环境样品中典型类固醇激素分析方法研究及应用

发布时间：2018-05-08 13:36

本文选题：类固醇激素 + 超高效液相色谱-串联质谱　；参考：《贵州大学》2017年硕士论文

【摘要】：类固醇激素作为一类典型的内分泌干扰物,因其在环境中普遍存在和较强的内分泌干扰效应,已经成为继臭氧层破坏、全球气候变暖之后的第三大环境问题。本文以环境中共存、检出率较高、毒性较大的雌酮(E1)、雌二醇(E2)、雌三醇(E3)、乙炔雌二醇(EE2)、睾酮(T)、雄烯二酮(ADD)、勃地酮(Bold)、诺龙(NDL)、孕酮(Pro)、醋酸甲地孕酮(MA)共10种典型类固醇激素为研究对象,对这10种类固醇激素化合物在质谱中的断裂方式和特征离子的结构式进行了理论推导,建立了超高效液相色谱串联质谱法(UPLC-MS/MS)和高效液相色谱串联质谱法(HPLC-MS/MS)同时测定环境水体中10种目标化合物的分析方法。确定SPE-ESI-UPLC-MS/MS测定10种典型类固醇激素的分析方法,采用Agilent Poroshell 120 Bonus-RP(100×2.1 mm,2.7μm)色谱柱,以含0.1%氨水的超纯水和乙腈作为流动相梯度洗脱,流速为0.5 mL/min,柱温为30℃,在优化后的色谱及质谱参数条件下对样品进行分析,在5.0 min内即可完成10种目标化合物的分析,方法在5个浓度范围内均具有良好的线性关系(R20.99)。将分析方法运用于经Oasis HLB固相萃取柱富集的70个地下水样品,方法检出限(LOD)在0.40~1.50 ng/L之间,检测到至少有一种类固醇激素化合物样品占所有水样的22.8%,T和E2是检出率最高的分析物。该方法也成功运用于经Oasis HLB和Silica固相萃取柱富集后的垃圾填埋场渗滤液,方法检出限(LOD)在1.45~3.01 ng/L之间,渗滤液中共检出7种目标化合物总浓度高达300.45 ng/L,经处理后出水中总浓度为22.10 ng/L,检出的目标物质的去除率都在78.71%以上。该方法可在同一样品中同时检测多种类固醇激素,检测效率与高效液相色谱串联质谱法相比提高了近3倍,提高了工作效率、降低了分析成本,可用于日常水体样品中类固醇激素残留及污染的检验,对污水排放的监控具有重大意义。对比已有的文献,目前很少有一次进样就能同时分析雌激素、雄激素和孕激素的分析方法。
[Abstract]:Steroid hormone, as a typical endocrine disruptor, has become the third major environmental problem following the ozone layer destruction and global warming because of its widespread and strong endocrine disrupting effects in the environment. In this paper, a high detection rate, high toxic estrone (E1), estradiol (E2), female three alcohol (E3), and B in the environment are coexisting in the environment. Estradiol (EE2), testosterone (T), steronene two ketone (ADD), bodione (Bold), NDL, progesterone (Pro), and megestrol acetate (MA), a total of 10 typical steroid hormones, were studied. The structural formula of the 10 steroid hormone compounds in the mass spectrum and the structural formula of the characteristic ions were theoretically derived, and a super high performance liquid chromatography series was established. Simultaneous determination of 10 target compounds in environmental water by tandem mass spectrometry (UPLC-MS/MS) and high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). The analytical method for the determination of 10 typical steroid hormones by SPE-ESI-UPLC-MS/MS was determined, and Agilent Poroshell 120 Bonus-RP (100 x 2.1 mm, 2.7 u m) column was used for the super purity of 0.1% ammonia. Water and acetonitrile are washed as mobile phase gradient, the flow rate is 0.5 mL/min, the column temperature is 30 C. The samples are analyzed under the optimized parameters of chromatography and mass spectrometry. The analysis of 10 target compounds can be completed within 5 min. The method has a good linear relationship (R20.99) within the 5 concentration range. The analytical method is applied to Oasis HL. 70 samples of groundwater were enriched by B solid phase extraction column. The detection limit (LOD) was between 0.40~1.50 ng/L and at least one steroid hormone compound was found to account for 22.8% of all water samples. T and E2 were the highest detection rates. The method was also successfully applied to landfill site infiltration after Oasis HLB and Silica solid phase extraction column. In the filtrate, the detection limit (LOD) is between 1.45~3.01 and ng/L. The total concentration of 7 target compounds is up to 300.45 ng/L, and the total concentration of the effluent is 22.10 ng/L after treatment. The removal rate of the target substances is above 78.71%. The method can detect a variety of steroid hormones in the same sample and detect the efficiency and efficiency. The liquid chromatography tandem mass spectrometry (GC MS) has been improved by nearly 3 times, increasing the efficiency and reducing the cost of analysis. It can be used to test the steroid hormone residues and pollution in the daily water samples. It is of great significance to the monitoring of the sewage discharge. Analysis of hormone.

【学位授予单位】：贵州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.63;X832

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