Determination of Hexabromocyclododecane and Tetrabromobisphenol A in Soil and Sediment by High Performance Liquid Chromatography-Triple Quadrupole Mass Spectrometry
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摘要: 为服务我国履行《关于持久性有机污染物的斯德哥尔摩公约》和新污染物监测的需要，建立了同步分析土壤和沉积物中3种六溴环十二烷(HBCDs)异构体和四溴双酚A (TBBPA)的高效液相色谱-三重四极杆质谱法. 样品经冷冻干燥，以正己烷与丙酮(体积比为1∶1)为提取溶剂进行加压流体提取，通过中性和酸性复合硅胶柱的净化处理，洗脱液转溶至甲醇后进行仪器分析，用同位素稀释内标法定量. 结果表明：①目标物在液相色谱上得到有效的基线分离，保留时间稳定，相对偏差小于3.0%，在2.0~200 ng/mL范围内标准曲线的平均相对响应因子的相对标准偏差小于15%. ②α-HBCD、β-HBCD、γ-HBCD和TBBPA的方法检出限分别为0.06、0.04、0.04和0.06 μg/kg. ③石英砂、背景土壤、工业土壤、河流沉积物和海洋沉积物的低中高浓度平行添加试验显示，方法的精密度为1.76%~10.6%，加标回收率为92.9%~121%. ④8种不同pH的土壤中目标物的加标回收率范围为85.9%~104%. 本研究建立的方法灵敏度高、适用性好，能够用于复杂土壤和沉积物样品中HBCDs和TBBPA的分析测试.
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关键词:
- 土壤 /
- 沉积物 /
- 六溴环十二烷(HBCDs) /
- 四溴双酚A (TBBPA) /
- 高效液相色谱-三重四极杆质谱
Abstract: A high performance liquid chromatography-triple quadrupole mass spectrometry method was developed to determine three hexabromocyclododecane (HBCD) isomers and tetrabromobisphenol A (TBBPA) in soil and sediment, for the needs of the Stockholm Convention on Persistent Organic Pollutants and new pollutants control in China. Samples were freeze-dried, extracted by pressurized fluid with n-hexane and acetone (volume ratio, 1∶1), and then cleaned up with neutral and acidic silica gel columns. They were quantitated by instrumental analysis using isotope dilution method. The results showed that: (1) Effective baseline separation was achieved by liquid chromatography, and the retention time was stable with relative deviation less than 3.0%. The relative standard deviation of the average relative response factor was less than 15% in the concentration range of 2.0-200 ng/mL. (2) The detection limits for α-HBCD, β-HBCD, γ-HBCD and TBBPA were 0.06, 0.04, 0.04 and 0.06 μg/kg, respectively. (3) The precision of the method was 1.76%-10.6%, and the recovery was 92.9%-121%. (4) Spiking experiments were carried out on eight soil types with different pH value. The recovery ranged from 85.9% to 104%. The established method has demonstrated high sensitivity and high applicability, and can be used for the determination of HBCDs and TBBPA in complex soil and sediment samples. -
图 1 不同溶剂提取目标物的回收率
注：校正回收率指基于同位素提取内标校正后的回收率，绝对回收率指基于进样内标的回收率.
Figure 1. The recoveries of the analytes on different extracting solvents
图 3 目标物在3种不同洗脱溶剂下的淋洗曲线
Figure 3. The elution curves of targets in three different solvents
图 4 不同流动相下目标物的归一化响应
Figure 4. Normalized response of targets in different mobile phases
图 6 不同柱温下HBCDs和TBBPA的MRM色谱图
Figure 6. MRM chromatograms of HBCDs and TBBPA in different column temperatures
表 1 目标物分析的梯度洗脱程序
Table 1. Gradient elution profile for the target compounds analysis
时间/min 流速/(mL/min) 流动相A/% 流动相B/% 0 0.3 70 30 2 0.3 30 70 3 0.3 20 80 5 0.3 20 80 8 0.3 15 85 9 0.3 70 30 14 0.3 70 30 注：9～14 min为两次样品分析间的平衡时间. 
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表 2 方法精密度和正确度数据
Table 2. The precision and accuracy of the developed method
样品类型 添加量 α-HBCD β-HBCD γ-HBCD TBBPA 平均值/
(μg/kg)相对标准
偏差/%加标回收
率/%平均值/
(μg/kg)相对标准
偏差/%加标回收
率/%平均值/
(μg/kg)相对标准
偏差/%加标回收
率/%平均值/
(μg/kg)相对标准
偏差/%加标回收
率/%石英砂 1 0.54 4.54 108 0.55 4.42 110 0.55 7.71 111 0.48 5.11 95.6 2 1.86 5.72 92.9 1.90 2.24 94.8 1.89 3.01 94.4 1.87 4.26 93.6 3 9.67 4.48 96.7 9.74 1.93 97.4 9.70 2.16 97.0 9.61 3.77 96.1 背景土壤 1 0.58 6.94 116 0.56 3.74 112 0.60 4.77 120 0.58 10.0 115 2 2.13 10.6 107 2.10 6.78 105 2.11 5.61 105 2.11 7.29 106 工业土壤 2 2.77 8.97 112 2.61 7.28 112 5.20 6.22 121 1.9 2.52 94.8 3 10.9 2.16 104 11.4 3.22 110 13.0 2.24 102 10.6 1.76 106 海洋沉积物 1 0.57 5.16 114 0.59 3.58 117 0.56 3.67 113 0.57 4.42 114 2 1.97 1.88 98.7 1.95 2.92 97.6 1.93 4.65 96.7 1.91 3.63 95.3 河流沉积物 2 2.30 5.01 115 2.24 7.97 112 2.32 5.57 116 2.22 4.91 111 3 10.8 3.48 108 11.1 3.19 111 11.4 1.84 114 11.7 2.62 117 注：添加量1、2、3代表目标物的添加浓度分别为0.5、2.0、10 μg/kg.
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