黄河三角洲作为典型的河口滨海湿地生态系统，同时也是我国重要的油气开采区，在石油开采、加工、运输等过程中不可避免的会产生土壤溢油污染，这对周边农业生产、人类生活均造成了一定的负面影响。随着经济的高速发展和河口区域人为活动加剧，研究区域内石油污染和重金属污染愈加严重，芦苇和碱蓬作为黄河三角洲典型湿地植物，其本身对重金属具有一定的富集能力。因此，研究石油污染对湿地植物富集重金属的影响，将为黄河三角洲石油-重金属复合污染的生物修复提供一定的科学依据和理论价值。

本论文主要通过野外采样与实验相结合，对土壤重金属、总石油烃（TPH）、多环芳烃（PAHs）以及湿地植物（芦苇、碱蓬）根茎叶中的重金属含量进行分析，探究了研究区域内重金属（Pb、Mn、Fe、Co、Ni、Zn）、石油烃的污染现状，进行了多环芳烃的源解析。此外，通过研究重金属在植物体内富集迁移能力随TPH的作用规律，进一步探讨不同油井区溢油污染物对植物富集重金属的影响；对比芦苇、碱蓬在相同浓度的溢油污染下对重金属的富集迁移系数，分析两者对溢油污染的耐受性高低，探究哪种植物更适宜在溢油污染区富集重金属。研究结果表明：

⑴研究区域表层石油烃污染程度较轻，且重金属Pb、Mn、Fe、Co、Ni、Zn低于国家土壤质量一级标准和山东省土壤背景值。而垂向上油井区Pb、Mn、Fe、Co、Zn主要在10—20 cm土层达到重金属浓度最大值，非油井区的垂向重金属变化不规律。这可能是由于溢油污染物影响范围主要在0—20 cm，使得浅层重金属累积。多环芳烃作为溢油的重要组分，研究区域污染水平在我国属于中等偏上，且多环芳烃主要来源为石油污染和燃烧的混合源。

⑵芦苇：必须元素Zn和Mn地上部分、地下部分分布较为均衡。其它4种重金属主要集中分布于根部，茎叶中含量较少。在新老油井区，芦苇对6种重金属的整体富集系数随TPH升高，均呈现出先升高后降低最后升高的趋势，这与不同浓度TPH对植物体作用效果不同有关。与对照相比，TPH对Zn、Mn具有一定的迁移促进作用。而对其他四种重金属表现为低浓度促进、高浓度抑制的迁移作用。

碱蓬：必需元素Zn主要分布于地上部位，其余5种重金属主要集中分布于根部。碱蓬对6种重金属的富集表现均表现为低浓度富集能力较强，随TPH升高逐渐下降，这可能是由于高浓度TPH对碱蓬根部影响较大。溢油污染下，碱蓬对Zn的迁移能力较好，整体大于1且大于对照区。但对除Zn以外的5种重金属表现出较差的向上迁移能力。

TPH对碱蓬根部影响较强，高浓度TPH不利于根部重金属富集。但与芦苇相比，碱蓬对Pb、Fe、Co、Ni、Zn的富集和迁移系数更大，这表明在油井区碱蓬比芦苇具有更好的重金属迁移富集特性，在研究的浓度范围内，碱蓬整体对溢油污染物耐性更好。

基于前人研究石油烃对植物的影响主要采用模拟实验的方法，对其生理特性和体内酶活性的影响较多，对原生环境下其影响富集迁移重金属的研究较少。本论文主要以此为出发点，通过实地采样探究石油烃污染下芦苇碱蓬的重金属富集规律，不同于盆栽实验，虽然实际获得石油烃影响浓度范围较窄但总体有助于对实际情况进行判断。以期为石油-重金属复合污染的生物修复研究提供一定的理论基础。

The Yellow River Delta is a typical estuarine and coastal wetland ecosystem, as well as one of the important oil and gas exploration area in China. Oil pollution is inevitably in the process of oil exploitation, processing and transportation, which has a negative impact on the surrounding agricultural production and human life. With the rapid development of economy and the intensification of human activities in estuary area, pollution of oil and heavy metal are becoming more and more serious in the study area. As wetland plants, Phragmites australis and Suaeda salsa have certain enrichment capacity for heavy metals. Therefore, the study of the impact of oil pollution on the accumulation of heavy metals in wetland plants will provide scientific basis and theoretical value for the bioremediation of oil-heavy metal complex pollution in the Yellow River Delta.

In this thesis, through filed sampling and the analysis of heavy metals in soil, total petroleum hydrocarbons (TPH), polycyclic aromatic hydrocarbons (PAHs) and wetland plants (Phragmites australis, Suaeda salsa) rhizomes and leaves, the pollution status of heavy metals (Pb, Mn, Fe, Co, Ni, Zn) and petroleum hydrocarbons in the study area were explored, and the source analysis of PAHs was carried out. In addition, by studying the effect of TPH on the accumulation and migration of heavy metals in plants, the influence of oil pollutants in different oil fields on the accumulation of heavy metals in plants were further discussed. Under the same concentration of oil pollution, comparing the enrichment and migration coefficients of heavy metals of Phragmites australis and Suaeda salsa to analyze their tolerance to oil pollution, and to explore which plant is more suitable to enrich heavy metals in oil pollution areas. The results showed that:

⑴ It shows a lower degree of surface petroleum hydrocarbons pollution in the study area. The concentration of Pb, Mn, Fe, Co, Ni and Zn in the surface layer was lower than the first-class national soil quality standard and the background value of Shandong soil. The main vertical direction of Pb, Mn, Fe, Co and Zn in oil fields reached the maximum concentration of heavy metals in 10—20 cm soil layer, while the vertical variation of heavy metals in non-oil well area was irregular. This may be due to the accumulation of heavy metals in shallow layers because of the role of oil pollutants. As an important component of oil pollutants, PAHs showed a medium pollution level in China and were mainly derived from mixed sources of petroleum pollution and combustion.

⑵ Phragmites australis: The distribution of essential elements Zn and Mn was more balanced in the above-ground and underground parts, while the Pb, Fe, Co and Ni was mainly concentrated in the root but less in the stem and leaf. In old and new oil fields, the overall enrichment coefficients of heavy metals in Phragmites australis showed a trend of first increasing, then decreasing and finally increasing with the increase of TPH concentration, which was related to the different effects of TPH on plants at different stages. In compared with the control, TPH can promote the migration of Zn and Mn in the range of concentration, while for the other four heavy metals, the migration was promoted by low TPH concentration (<400μg•g^-1) and inhibited by high TPH concentration.

Suaeda salsa: Essential element Zn mainly distributed in the above-ground parts, while the other heavy metals mainly distributed in roots. Of all heavy metals, Suaeda salsa showed strong enrichment ability at low concentration, and gradually decreased with the increase of TPH. This may be due to the biger influence of high TPH on the root of Suaeda salsa. Under oil pollution, the migration ability of Zn in Suaeda salsa was better, which was greater than 1 and larger than the control area, while for the other five heavy metals the migration ability was poor.

The root of Suaeda salsa was more sensitive to TPH. High TPH concentration was not conducive to the absorption of heavy metals in root. However, compared with Phragmites australis, Suaeda salsa had a larger accumulation and migration coefficient of Pb, Fe, Co, Ni and Zn, which indicated that Suaeda salsa had better migration and enrichment characteristics of heavy metals than Phragmites australis in oil filed. Within the concentration range studied, Suaeda salsa has better tolerance to oil pollutants.

Previous studies on the effects of petroleum hydrocarbons on plants mainly used the method of simulation experiments, and it mainly focused on its physiological characteristics and activities of enzymes in vivo. Few studies have been conducted on the influence of primary environment on the enrichment and migration of heavy metals. In this thesis, the heavy metal enrichment of Suaeda salsa and Phragmites australis under oil pollution was investigated by field sampling. Different from simulation experiments, although the actual concentration range of petroleum hydrocarbons is narrow, it is generally helpful to judge the actual situation. It is expected to provide a theoretical basis for the bioremediation of oil-heavy metal complex pollution.

目 录
第1章
引言... 1
1.1 研究背景... 1
1.1.1 土壤石油污染现状... 1
1.1.2 土壤石油污染的危害... 2
1.1.3 多环芳烃污染现状及其生理毒性... 3
1.1.4 土壤重金属污染现状... 5
1.1.5 土壤重金属污染危害... 6
1.1.6 石油烃-重金属复合污染的生态毒性研究... 8
1.1.7 黄河三角洲土壤石油烃、重金属污染现状... 9
1.1.8 碱蓬和芦苇生理特性... 10
1.2 研究目的及研究内容... 11
1.2.1 研究目的... 11
1.2.2 研究内容与技术路线... 12
1.3 小结... 13
第2章 研究区域与研究方法... 14
2.1 研究区概况... 14
2.2 研究方法... 16
2.2.1 样品采集... 16
2.2.2 实验仪器... 17
2.2.3 样品预处理... 17
2.2.4 土壤粒度测定... 17
2.2.5 重金属测定... 18
2.2.6 土壤总石油烃（TPH）测定... 18
2.2.7 土壤多环芳烃（PAHs）测定... 18
2.2.8 总碳（TOC）、总氮（TN）测定... 19
2.3 数据处理... 19
第3章 黄河三角洲土壤重金属、石油烃、多环芳烃分布特征及来源解析 21
3.1 表层土壤中重金属以及石油烃含量分布... 21
3.1.1 土壤理化性质——粒度、TOC.. 21
3.1.2 石油烃分布及其与土壤理化性质相关性分析... 23
3.1.3 重金属分布及其与土壤理化性质相关性分析... 24
3.2 石油污染物影响土壤垂向重金属分布规律... 27
3.2.1 油井区与非油井区重金属垂向分布... 27
3.2.2 垂向重金属与粒度、TOC的关系... 29
3.3 多环芳烃的分布与来源解析... 31
3.3.1 多环芳烃分布... 31
3.3.2 多环芳烃主要来源解析... 33
3.4 小结... 35
第4章 黄河三角洲石油污染物对芦苇、碱蓬富集转运重金属的影响... 37
4.1 石油污染物对芦苇富集转运重金属的影响... 37
4.1.1 石油污染下，芦苇各部分重金属分布... 37
4.1.2 石油污染物对芦苇富集重金属的影响... 40
4.1.3 不同石油污染区重金属富集规律对比... 44
4.1.4 石油污染物对重金属迁移的影响... 45
4.2 石油污染物对碱蓬富集转运重金属的影响... 48
4.2.1 石油污染下，碱蓬各部分重金属分布... 48
4.2.2 石油污染物对碱蓬富集重金属的影响... 51
4.2.3 石油污染物对碱蓬重金属迁移的影响... 54
4.3 芦苇和碱蓬富集迁移能力对比... 56
4.4 小结... 57
第5章 结论与展望... 59
5.1 结论... 59
5.2 创新点... 60
5.3 不足与展望... 61
参考文献... 63
致谢... 77
作者简历及攻读学位期间发表的学术论文与研究成果... 79