土壤有机质和活性铁组分对γ--666光解动力学的影响研究

研究了γ 6 6 6在有机碳含量分别为 <0 0 8% ,0 40 %± 0 0 6 %和 1 0 0 %± 0 2 8%而铁含量依次增加的三组土样中的光解动力学 ,γ 6 6 6的光解符合准一级动力学方程 .当土样中的铁含量相对不变时 ,γ 6 6 6的光降解动力学常数与有机质含量成负相关 ;而当土样中的有机碳含量相对不变时 ,光解动力学常数与铁含量成线性正相关 .为进一步验证土壤有机质对γ 6 6 6的光解的作用 ,采用土壤化学逐级分离法将一土样中的碳酸钙和有机质逐一去除而得到一级和二级土样 ,发现γ 6 6 6在这两级土样中的光解动力学常数依次为 0 0 12 9h-1和 0 0 2 31h-1,再次证明土壤有机质对γ 6 6 6的光解有明显抑制作用     

紫外光照射与生物降解耦合用于PCBs降解的研究

介绍了PCBs紫外光降解的机理及研究进展 ,讨论了影响PCBs光降解的主要因素 ,即环上的氯原子数目、取代位置及所处的微环境均显著地影响PCBs的光降解速率。简述了PCBs生物降解的研究进展 ,重点概述了好氧降解、厌氧降解及好氧厌氧协同作用的机理及特点。最后 ,讨论了PCBs生物降解和光降解的互补性 ,介绍了最近的研究进展 ,指出光降解和生物降解耦合将加快PCBs的移走速率 ,提出了PCBs污染土壤原位修复需要进一步解决的问题。     

新型无极紫外灯的光氧化性能研究

本实验对新型无极紫外灯的发射光谱、不同波长光线在溶液中的传播、·OH和O3的生成量、活性艳红X-3B溶液的降解情况进行了测定,并与普通中压汞灯进行了比较.结果表明,无极紫外灯在紫外区光强约为相近功率的普通中压汞灯的20倍;在溶液中紫外光比可见光更易被吸收;·OH生成与溶液对短波长光子的吸收存在对应关系,本实验中无极紫外灯的最大氧化距离约为6 cm;O3的生成量随着空气曝气量或254 nm处的光强的增大呈指数增加;降解活性艳红X-3B溶液的过程符合负一级动力学关系,降解效果明显好于普通中压汞灯,并且证明了无极紫外灯与生成的臭氧在活性艳红X-3B的降解过程中存在协同作用.     

Photodegradation and volatility of pesticides

BACKGROUND AND OBJECTIVES: Among the factors affecting the environmental fate of surface-applied pesticides several biological as well as abiotic factors, such as volatilization and photochemical transformations are of particular interest. Whereas reliable measurement methods and models for estimating direct photodegradation are already available for the compartments of water and atmosphere and individual subprocesses have already been described in detail, there is still a need for further elucidation concerning the key processes of heterogeneous photodegradation of environmental chemicals on surfaces. METHODS: In order to systematically examine the direct and indirect photodegradation of 14C-labeled pesticides on various surfaces and their volatilization behavior, a new laboratory device ('photovolatility chamber') was designed according to US EPA Guideline 161-3. Model experiments under controlled conditions were conducted investigating the impact of different surfaces, i.e. glass, soil dust and radish plants, and environmental factors, i.e. irradiation and atmospheric ozone (O3), on the photodegradation and volatilization of surface-deposited [phenyl-UL-14C]parathion-methyl (PM). RESULTS AND DISCUSSION: Depending on the experimental conditions, parathion-methyl was converted to paraoxon-methyl, 4-nitrophenol, unknown polar products and 14CO2. With respect to the direct photodegradation of PM (experiments without O3), the major products were polar compounds and 14CO2, due to the rapid photochemical mineralization of 4-nitrophenol to 14CO2. Paraoxon-methyl and 4-nitrophenol formation was mainly mediated by the combination of light, O3, and *OH radicals. In radish experiments PM photodegradation was presumably located in the cuticle compartment, which exhibited a sensitized photodegradation, as more unknown products were yielded compared to the glass and soil dust experiments. This could be explained by intensifying the inherent PM degradation in the dark with the same product spectrum. Due to photochemical product formation, which is an antagonistic process to the volatilization of parent compound, the volatilization of unaltered parathion-methyl from each surface generally decreased in the presence of light, particularly in combination with increasing O3 concentrations and *OH radical production rates. CONCLUSION: First results demonstrated that the photovolatility chamber provides a special tool for the systematic evaluation of (a) photodegradation of surface-located pesticide residues, i.e. measuring qualitative aspects of direct and indirect photodegradation together with relative photodegradation rates, and (b) volatilization of pesticides on surfaces by including and optionally varying relevant parameters such as light, atmospheric O3 concentration, surface temperature, air temperature, air flow rate. OUTLOOK: The experimental facility represents an important complement to lysimeter and field studies, in particular for experiments on the volatilization of pesticides using the wind tunnel system. With the photovolatility chamber special experiments on photodegradation, volatilization and plant uptake can be conducted to study key processes in more detail and this will lead to a better understanding of the effects of certain environmental processes on the fate of released agrochemicals contributing to an improved risk assessment.     

Ferrioxalate-mediated photodegradation and mineralization of 4-Chlorophenol

INTENTION, GOAL, SCOPE, BACKGROUND: Advanced oxidation processes are powerful methods which are capable of transforming refractory, nonbiodegradable and/or toxic organic compounds into harmless end products such as carbon dioxide and water. However, one commen problem of all advanced oxidation processes is the high demand of electrical energy for ultraviolet lamps, which causes high operational costs. Minimization of the required irradiation time, and therefore the energy consumption, by optimization of other reaction conditions such as catalyst-oxidant type and concentration, pH, temperature, pollutant/oxidant ratio etc., therefore continues to gain importance. OBJECTIVE: The main objective of this study was the minimization of the required irradiation time through optimization of the use of a newly patented catalyst, ferrioxalate, and also to compare the performance of this catalyst with the performance of other AOPs. METHODS: Oxidation of 4-chlorophenol by photo-Fenton process using potassium ferrioxalate as a mediator was studied in a lab scale photoreactor. The influence of parameters such as hydrogen peroxide and ferrioxalate concentrations, initial pH, power-output, oxalate/iron ratio and different iron sources was evaluated. An upflow photoreactor equipped with a 1000 Watt high-pressure mercury vapour lamp and operating in a recirculation mode was used during photodegradation experiments. The extent of the reduction of 4-chlorophenol, Total Organic Carbon and Chemical Oxygen Demand was used to evaluate the photodegradation reaction. RESULTS AND DISCUSSION: The optimum pH range observed was found to be 2.7-3. The efficiency of 4-chlorophenol oxidation increased with increasing concentrations of hydrogen peroxide and ferrioxalate, reaching a plateau after the addition of 10 and 0.072 mM of those reagents, respectively. Using an Oxalate/iron ratio of 12 was 18% less efficient than using a ratio of 3:1. The efficiency increased with increasing radiation power. However, this increase was not linear. The UV/ferrioxalate/H2O2 process, by which complete mineralization of 100 mg l(-1) 4-chlorophenol was achieved in 20 min of total reaction time, was the most efficient process among the alternatives applied. CONCLUSIONS: The use of ferrioxalate as the catalyst was found to be more efficient than the use of Fe(II) and Fe(III) iron species. It was possible to completely mineralize 4-chlorophenol. RECOMMENDATION AND OUTLOOK: The results of this study demonstrate that the ferrioxalate-mediated degradation of 4-chlorophenol requires less irradiation times than other advanced oxidation processes. There are mainly 19 phenol isomers and other toxic and nonbiodegradable organic compounds. We recommend that similar studies should be performed on many such compounds in order to attain a clear understanding of the performance of this catalyst. Because of its light sensitivity, this catalyst should be used immediately after its preparation. The use of low pressure mercury vapour lamps in this process should also be considered, since low power outputs may be enough for the process.     

非均相Fenton反应技术研究进展

Fenton氧化法是较为常用的一种高级氧化技术。非均相Fenton反应适用的pH值范围较宽，能避免均相Fenton反应产生铁泥沉淀的缺点，成为近年来Fenton反应的重要研究方向。本文对非均相Fenton氧化技术的研究现状及发展动态进行较为详尽的评述。     

气溶胶中多环芳烃光降解的初步研究

本文以大容量空气脱悬浮微粒采样器采集了大气中的气溶胶样品,以石英滤膜为载体,研究了气溶胶中的多环芳烃在紫外光照下的光降解规律。     

光照法处理垃圾渗滤液试验研究

采用直接光照处理青山垃圾填埋场和流芳垃圾填埋场的渗滤液,结果表明,直接光照处理4h,COD去除率分别为31%和18%,其主要原因在于青山垃圾填埋场中含有较多Fe和Cu等光催化物质及自身的光降解.直接光照对NH3-N和总-N的处理效果不佳.     

水体表面微层中酞酸酯的光降解研究

研究了水体表面微层中酞酸酯化合物光降解的动力学,指出光催化降解符合一级动力学过程,实验证明：催化剂ＴｉＯ２为２ｇ．ｌ＾－１,ｐＨ为６,并有Ｈ２Ｏ２存在时,是ＤＢＰ,ＤＥＨＰ光降解的最佳条件,溶解氧增加有利于光降解,实际表面微层水样的光催化降解速率比模拟水样快。     

工程对环境影响系统分析中有关二次影响问题的探讨

就水电工程对生态与环境二次影响问题的系统分析,提出一种便于应用的交互矩阵方法,并讨论了二次影响程度如何在度量规范中进行追加计算。