| 摘要: |
| 黄河入海口是我国三大河口之一。解析卤代化合物在该区域沉积物环境中的污染特征，并发现其未知卤代化合物，有助于正确评估该类物质对该区域环境的潜在风险。于2021年6月采集了黄河入海口46个海洋表层沉积物，分析样品中32种多氯联苯（PCBs）、27种多溴二苯醚（PBDEs）和16种新型卤代阻燃剂（EHFRs）的浓度组成和分布特征，进而基于全二维气相色谱-时间飞行高分辨质谱（GC×GC/HR-TOF/MS）对样品中未知卤代化合物进行了非靶向筛查。结果表明，沉积物中ω（PCBs）、ω（PBDEs）和ω（EHFRs）的范围分别为未检出（ND）～976.1 pg/g（干重，dw），ND～2 045.5 pg/g（dw）和ND～1 625.8 pg/g（dw）。PCBs以五氯联苯（Penta-PCBs）、三氯联苯（Tri-PCBs）和四氯联苯（Tetra-PCBs）为主；十溴二苯醚（BDE-209）是PBDEs主要的污染物，且表现出明显的区域差异特征，入海口以南区域显著性高于北部区域；EHFRs中，反式得克隆（anti-DP）、顺式得克隆（syn-DP）、五溴甲苯（PBT）、五溴苯（PBBz）和六溴苯（HBBz）是其主要检出的污染物，尤其是anti-DP和syn-DP在沉积物中普遍检出，且anti-DP和总得克隆（ΣDP）的比值与工业产品一致，表明沉积物中DP并未发生明显降解；借助GC×GC/HR-TOF/MS，在沉积物样品中识别出11种目标化合物之外的新型卤代化合物，其中8种是定量分析加入的内标化合物，其余3种的化学结构仍需进一步分析确证。环境风险评估结果表明，大部分点位的PBDEs和DP不会对当地环境造成风险；BDE-209可能存在中低风险，应引起重视。PCBs对黄河入海口生态环境不会产生不良影响。 |
| 关键词: 多氯联苯 多溴二苯醚 新型卤代阻燃剂 空间分布 非靶向筛查 风险评估 |
| DOI：DOI：10.3969/j.issn.1674-6732.2024.06.011 |
| 分类号:X55 |
| 基金项目:国家自然科学基金项目（21976088）；江苏省杰出青年基金项目（BK20211521） |
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| Pollution Characteristics and Non-targeted Screening of Halogenated Compounds in Sediments in the Yellow River Estuary |
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TU Yuanyang
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School of Environmental and Biological Engineering，Nanjing University of Science and Technology，Nanjing，Jiangsu 210094，China
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| Abstract: |
| The Yellow River estuary is one of the three major estuaries in China. Analyzing the contamination characteristics of halogenated compounds in the sediment environment of the region and discovering their unknown halogenated compounds can help to correctly assess the potential risk of such substances to the environment of the region. Forty six marine surface sediments from the Yellow River estuary were collected in June 2021 to analyze the concentration composition and distribution characteristics of 32 polychlorinated biphenyls（PCBs）， 27 polybrominated diphenyl ethers（PBDEs）， and 16 emerging halogenated flame retardants（EHFRs） in the samples， and then based on the full two-dimensional gas chromatography-time-of-flight high-resolution mass spectrometry（GC×GC/HR-TOF/MS）， a non-targeted screening was carried out for the samples. Unknown halogenated compounds were non-targeted screened.The results showed that the ranges of ω（PCBs），ω（PBDEs） and ω（EHFRs） in the sediment were ND（not detected）～976.1 pg/g（dw）， ND～2，045.5 pg/g（dw） and ND～1，625.8 pg/g（dw）， respectively. PCBs were dominated by pentachlorobiphenyl（Penta-PCB）， trichlorobiphenyl（Tri-PCB） and tetrachlorobiphenyl（Tetra-PCB）； decabromodiphenyl ether（BDE-209） was the main pollutant of PBDEs and showed obvious regional differences， with the significance of the region to the south of the estuary higher than that in the northern region； among the EHFRs， the pollutants were anti Dechlorane Plus（anti-DP）， syn Dechlorane Plus（syn-DP）， pentabromotoluene（PBT）， pentabromobenzene（PBBz） and hexabromobenzene（HBBz）. Hexabromobenzene（HBBz） were the main detected contaminants， especially anti-DP and syn-DP were commonly detected in the sediments， and the ratio（anti） of anti-DP to total degron（ΣDP） was consistent with that of industrial products， indicating that DP was not degraded significantly in the sediments；Based on the GC×GC/HR-TOF/MS， 11 emerging halogenated compounds other than the target compounds were identified in the sediment samples， of which 8 were internal standard compounds added for quantitative analysis， and the chemical structures of the remaining 3 still need to be further analyzed and confirmed. The results of the environmental risk assessment indicate that PBDEs and DPs at most points do not pose a risk to the local environment； BDE-209 may pose a low to medium risk and should be emphasized. PCBs will not have an adverse impact on the ecological environment of the Yellow River estuary. |
| Key words: Polychlorinated biphenyls（PCBs） Polybrominated diphenyl ethers（PBDEs） Emerging halogenated flame retardant（EHFRs） Spatial distribution Non-targeted screening Risk assessment |
