Simultaneous Analysis of Organochlorinated Pesticides and Polychlorinated Biphenyls from Animal Tissue using Gas Chromatography-Mass Spectrometry Combined with Accelerated Solvent Extraction
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摘要: 动物组织样品油脂含量大、干扰杂质多，对其中低含量有机氯农药及多氯联苯的分析会造成较大程度的影响。针对动物组织样品基质复杂的特点，本文以二氯甲烷-丙酮(体积比为1:1)的溶剂体系，采用加速溶剂萃取技术对样品进行提取，在提取过程中尽量减少脂肪的共提出，然后采用凝胶渗透色谱技术去除样品中的大部分油脂，再结合弗罗里硅土为填料的固相萃取方法对样品进一步净化，能够达到充分去除油脂和小分子杂质的目的。采用气相色谱-质谱分析17种有机氯农药及7种指示性多氯联苯，各化合物的回收率在81.6%~113.4%之间，检出限在1.02~3.59 ng/g之间，技术指标优于部分国家标准。本方法改进了动物样品的净化效果，建立了凝胶渗透色谱结合固相萃取技术的净化方法，达到了样品快速自动提取、溶剂用量少、基质净化彻底的目的，降低了方法检出限，能够满足快速、准确检测动物组织中低含量持久性有机污染物的要求。Abstract: The majority of fat and impurities in animal tissues influence the analysis result for low concentration organic compounds. To overcome this issue, the animal sample was extracted by accelerated solvent extraction (ASE) with methylene chloride/acetone (V:V=1:1), which reduced the co-extraction lipids during the extraction process. Gel Permeation Chromatography (GPC) combined with solid phase extraction (SPE) was applied to remove lipids from the sample solution. The GPC can remove most of the macromolecular lipids in samples, and the SPE with florisil can sufficiently reduce fat and small molecule impurity. The accuracy and sensitivity of the method can be improved by this pretreatment process. The compounds, including 17 organochlorinated pesticides and 7 indicator polychlorinated biphenyls in animal tissue, can be simultaneously analysed by Gas Chromatography Mass Spectrometry. The recoveries of 25 of the target compounds were in the range of 81.6%-113.4% and the method detection limits for dry samples were 1.02-3.59 ng/g. These results were superior to those of the national standard. This method improved the purification effect of animal samples, reduced the method detection limit, and enhanced the accuracy. It can be used to quickly and accurately determine the low content of persistent organic pollutants in animals.
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表 1 采用不同净化方法时样品提取液的脂肪含量
Table 1. The lipids content of the sample extracted by different clean-up methods
样品 脂肪含量(g) 脂肪含量 SEP 净化后的
脂肪含量GPC净化后的
脂肪含量GPC 结合SEP净化后的
脂肪含量猪肉 0.4048 0.3465 0.0032 0.0007 牛肉 0.4072 0.3759 0.0038 0.0006 鸡肉 0.1015 0.0801 0.0034 0.0007 鱼肉 0.2263 0.1903 0.0023 0.0006 
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表 2 25种化合物的GC-SIS-MS分析定性、定量离子及标准曲线相关系数
Table 2. The quantitative ions and qualitative ions of GC-SIS-MS and correlation coefficient of standard work curve for 25 compounds
化合物 时间窗口
(min)定量离子
(m/z)定性离子
(m/z)相关系数
(r2)α-HCH 10.00~10.51 217+219 183,217,219 0.999 六氯苯 284 284,286,288 0.998 β-HCH 10.51~11.41 217+219 183,217,219 0.998 γ-HCH 217+219 183,217,219 0.998 PCB 15 222 152,222,224 0.999 δ-HCH 217+219 183,217,219 0.994 PCB 28 11.41~12.08 256 186,256,258 0.997 七氯 272 235,237,272 0.999 PCB 52 12.08~12.43 292 220.222,292,294 0.998 艾氏剂 12.43~12.85 263 261,263,265，291,293, 0.999 环氧七氯 12.85~13.82 353 353,355,357 0.999 反式-氯丹 13.82~14.86 375 373,375,377 0.997 PCB 101 326 254,256,326,328 1.000 顺式-氯丹 13.82~14.86 375 373,375,377 0.999 p,p'-DDE 14.86~15.81 246 246,248316,318 0.999 狄氏剂 263 235,237, 263,265 0.997 异狄氏剂 15.81~17.21 263 245,261,263,265 0.997 PCB 118 326 254,256,326, 328 0.999 p,p'-DDD 237 165,235,237 0.999 o,p'-DDT 237 165,235,237 0.996 PCB 153 17.21~20.15 360 290,292,360，362 0.999 p,p'-DDT 237 165,235,237 0.999 PCB 138 360 290,292,360，362 1.000 PCB 180 20.15~22.71 396 359,361,394,396 0.998 灭蚁灵 22.71~23.98 272 235,237,272,274 0.999 替代物 时间窗口
(min)定量离子
(m/z)定性离子
(m/z)相关系数
(r2)TCMX
(2,4,5,6-
四氯间二甲苯)9.00~10.00 242 207,209,242,244 - PCB 103 12.85~13.82 326 254,256,326,328 - PCB 204 20.15~22.71 358 358,360,428,432 -
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表 3 精密度、准确度及方法检出限
Table 3. The precision, accuracy and detection limits of the method
化合物 低添加浓度水平(n=7) 高添加浓度水平(n=7) 检出限
(ng/g)平均回收率
(%)RSD
(%)平均回收率
(%)RSD
(%)α-HCH 84.3 11.9 86.1 8.0 3.48 六氯苯 98.1 10.2 83.9 7.1 3.46 β-HCH 102.0 4.3 98.1 11.1 1.52 γ-HCH 85.7 6.8 88.1 10.0 2.01 PCB 15 93.7 6.5 98.6 7.6 1.06 δ-HCH 90.1 11.0 90.9 9.8 3.40 PCB 28 105.1 12.0 93.6 6.8 2.18 七氯 95.5 7.6 88.8 8.4 2.51 PCB 52 101.5 9.4 89.5 7.4 1.66 艾氏剂 99.3 7.1 81.6 3.2 2.45 环氧七氯 108.5 9.0 91.3 7.0 3.39 反式-氯丹 113.4 4.7 91.5 9.5 1.84 PCB 101 106.6 9.9 95.9 7.1 1.84 顺式-氯丹 106.8 5.8 91.6 6.7 2.14 p,p'-DDE 95.7 7.6 96.0 10.9 2.53 狄氏剂 92.5 4.5 96.9 9.8 3.59 异狄氏剂 106.3 3.0 88.2 5.8 2.24 PCB 118 98.5 6.0 101.8 7.1 1.02 p,p'-DDD 90.4 9.5 95.3 12.1 2.98 o,p'-DDT 100.0 9.6 92.9 4.5 3.35 PCB 153 101.7 6.4 94.3 7.5 1.13 p,p'-DDT 95.6 6.2 96.8 9.3 2.04 PCB 138 92.6 10.5 96.5 9.7 1.68 PCB 180 93.2 7.2 96.9 11.8 1.16 灭蚁灵 100.4 3.7 91.3 9.7 1.29 替代物 平均回收率
(%)RSD
(%)平均回收率
(%)RSD
(%)- TCMX 74.3 4.1 73.3 4.2 - PCB 103 103.3 4.2 86.9 7.2 - PCB 204 104.9 5.7 94.0 5.8 -
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表 4 实际样品检测结果
Table 4. Analysis results of actual samples
化合物 含量(ng/g) 鲤鱼 虾 牛肉 猪肉 六氯苯 5.00 1.26 - - p,p'-DDE 15.36 2.97 4.76 3.57 p,p'-DDD 6.31 - - - o,p'-DDT 4.37 - - - p,p'-DDT 5.61 - - - 替代物 回收率(%) 2,4,5,6-四氯间二甲苯 80.3 83.2 73.0 79.9 PCB 103 93.0 95.7 107.1 97.9 PCB 204 105.9 100.4 107.9 99.5
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