摘  要

多环芳烃（Polycyclic aromatic hydrocarbons，简称PAHs）是一类持久性有毒有害污染物，因其致畸、致癌和致突变的特性，对人体健康和生态环境构成严重威胁。土壤是多环芳烃最主要的储存库，焦化场地土壤多环芳烃污染程度一般较重。多种化学氧化修复技术可用于去除土壤多环芳烃，其中芬顿氧化因其快速高效，应用范围广，无二次污染等优点而被广泛应用于多环芳烃污染场地土壤修复。实际污染场地土壤多环芳烃成分复杂，筛选适宜的芬顿氧化体系有助于提高修复效率。但是芬顿氧化在去除多环芳烃的同时会对土壤微生物以及土壤质量产生负面影响。土壤中多环芳烃的生物转化主要依赖细菌等微生物，探究不同芬顿氧化下土壤细菌群落的响应及演替对于污染场地的持续管理具有重要意义。针对芬顿氧化对土壤微生物的不利影响，对受损微生物群落进行生态救援（ecological rescue）可以帮助其从胁迫中恢复过来从而提高后续生物降解PAHs的效率，进一步改善化学氧化后生物降解的潜力。

本论文以陕西某焦化场地污染土壤为研究对象，探讨了芬顿氧化对土壤细菌群落的胁迫效应及其缓解方法。首先，设置不同过氧化氢和亚铁离子浓度配比以及不同螯合剂，根据多环芳烃（PAHs）去除率和苯并[a]芘（BaP）毒性当量变化以确定较优芬顿氧化体系；其次，以BaP为模式污染物，结合同位素示踪、高通量测序等技术，探究了不同浓度芬顿氧化下PAHs的降解效果与土壤细菌群落的响应及演替。最后，在芬顿氧化后，添加生物刺激材料或接种原始土壤进行生态救援，以BaP为模式污染物，结合同位素示踪、高通量测序等技术，从污染物降解、微生物群落演替等方面探究这些措施的微生物组效应及对土壤修复的影响。主要研究结果如下：

（1）设置不同过氧化氢（H₂O₂）和亚铁离子（Fe²⁺）浓度配比以及不同螯合剂，利用芬顿氧化技术处理焦化场地污染土壤。结果显示，芬顿氧化可以显著促进土壤PAHs去除，导致BaP与BaP毒性当量的明显下降。芬顿氧化去除PAHs的效率随氧化剂浓度的增加而上升，但过高剂量的氧化剂也会产生额外消耗，导致氧化剂利用效率降低。H₂O₂：Fe²⁺比例为20:1时PAHs去除效率略高于10:1，显著高于100:1。相较于有机螯合剂，无机螯合剂焦磷酸钠具有更好修复效果。基于此，针对该焦化场地的污染土壤，构建了H₂O₂：Fe²⁺比例为20:1，螯合剂为焦磷酸钠的芬顿氧化体系，为后续实验提供基础。

（2）在研究结果（1）构建的芬顿氧化体系下，设置了从低到高不同浓度芬顿氧化的微宇宙培养实验。结果显示，芬顿氧化法能快速促进土壤中PAHs的去除（8.06%-37.0%）和BaP的矿化（0.037%-1.28%），且效果与H₂O₂的用量呈正相关。同时芬顿氧化显著降低土壤细菌丰度、多样性，导致共现网络结构更为简单，群落组成也显著变化，假单胞菌（Pseudomonas）、芽孢杆菌（Bacillus）、Paenibacillus等环境耐受性强的菌属占据优势。随着培养时间的增加，微生物多样性有一定恢复，但高浓度芬顿的影响持续存在。

（3）在前期研究基础上选择中等浓度芬顿氧化，其后添加秸秆、原始土壤等对芬顿氧化后的受损土壤微生物组实施生态救援促进微生物恢复。结果表明芬顿氧化后添加秸秆（FS）进一步促进了BaP矿化和有机结合态，同时显著提高了细菌多样性以及相关降解基因丰度。添加原始土壤（FA）并未提高细菌丰度及多样性，但BaP降解功能有所恢复从而促进了BaP的矿化。联合施加秸秆和原始土壤（FSA）具有最佳的BaP矿化（8.12%）以及PAHs去除效果（53.4%），在培养12周后，四种多样性指数都恢复至同等甚至超过CK水平，细菌16S rRNA基因、PAH-RHDα GP基因拷贝数也较CK处理显著增加，同时简化了网络结构减少了种群竞争。通过细菌组成以及LEfSe分析发现，unclassified Sphingomonadaceae、unclassified Microscillaceae、Devosia、Ensifer和Rhizobium等属在联合修复处理显著富集并成为特异性生物标志物。这些菌属在降解PAHs以及土壤氮元素供给方面可能具有重要作用，为微生物降解PAHs提供了有利条件。

综上，本研究针对PAHs污染程度较重的焦化场地土壤，筛选出较优的芬顿氧化体系，在消除污染物和减少对微生物的胁迫之间进行权衡，并进一步研究了适宜浓度芬顿氧化+生态救援的联合修复技术手段。利用生物强化和生物刺激联合手段对化学氧化后受损的土壤微生物群落提供生态救援以帮助微生物群落更好地恢复，为化学氧化修复后污染场地的长期管控提供相关参考。

ABSTRACT

Polycyclic aromatic hydrocarbons (PAHs) are a class of persistent toxic and hazardous pollutants that pose a serious threat to human health and the ecological environment because of their teratogenic, carcinogenic and mutagenic properties. Soil is the most important reservoir of PAHs, and the degree of soil PAH contamination at coking sites is generally high. A variety of chemical oxidative remediation technologies can be used to remove soil PAHs, among which Fenton oxidation is widely used in soil remediation of PAH-contaminated sites due to its advantages of fast and efficient, wide range of applications, and no secondary pollution. As the PAH composition of soil is complex, screening of suitable Fenton oxidation system can help to improve the remediation efficiency. However, Fenton oxidation can negatively affect soil microorganisms and soil quality while removing PAHs. The biotransformation of PAHs in soil mainly relies on microorganisms such as bacteria, and it is important to investigate the response and succession of soil bacterial communities under different Fenton oxidation systems for the sustainable management of contaminated sites. In response to the adverse effects of Fenton oxidation on soil microorganisms, ecological rescue of damaged microbial communities can help them recover from the stress and improve the efficiency of subsequent biodegradation of PAHs and further improve the potential for biodegradation after chemical oxidation.

In this dissertation, the stress effect of Fenton oxidation on soil bacterial community and its mitigation methods were investigated in a contaminated soil of a coking site in Shaanxi. Firstly, different hydrogen peroxide and ferrous ion concentration ratios and different chelating agents were set to determine the preferred Fenton oxidation system based on the removal rate of polycyclic aromatic hydrocarbons (PAHs) and the change of benzo[a]pyrene (BaP) toxicity equivalents; secondly, the degradation of PAHs under different concentrations of Fenton oxidation was investigated in relation to the response and succession of soil bacterial communities using BaP as a model pollutant in conjunction with isotope tracing and high throughput sequencing techniques. community response and succession. Finally, after Fenton oxidation, biostimulatory materials were added or raw soil was inoculated for ecological rescue, and BaP was used as a model pollutant, combined with isotope tracing, high-throughput sequencing and other techniques to investigate the microbiome effects of these measures and their impact on soil remediation in terms of pollutant degradation and microbial community succession. The main research results are as follows:

Different hydrogen peroxide (H₂O₂) and ferrous ion (Fe²⁺) concentration ratios as well as different chelating agents were set up to treat contaminated soil from coking sites using Fenton oxidation. The results showed that Fenton oxidation could significantly promote the removal of PAHs from soil, leading to a significant decrease in the toxic equivalents of BaP and BaP. The PAHs removal efficiency of Fenton oxidation increased with the increase of the concentration of oxidant, but the high dose of oxidant also produced extra consumption, which led to the decrease of the efficiency of oxidant utilization.The PAHs removal efficiency was slightly higher than 10:1 at the ratio of 20:1 H₂O₂:Fe²⁺, and was significantly higher than 100:1.The inorganic chelator sodium pyrophosphate had a better remediation effect than the organic chelating agent. Based on this, a Fenton oxidation system with a H₂O₂:Fe²⁺ ratio of 20:1 and a chelating agent of sodium pyrophosphate was constructed for the contaminated soil of this coking site, which provided the basis for the subsequent experiments.

Under the Fenton oxidation system constructed in the research results (1), microcosm incubation experiments with different concentrations of Fenton oxidation from low to high were set up. The results showed that Fenton oxidation rapidly promoted the removal of PAHs (8.06%-37.0%) and mineralization of BaP (0.037%-1.28%) in soil, and the effect was positively correlated with the amount of H2O2. Meanwhile, Fenton oxidation significantly reduced the bacterial abundance and diversity of soil bacteria, leading to a simpler structure of the co-occurrence network and a significant change in the community composition, with the dominance of environmentally tolerant genera such as Pseudomonas, Bacillus and Paenibacillus.There was some recovery of microbial diversity with increasing incubation time, but the effects of high Fenton concentrations persisted.

(3) On the basis of the previous study, a medium concentration of Fenton oxidation, followed by the addition of straw and virgin soil, was chosen to implement ecological rescue to promote microbial recovery of the damaged soil microbiome after Fenton oxidation. The results showed that the addition of straw (FS) after Fenton oxidation further promoted BaP mineralization and organic incorporation, and significantly increased the bacterial diversity as well as the abundance of related degradation genes. The addition of virgin soil (FA) led to the restoration of BaP degradation function and thus promoted BaP mineralization. Combined application of straw and virgin soil (FSA) had the best BaP mineralization (8.12%) as well as PAHs removal (53.4%), and after 12 weeks of incubation, all four diversity indices were restored to equal or even exceeded the CK level, and the copy number of bacterial 16S rRNA genes and PAH-RHDα GP genes were also significantly increased compared with the CK treatment, as well as simplified the network structure to reduce population competition was reduced. Bacterial composition and LEfSe analysis revealed that the genera unclassified Sphingomonadaceae, unclassified Microscillaceae, Devosia, Ensifer, and Rhizobium were significantly enriched in the co-remediation treatment and became specific biomarkers. These genera may have important roles in the degradation of PAHs as well as soil nitrogen supply, providing favorable conditions for microbial degradation of PAHs.

In summary, in this study, for the soil of coking site with heavy pollution degree of PAHs, we screened the better Fenton oxidation system, made a trade-off between elimination of pollutants and reduction of stress on microorganisms, and further investigated the combined remediation technical means of Fenton oxidation + ecological rescue with suitable concentration. The combined means of bio-enhancement and bio-stimulation were utilized to provide ecological rescue to the damaged soil microbial community after chemical oxidation, which provides relevant reference for the sustainable biodegradation of pollutants after chemical oxidation.

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