Determination of Polybrominated Diphenyl Ethers and Bioaccumulation in Freshwater Fish Surrounding a Flame Retardant Manufacturing Plant by Gas Chromatography-Mass Spectrometry
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摘要: 近年来多溴联苯醚（PBDEs）的研究集中在电子行业发达地区、电子废物处置区、塑料制品生产区等重点污染区域。对阻燃剂生产厂周边PBDEs的研究有助于更好地理解PBDEs的累积特征和环境过程。本文选择江苏某PBDEs生产厂周边的淡水河流，采用气相色谱-质谱法（GC-MS）分析该河流5种淡水鱼中13种PBDEs同族体的浓度。结果显示，淡水鱼样品肌肉、肝脏和鱼卵组织中∑13PBDEs（BDE17、28、71、47、66、100、99、85、154、153、138、183、190）的浓度平均值分别为34.5 ng/g.lip、41.5 ng/g.lip和18.2 ng/g.lip。研究水域不同种类淡水鱼的食性、习性和代谢能力等是影响鱼体中PBDEs浓度的主要因素。鱼体中BDE47是主要的同族体，但是与大多数已报道的研究数据相比，鱼体中含有的六溴（BDE153、154）和七溴同族体（BDE183）比例较高，这与河流附近工厂生产八溴联苯醚工业品（以六溴、七溴和八溴同族体为主）相符。工厂生产的八溴联苯醚工业品以及河流上游径流带来的其他区域生产和使用的多溴联苯醚工业品释放到环境中，被河流中的淡水鱼类选择性地积累和代谢，形成了本研究区淡水鱼体中PBDEs特殊的同族体分布。Abstract: In recent years, the research on polybrominated diphenyl ethers (PBDEs) has been heavily concentrated in polluted areas, such as the developed areas of the electronic industry, electronic waste disposal arrears, and plastic materials production areas. Research on PBDEs surrounding a flame retardant manufacturing plant may contribute to a better comprehension of their bioaccumulation characteristics and environmental processes. Five species of fish were collected from a freshwater environment surrounding a PBDE technical mixtures manufacturing plant in Jiangsu Province. Concentrations of thirteen PBDE congeners were determined by Gas Chromatography-Mass Spectrometry (GC-MS). Results show that the average concentrations of ∑13PBDEs (BDE17, 28, 71, 47, 66, 100, 99, 85, 154, 153, 138, 183, 190) in muscle, liver and egg tissues are 34.5 ng/g.lip, 41.5 ng/g.lip and 18.2 ng/g.lip, respectively. Feeding and living habits as well as metabolic ability may influence the occurrence of PBDEs in fish in this area. BDE47 was the predominant compound in most fish samples, however, the fish in the present study have a higher proportion of hexa-and hepta-BDEs such as BDE153, BDE154 and BDE183 compared to the data reported in other studies, which is consistent with the octa-BDE technical mixtures (dominated by hexa-, hepta-and octa-BDEs) from the manufacturing plant near the river. The octa-BDE technical mixtures produced here, and the PBDE technical mixtures produced and used in other regions were carried in by upstream runoff and released into the environment, which were selectively bioaccumulated and metabolized by freshwater fish, resulting in the specific distribution of PBDE congeners in fish in this area.
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表 1 淡水鱼样品信息
Table 1. Sample information of freshwater fish
鱼类 鱼样数量 鱼样长度
(cm)鱼样质量
(g)δ15N值范围
(均值，‰)脂肪含量范围
(均值，%)食性 习性 鲫鱼 3 19~20 143~238 6.8~15
(12)肌肉2.9~7.0(4.3)
肝脏8.2~10 (9.0)
鱼卵6.7~10 (8.4)杂食性 底栖 鲤鱼 4 26~51 264~1817 8.9~16
(13)肌肉2.8~6.3(4.7)
肝脏14~22(19)
鱼卵12杂食性 底栖 餐条 3 14~24 38~190 13~16
(15)肌肉6.1~18(11)
肝脏11~30(22)
鱼卵14杂食性 中上层 鲶鱼 3 23~39 180~519 8.1~17
(14)肌肉2.2~14(6.5)
肝脏5.0~15(9.6)
鱼卵9.7~11(10)肉食性 底栖 黑鱼 3 20~24 135~185 13~15
(14)肌肉2.3~3.2(2.7)
肝脏13~31(25)肉食性 底栖 
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表 2 二级质谱扫描和选择离子扫描PBDEs及内标特征离子
Table 2. Characteristic ions of PBDEs and internal standard for mass/mass and SIM scanning conditions
PBDEs
同族体二级质谱(MS/MS) 选择离子模式(SIM)
特征离子(m/z)母离子
(m/z)子离子
(m/z)三溴同族体 405.8 238~258/395~415 248.0/405.8 四溴同族体 485.6 315~335/475~495 326.0/485.6 五溴同族体 563.5 393~413/553~573 405.8/563.5 六溴同族体 643.4 473~493/633~653 483.7/643.4 七溴同族体 723.3 551~571/713~733 563.7/723.3 回收率指示物
13C-BDE139653.4 485~505/645~665 495.6/653.4 定量内标
13C-PCB178407.8 140~350 372.9/407.8
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表 3 国内外鱼体中PBDEs的浓度
Table 3. Concentration of PBDEs in fishes from different locations
地区 ∑PBDEs浓度均值 BDE47浓度均值 所测PBDEs同族体 参考文献 脂重
(ng/g.lip)湿重
(pg/g.ww)脂重
(ng/g.lip)湿重
(pg/g.ww)本研究水域
(江苏)34.5 251 12.7 92.9 BDE17，28，47，66，71，85，99，100，138，153，154，183，190 本文 东江 81 519 51 - BDE28，47，66，85，99，100，138，153，154，183 [19] 长江 120 - 37 - BDE3，15，28，47，99，100，153，154，183，196，197，206，207，209 [16] 浙江台州 5366.07 65170 - 31000 BDE47，99，100，153，154，183 [20] 欧洲 119 - 81.8 - BDE47，99，100，153，154 [21] 北美 1050 - 622 - BDE47，99，100，153，154 [21] 美国哈德利湖 1600 - 809 - BDE47，99，100，153，154，190，209 [22]
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