Determination of Steroid Estrogens in Different Water Samples Using SPE-derivatization Coupled with GC-MS
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摘要: 针对地下水及地表水体样品中痕量类固醇雌激素（SEs）污染问题，本文建立了固相萃取-衍生化-气相色谱-质谱联用（SPE-GC-MS）同时测定不同水体中5种SEs：雌酮（E1）、17α-雌二醇（17α-E2）、17β-雌二醇（17β-E2）、17α-乙炔基雌二醇（EE2）、雌三醇（E3）的分析检测方法。通过优化固相萃取过程和衍生化条件以及复杂样品的二次净化过程，发现用Oasis HLB柱萃取，用乙酸乙酯洗脱，40℃条件衍生化20 min可以达到最佳效果，并且经甲醇活化过的Generik NAX柱对复杂样品的二次净化效果较好。本方法对E1、17α-E2、17β-E2和EE2、E3检测的线性范围分别为5~1000 ng/L和10~1000 ng/L；方法检出限和定量限分别为2~3 ng/L和6.5~10 ng/L；对水样的加标回收率范围为80%~120%；该方法测定SEs峰面积的日内相对标准偏差为6.8%~10%。应用此方法对鱼塘水、河水、地下水、污水处理厂二级出水进行了SEs污染水平检测，结果表明该检测技术可以有效应用于不同水质地表及地下水体类固醇雌激素化学风险识别与评估。Abstract: In order to solve trace-level steroid estrogen pollution in groundwater and surface water, a SPE-GC-MS approach to determine five steroid estrogens (SEs), E1, 17α-E2, 17β-E2, EE2 and E3, by optimizing of solid phase extraction (SPE), derivatization conditions and the secondary purification process of complex samples has been developed. The results show that Oasis HLB column, ethyl acetate elution and derivatizing at 40℃ for 20 min can achieve the best results for extraction. Moreover, the Generik NAX column activated by methyl is suitable for the secondary purification of complex samples. The linear ranges of E1, 17α-E2, and 17β-E2 are 5-1000 ng/L, whereas those of EE2 and E3 are 10-1000 ng/L. The detection and quantitation limits are 2-3 ng/L and 6.5-10 ng/L, respectively. The standard solution added recoveries of water samples range from 80% to 120%. The relative standard deviations of daily peak areas in the SEs determination range from 6.8% to 10%. This method was used to determine the SEs pollution levels of waters from pond, river, groundwater and sewage treatment plant effluent and results show that this detection technique can be effectively applied to the identification and evaluation of estrogen risk in surface water and groundwater samples.
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表 1 目标SEs的保留时间及其特征离子
Table 1. Retention times and characteristic ions of the target steroid estrogens
化合物 保留时间
(min)定性离子
(m/z)定量离子
(m/z)E1 23.24 342，218，257 342 17α-E2 22.81 285，326，416 285 17β-E2 23.40 285，326，416 285 17β-E2-d4 23.40 285，129，416 285 EE2 25.19 425，232，285 425 E3 26.56 311，386 311 
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表 2 衍生化时间和温度对目标化合物回收率的影响
Table 2. The effects of derivatization time and temperature on recoveries of the target compounds
化合物 回收率(%)±标准偏差(%) 20℃ 40℃ 60℃ 80℃ 40℃ 60℃ 80℃ 40℃ 60℃ 80℃ 20 min 40 min 60 min E1 88.8±2.8 98.4±2.9 101.2±3.4 101.3±3.1 100.2±3.7 103.1±3.9 96.7±5.0 105.5±3.4 105.6±6.1 108.1±4.3 17α-E2 90.7±2.9 98.2±2.9 95.8±7.0 98.2±5.0 99.3±3.2 99.2±4.5 93.9±8.6 100±3.4 102.8±3.6 99.1±5.8 17β-E2 90.5±7.0 98.8±5.0 98.1±3.4 98.5±2.6 96.1±6.4 98.9±4.5 93.8±5.8 99.8±4.4 103±8.2 100.6±3.1 EE2 86.8±4.3 99.9±5.2 99.8±5.4 96.5±8.8 101.3±3.3 97±7.6 95.9±8.8 108±4.2 100.6±7.0 100.3±8.4 E3 88.7±6.1 102.3±2.4 103.4±4.1 109.5±5.3 103.4±2.8 111.8±5.3 86.8±8.4 111.8±5.3 109.4±4.1 109.7±4.8
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表 3 五种类固醇雌激素的线性方程、相关系数、线性范围、检出限和定量限
Table 3. Linear equation, correlation coefficient, linear range, LOD and LOQ of five estrogens
化合物回归方程 相关系数
(R2)线性范围
(ng/L)检出限
(S/N=3，ng/L)定量限
(S/N=10，ng/L)E1 Y=-3987.67+1312.43X 0.9984 5~1000 2 6.5 17-α E2 Y=-32075.1+1541.75X 0.9982 5~1000 2 6.5 17-β E2 Y=-36461.6+1694.59X 0.9981 5~1000 2 6.5 EE2 Y=-7596.5+291.442X 0.9963 10~1000 3 10 E3 Y=-5898.03+425.589X 0.9986 10~1000 3 10
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