oysters indicate that these stressors can synergistically impact energy homeostasis, performance and survival of oysters in polluted estuaries and have significant consequences for transfer of Cd and bacterial pathogens to the higher levels of the food chain.     

Degradation of rhodamine B by Fe(0)-based Fenton process with H2O2

Degradation of rhodamine B by Fe(0)-based Fenton process with H₂O₂ was investigated. The effects of H₂O₂ dose, Fe(0) dose, initial concentration of rhodamine B and initial pH value on the degradation of rhodamine B were examined. The results showed that the degradation and mineralization of rhodamine B occurred with low dose of H₂O₂ and Fe(0). The intermediates of rhodamine B were analyzed with UV-Vis spectrophotometry and ion chromatography and the mechanism of oxidative degradation of rhodamine B was also discussed. The reactive oxygen species (·OH) produced in Fe(0)-based Fenton process with H₂O₂ is the key to the degradation of rhodamine B by ways of N-de-ethylation, chromophore cleavage, ring-opening and mineralization.     

Fenton试剂预处理化工综合废水的研究

以化学工业园区废水为研究对象初步研究了Fenton试剂预处理化工综合废水时各影响因子的作用机制,通过正交实验确定了Fenton反应的最佳操作条件为：反应时间70 min,硫酸亚铁投加量为2.6 mmol/L,温度为40℃,初始pH3.5,二价铁离子和过氧化氢的摩尔比为1∶8时,COD的去除率可达到60%以上,B/C值可...     

Fenton氧化法预处理难降解高浓度化工废水

难降解高浓度化工废水直接采用生化法处理较为困难,为了减少后续水处理系统处理难降解物质的量,采用Fenton氧化法对难降解高浓度化工废水进行预处理且非常有效.重点考察了pH、投药比例、投药量以及反应时间对Fenton氧化法预处理高浓度化工废水的影响.经过实验得出最佳条件:pH为3.5,投药比例为1.0 mL 50％(质量...     

Combustion in porous media and its applications – A comprehensive survey

The rapid advances in technology and improved living standard of the society necessitate abundant use of fossil fuels which poses two major challenges to any nation. One is fast depletion of fossil fuel resources; the other is environmental pollution. The porous medium combustion (PMC) has proved to be one of the technically and economically feasible options to tackle the aforesaid problems to a remarkable extent. PMC has interesting advantages compared with free flame combustion due to the higher burning rates, the increased power dynamic range, the extension of the lean flammability limits, and the low emissions of pollutants. This article provides a comprehensive picture of the global scenario of research and developments in PMC and its applications that enable a researcher to decide the direction of further investigation. The works published so far in this area are reviewed, classified according to their objectives and presented in an organized manner with general conclusions. A separate section is devoted for the numerical modeling of PMC.     

餐饮业烟道油垢燃烧特性及动力学模型

利用热重分析仪研究了餐饮业油烟道油垢在不同升温速率下的燃烧特性.所采用的升温速率分别为5℃/min、15℃/min和25℃/min.吹扫气体为干空气,流量为20 mL/min.结果表明,试样从常温至800℃的升温燃烧经历了第1步水分析出、第2～5步燃烧失重过程.采用Doyle和Coats-Redfern方法建立了"4阶段1级反应动力学模型",计算燃烧反应的动力学参数.并用试验热重曲线验证了模型的可靠性.研究表明,油垢燃烧失重的4个主要过程均可用简单反应动力学模型进行简化,反应级数为1;燃烧总趋势是随升温速率提高,活化能增大.