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石油烃主要包括正构烷烃、异构烷烃、环烷烃、芳香烃以及树脂和沥青等,石油污染在不同程度上影响了海洋微生物、植物和动物的生长繁殖[1]. 海洋环境中的石油烃主要来源于成岩转化、生物合成、工业民用废水排放、港口和船舶作业含油污水排放以及燃油泄漏等突发污染事故[2-3]. 研究正构烷烃的分布特征,对正构烷烃多种特征指数进行综合评价,是国内外广泛采用的海洋沉积物石油烃来源分析方法[2,4]. 多环芳烃是石油烃的重要组成成分,是具有致癌、至畸、致突变作用的持久性有机污染物,多环芳烃在海洋生物体内不断富集并通过食物链传递与放大进入人体,最终威胁人体健康[5]. 海洋环境中的多环芳烃很少部分来自自然源,大部分来自生物质和化石燃料不完全燃烧或石油泄漏等人为源[6].
海洋沉积物是环境中石油烃等多种有机污染物的主要归宿,近岸海洋沉积物中石油烃赋存状况受沿海地区生产活动的影响较为显著. 江苏小洋口地区位于我国中部江淮下游,濒临南黄海,研究区域内建有洋口化学工业园和LNG码头,存在较为密集的沿海化工生产和航运活动. 近年来对南黄海的溶解氧分布、浮游动物群落特征以及沉积物中有机质来源等已有较多的分析和研究[7-9],但对南黄海近岸海域沉积物中石油烃类污染物的研究较少. 本研究对小洋口地区近岸海域表层沉积物中石油烃总量和多环芳烃含量进行了分析,研究了正构烷烃分布特征并探讨了石油烃来源,为掌握该地区的污染状况提供基础数据.
江苏小洋口近岸海域沉积物中石油烃类物质分布特征及来源
Distribution characteristics and sources of petroleum hydrocarbons in sediments from Xiaoyangkou coastal area in Jiangsu Province
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摘要: 为深入了解江苏小洋口地区近岸海域表层沉积物中石油烃污染状况,分析近岸生产活动对海洋环境的影响,于2020年在小洋口近岸海域采集了10个点位的沉积物样品,采用气相色谱法和气相色谱质谱法分析测定其中的石油烃及多环芳烃总量,揭示了正构烷烃(n-Alkane)分布特征并探讨了石油烃来源. 结果表明,小洋口近岸海域表层沉积物中石油烃总量介于3.95—13.28 μg·g−1之间,碳数分布为C11—C36;洋口港、洋口化学工业园附近海域沉积物中石油烃含量相对较低,港口和化工生产项目未对邻近海域中石油烃浓度产生明显影响. 河口附近石油烃含量相对较高,可能受陆源输入影响较大. 大部分点位沉积物中石油烃为陆海混合来源,个别点位沉积物中石油烃以陆源输入为主;数据显示该海域可能受到轻度石油污染. 此外,小洋口近岸海域表层沉积物中多环芳烃总量介于53.1—117.0 ng·g−1之间,与该海域其它研究浓度相当,在国内处于相对较低水平;以三环和四环芳烃为主,可能是燃烧与石油混合来源的结果.Abstract: In order to understand the pollution status of petroleum hydrocarbons in surface sediments of Xiaoyangkou coastal area and analyze the impact of nearshore production activities on the marine environment,10 sediment samples were collected in 2020 and analyzed for the content of petroleum hydrocarbons by gas chromatography and polycyclic aromatic hydrocarbons (PAH) by gas chromatography- mass spectrometry. The distribution characteristics of n-alkane and the source of petroleum hydrocarbons were studied. The results showed that the content of total petroleum hydrocarbons (TPH) varied from 3.95 μg·g−1 to 13.28 μg·g−1, and the carbon number distribution was from 11 to 36. The content of TPH in the sediments near Yangkou Port and Yangkou Chemical Industrial Park were relatively low, which indicated that the port and chemical production projects had no obvious influence on the concentration of petroleum hydrocarbon in the adjacent sea areas. The TPH content near the river mouth was at a relatively high level, which may be greatly affected by terrigenous input. Petroleum hydrocarbons in most of the samples were from terrigenous and marine mixed sources, while terrigenous input was dominant in a small part of samples. It was possible that this area was slightly contaminated by petroleum. The total amount of PAHs ranged from 53.1—117.0 ng·g−1, which was consistent with other studies in this sea area and at a relatively low level compared with other sea areas in China. Tricyclic and tetracyclic aromatic hydrocarbons were predominant, which was probably as a result of combustion mixed with petroleum sources.
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Key words:
- Xiaoyangkou /
- marine sediment /
- petroleum hydrocarbons /
- distribution characteristics.
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表 1 研究采用指数计算方法及意义
Table 1. The calculation method and meaning of the index adopted in this study
指数名称
Index计算方法
Calculation method指数含义
Meaning /C16$ \displaystyle\sum \text{n}-\text{Alk} $ 正构烷烃总量与正十六烷含量比值 用于评价沉积物是否受到石油污染. $ \text{L}/\text{H} $ $ \text{L}/\text{H}=\left(\displaystyle\sum {\text{C}}_{\text{23-}}\text{/}\displaystyle\sum {\text{C}}_{\text{24+}}\right) $ 用于评价正构烷烃主要来源,如高等植物、海洋动物、细菌、石油等. $ \text{TAR} $ $ \text{TAR=}\left({\text{n}\text{C}}_{\text{27}}+{\text{n}\text{C}}_{\text{29}}+{\text{n}\text{C}}_{\text{31}}\right)\text{/}\left({\text{n}\text{C}}_{\text{15}}+{\text{n}\text{C}}_{\text{17}}+{\text{n}\text{C}}_{\text{19}}\right) $ 用于评价正构烷烃陆源、海源相对贡献. $ {\text{CPI}}_{\text{1}} $ $\begin{aligned} {\text{CPI} }_{\text{1} }=&\text{1/2}\Big[\displaystyle\sum {\text{C} }_{\text{15-21} }\left(\text{奇碳}\right)\text{/}\displaystyle\sum {\text{C} }_{\text{14-20} }\left(\text{偶碳}\right)+\\ & \displaystyle\sum {\text{C} }_{\text{15-21} }\left(\text{奇碳}\right)\text{/}\displaystyle\sum {\text{C} }_{\text{16-22} }\left(\text{偶碳}\right)\Big]\end{aligned}$ 短链烷烃碳优势指数,用于区分正构烷烃来源. $ {\text{}\text{CPI}}_{\text{2}} $ $\begin{aligned} {\text{CPI}}_{\text{2}}=&\text{1/2}\Big[\displaystyle\sum {\text{C}}_{\text{25-35}}\left(\text{奇碳}\right)\text{/}\displaystyle\sum {\text{C}}_{\text{24-34}}\left(\text{偶碳}\right)+\\& \displaystyle\sum {\text{C}}_{\text{25-35}}\left(\text{奇碳}\right)\text{/}\displaystyle\sum {\text{C}}_{\text{26-36}}\left(\text{偶碳}\right)\Big] \end{aligned}$ 长链烷烃碳优势指数,用于区分正构烷烃来源. C18/Ph 正十八烷含量与植烷含量比值 用于评价石油降解程度. U/R 复杂化合物与可分离烷烃含量比值 用于推断沉积物是否受到石油污染. 表 2 研究海域各点位石油烃总量及正构烷烃总量
Table 2. The contents of total petroleum hydrocarbons and total n-alkanes at each point in the study areas
点位
Sampling points石油烃总量/(μg·g−1)
TPH正构烷烃总量/(μg·g−1)
$ \sum n-Alk $ 1 10.40 1.99 2 9.35 1.36 3 7.50 1.30 4 6.19 1.57 5 13.28 4.31 6 5.19 1.74 7 6.60 1.67 8 6.33 2.07 9 7.12 1.72 10 3.95 1.23 均值 7.59 1.90 表 3 近岸海域表层沉积物中总石油烃浓度比较
Table 3. Comparison of total petroleum hydrocarbon concentrations in surface sediments of coastal waters
表 4 研究海域正构烷烃相关指数
Table 4. The index calculated from n-alkanes in the study areas
点位
Sampling points /C16$ \sum n-Alk $ L/H TAR CPI1 CPI2 C18/Ph U/R 1 15.3 0.73 3.40 0.44 1.34 2.52 3.19 2 12.7 0.72 5.68 0.17 1.42 2.45 4.33 3 11.4 0.79 3.99 0.19 1.18 2.18 3.46 4 13.1 0.67 6.73 0.15 1.71 2.47 2.25 5 41.4 0.23 10.8 0.43 1.14 2.39 2.04 6 15.6 1.12 2.72 0.53 1.47 2.75 1.24 7 15.2 0.76 7.26 0.15 2.37 2.69 2.15 8 17.3 0.93 2.95 0.61 1.81 2.43 1.27 9 15.6 0.82 3.31 0.55 2.10 2.06 1.83 10 12.7 1.56 1.29 0.47 0.86 2.46 1.51 均值 17.0 0.83 4.82 0.37 1.54 2.44 2.33 表 5 研究海域各点位16种多环芳烃总量
Table 5. Total contents of 16 PAHs at each point in the study area
点位
Sampling points多环芳烃总量/(ng·g−1)
Total content of PAHs1 88.0 2 56.5 3 117.0 4 59.3 5 68.2 6 46.6 7 53.1 8 76.4 9 62.7 10 69.3 均值 69.7 -
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