高效液相色谱-三重四极杆质谱法测定土壤和沉积物中六溴环十二烷和四溴双酚A

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. 

Determination of Hexabromocyclododecane and Tetrabromobisphenol A in Soil and Sediment by High Performance Liquid Chromatography-Triple Quadrupole Mass Spectrometry

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.