多环芳烃（PAHs）场地污染造成的环境危害是世界各国面临的重大难题， 电动力学（EK）技术作为一种新型的土壤修复技术成为缓解该问题的有效途径。 本文研究了单独 EK 及其强化技术修复菲和蒽污染土壤，同时阐述了漆酶作为 EK 联用技术的可行性，为 EK/漆酶联用技术的实际应用提供了实验及理论基础。 本文选取菲和蒽作为代表污染物，研究并分析了非均匀电场和阳极强化电动 力学技术作用下菲及蒽的迁移特征和机理；同时，为了解决漆酶易失活的缺陷， 研究了提高漆酶稳定性的方法，主要研究结论如下， 电动力学过程能有效促进土壤中菲的解吸和迁移，其迁移效果与电场施加方 式密切相关。均匀电场对高岭土中的菲没有明显迁移效果，而非均匀电场对菲有 明显的迁移效果，能够使土壤中的菲向场强较大的电极区迁移。非均匀电动力学 对土壤中菲迁移的主要机理是介电迁移。 电动力学方法对土壤中蒽的迁移变化影响极小，极少量蒽随着电渗流的迁移 被带到阴极附近。 采用大分子修饰法可有效提高酶的酸碱及热稳定性，且修饰漆酶 Dex-lac 的 稳定性更优于 SA-lac，其适宜催化的 pH 范围拓宽到 pH 3.5~5。 关键词，菲；蒽；漆酶；土壤修复；化学修饰II Abstract Environmental harm by sites contaminated with Polycylic Aromatic Hydrocarbons (PAHs) is a major problem to the world. This can be effectively mitigated by Electrokinetics (EK) technology which as a new soil remediation technology. In this paper, the remediation of EK technology alone and its enhanced technology were studied, the feasibility of laccase as EK coupled techniques was elaborated, and provided the experimental and theoretical foundation for practical application of a combined EK/ laccase process. Phenanthrene and anthracene were chosen as typical pollutant. The characteristic and the mechanism of phenanthrene and anthracene migration under anolyte enhanced and non-uniform field electrokinetic remediation technologies were analyzed. Due to the easy deactivation of laccase, the method of improve the stability of laccase was studied. The main research conclusions are as follows: Electrodynamics process can effectively promote the desorption and migration of phenanthrene in soil and the migration effect is closely related to the way of electric field. Phenanthrene in kaolin has no apparent migration effect under uniform field, but there has apparent migration effect in non-uniform field. Phenanthrene can migrate to a larger electrode area in non-uniform field. The main mechanism of phenanthrene in soil is dielectric migration under non-uniform field. Electrodynamics method made a minimal migration effect to anthracene in soil. Very little anthracene was taken to the near of cathode by the migration of electroosmotic fiow. The stability against high temperature and acid-base of modified laccase were efficient improved by macromolecular modification. The stability of Modified laccase Dex-lac is higer than SA-lac. Tts suitable catalytic pH range widen to pH 3.5~5. Keywords: Phenanthrene; Anthracene; Laccase; Soil remediation; Chemical modificationIII 目录 摘要.............................................................................................................................I Abstract ......................................................................................................................... II 第 1 章 引 言............................................................................................................1 1.1 土壤 PAHs 污染的概述 ..................................................................................1 1.1.1 土壤 PAHs 污染的来源和特点 .............................................................1 1.1.2 土壤 PAHs 污染的危害和修复的必要性 .............................................1 1.2 土壤中 PAHs 的吸附解吸行为特征研究进展 ..............................................2 1.3 土壤 PAHs 污染修复技术和目标污染物的选择 ...........................................2 1.4 EK 修复 PAHs 污染土壤的研究进展 .............................................................3 1.4.1 电动修复技术的基本原理....................................................................3 1.4.2 电动修复技术的研究进展....................................................................4 1.5 本课题的研究目的、内容、创新点及课题来源..........................................6 1.5.1 研究目的................................................................................................6 1.5.2 研究内容................................................................................................7 1.5.3 课题创新点............................................................................................7 1.5.4 课题来源................................................................................................7 第 2 章 土壤中菲和蒽的吸附行为特征研究............................................................8 2.1 实验材料..........................................................................................................8 2.1.1 模拟菲及蒽废水的配置.........................................................................8 2.1.2 实验仪器及药品....................................................................................8 2.2 实验方法..........................................................................................................9 2.2.1 吸附实验................................................................................................9 2.2.2 模拟土壤中菲和蒽浓度的测定..........................................................10 2.2.3 菲和蒽标准曲线的绘制......................................................................10 2.3 结果与分析.................................................................................................... 11 2.3.1 菲和蒽的吸附动力学.......................................................................... 11 2.4 本章小结.........................................................................................................13 第 3 章 EK 及其强化技术修复 PAHs 污染土壤的研究..........................................14 3.1 实验材料........................................................................................................14 3.1.1 电动力学修复装置..............................................................................14 3.1.2 模拟菲及蒽污染土壤的配置..............................................................15 3.1.3 实验仪器与药品..................................................................................15 3.2 实验方法........................................................................................................16IV 3.2.1 菲及蒽浓度的测定..............................................................................16 3.2.2 实验参数的确定..................................................................................16 3.3 实验设计及结果讨论....................................................................................17 3.3.1 不同电场方式对 EK 修复菲污染土壤的影响 ..................................17 3.3.2 控制阳极 pH 对 EK 修复菲污染土壤的影响 ...................................20 3.3.3 电动力学修复蒽污染土壤的研究......................................................24 3.4 本章小结.........................................................................................................26 第 4 章 漆酶作为 EK 联用技术修复 PAHs 污染土壤的可行性研究.....................27 4.1 研究方案依据................................................................................................27 4.1.1 EK 修复 PAHs 污染土壤存在的主要问题 .........................................27 4.1.2 漆酶修复有机污染土壤的现状及作为 EK 联用技术的可行性 ......27 4.1.3 漆酶修复有机污染土壤存在的问题..................................................28 4.1.4 漆酶稳定方法的选择...........................................................................28 4.2 实验材料........................................................................................................29 4.2.1 酶制剂..................................................................................................29 4.2.2 化学试剂..............................................................................................30 4.2.3 实验仪器与设备.....................