渤、黄海近海水体中芳香族有机化合物的分子识别和风险评估

Molecular identification and risk assessment of aromatic organic compounds in offshore waters of Bohai and Yellow Seas

  • 摘要: 传统上,有关芳香族有机化合物(aromatic organic compounds, AOCs)赋存特征、迁移传输行为和潜在生态风险评估的研究,往往关注美国环境保护署于20世纪提出的16种优控母体多环芳烃(polycyclic aromatic hydrocarbons, PAHs),然而越来越多的研究表明,包括PAHs衍生物在内的AOCs具有更强的毒性效应。鉴于环境介质中AOCs分子组成的复杂性,本文依托具有较强色谱分离能力的全二维气相色谱−飞行时间质谱(comprehensive two-dimensional gas chromatography- time of flight mass spectrometry, GC×GC-TOFMS),筛选并初步建立我国近海海水中AOCs分子组成高通量数据库,进而对渤、黄海近岸水体中AOCs的组成特征、空间分布、季节差异及其潜在水生生态风险进行初步研究。通过解析海水有机提取物的GC×GC-TOFMS谱图发现,渤、黄海近海表层水体中AOCs的分子数量占半挥发性有机化合物的50%以上。其中筛选出的79种AOCs表现出秋季最高、春季次之、夏季最低的季节差异特征,其平均总浓度分别为(2238±86)ng/L、(1266±486)ng/L和(1064±826)ng/L。在空间分布上,渤海湾近海表层水体中AOCs的浓度高于黄海,陆源输入强度和海水环流驱动等因素调控海水AOCs的时空异质性。进一步运用危险熵值(hazard quotients, HQs)和苯并a芘等效风险(BaP equivalent risk, BaPE)两种模型分别评估了AOCs的潜在水生生态风险。评估结果表明,相较于母体PAHs,将79种AOCs全部纳入评估模型的水生生态风险显著增加。本研究建立的AOCs分子鉴定和高通量数据库对于正确认识人类活动排放AOCs对海洋生态的潜在影响具有参考意义。

     

    Abstract: Traditional studies on the occurrence, transport behavior and potential ecological risk of aromatic organic compounds (AOCs) often focus on the 16-priority controlled polycyclic aromatic hydrocarbons (PAHs) proposed by the United States Environmental Protection Agency (EPA) in the last century. However, more and more studies have shown that AOCs have stronger toxic effects compared with priority-controlled PAHs. In view of the complexity of AOCs molecular composition in environmental media, this study relies on comprehensive two-dimensional gas chromatography-time of flight mass spectrometry (GC×GC-TOFMS) with stronger chromatographic separation capability to screen and initially establish a high-throughput database of AOCs molecular composition in offshore seawater in China. The composition characteristics, spatial distribution, potential aquatic ecological risks and their seasonal differences of AOCs in the Bohai Sea and the Yellow Sea were studied. By analyzing the GC×GC-TOFMS spectra of organic extracts from seawater, it was found that AOCs accounted for more than 50% of semi-volatile organic molecules in the surface water of the Bohai Sea and the Yellow Sea. The 79 AOCs showed the highest concentration in autumn, followed by spring, and the lowest concentration in summer. The average total concentration was (2238±86) ng/L, (1266±486) ng/L and (1064±826) ng/L, respectively. In terms of spatial distribution, the concentrations of AOCs in the surface waters of Bohai Bay is significantly higher than that in the Yellow Sea. The spatial and temporal heterogeneity of AOCs is regulated by the intensity of land-based input and the drive of sea circulation. The potential aquatic ecological risk of AOCs was further evaluated based on hazard quotient (HQs) and Benzoapyrene equivalent risk (BaPE) models respectively. The evaluation results showed that the aquatic ecological risk was significantly increased when 79 AOCs were included in the evaluation model compared to the parent PAHs. The molecular identification of AOCs and the high-throughput database established in this study are of reference significance for understanding the potential ecological impacts of AOCs emitted by human activities.

     

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