地表水中糖皮质激素检测方法的建立和优化及其在北京市清河水体中的应用

发布时间：2018-04-17 15:58

本文选题：糖皮质激素 + 地表水　；参考：《南京师范大学》2015年硕士论文

【摘要】：内分泌干扰物质(EDCs)因其在低浓度下干扰生物机体的内分泌系统正常功能而备受研究者关注,与雌激素相比,种类繁多的糖皮质激素更广泛地应用于人畜医疗,作为一类新型内分泌干扰物质,其直到近几年才被人们关注,目前关于地表水中糖皮质激素的检测方法报道还非常少,对于其在环境中的迁移和毒理效应一直受检测手段的制约。因此建立灵敏、可靠的检测方法是研究地理环境中糖皮质激素环境污染及其生态效应和风险的前提条件和重要基础。本文基于超高效液相色谱串联质谱技术结合固相萃取前处理方法建立了同时检测地表水体中18种糖皮质激素的高效方法；并针对北京部分水体,利用建立的检测方法研究糖皮质激素的环境污染水平和空间分布特征。配制18种糖皮质激素的标准溶液,利用超高效液相色谱质谱联用仪,在多反应选择检测模式(MRM)下,分别对糖皮质激素检测方法的正负离子模式、母离子、定量/定性离子、锥孔电压、碰撞能量等相关质谱采集参数和分离洗脱流动相程序进行优化,最终选择ESI(-)模式,乙酸加合物作为母离子,甲醇/0.1%乙酸水溶液流动相等作为最终条件。通过考察标样添加回收率结果,优化固相萃取前处理方法中的关键环节,包括萃取柱、净化柱和洗脱溶剂的选择等。发现对于地表水样,以亲水亲油平衡(HLB)柱为萃取柱,乙腈/乙酸乙酯(1：1,体积比)为洗脱溶剂就可以满足分析要求,氨基柱等作为净化柱并没有显示显著的净化效果。对检测方法的考察结果表明：方法回收率在65～108%之间,相对标准偏差小于15%,方法检出限除醋酸可的松和醋酸氢化可的松为10 ng/L外,其他物质均在0.1～1.0 ng/L之间,该方法较为简便、经济、高效,能满足日常检测的要求。利用建立的方法对北京清河中的糖皮质激素污染状况进行研究,共检出8种糖皮质激素,浓度水平范围为0.20 ng/L(地塞米松)～476 ng/L(醋酸氢化可的松),其中曲安西龙,曲安奈德,醋酸氢化可的松和丙酸氯倍他索是首次检出；与国内外糖皮质激素污染状况进行比,发现调查水体中糖皮质激素的污染处于相对严重的水平；分析其在清河水体中的空间分布特征,发现糖皮质激素的浓度水平为：清河中游中上游下游；沿岸人口分布密度和土地利用类型是造成这种分布的主要原因。
[Abstract]:Endocrine disrupting substance (EDCs) has attracted the attention of researchers because it interferes with the normal function of endocrine system of organism at low concentration. Compared with estrogen, many kinds of glucocorticoids are widely used in human and animal medicine.As a new type of endocrine disrupting substance, it has not been paid much attention until recent years. At present, there are few reports on the detection of glucocorticoid in surface water.Its migration and toxicological effects in the environment are always restricted by the means of detection.Therefore, the establishment of a sensitive and reliable detection method is the precondition and important basis for studying the environmental pollution of glucocorticoid and its ecological effects and risks in geographical environment.In this paper, an efficient method for simultaneous detection of 18 kinds of glucocorticoids in surface water was established based on ultra-high performance liquid chromatography tandem mass spectrometry combined with solid phase extraction (SPE) pretreatment.The environmental pollution level and spatial distribution of glucocorticoids were studied by using the established detection method.18 standard solutions of glucocorticoids were prepared. The positive and negative ion mode, mother ion, quantitative and qualitative ion of glucocorticoid detection method were determined by super high performance liquid chromatography-mass spectrometer under multi-reaction selective detection mode (MRM).The parameters of mass spectrometry such as cone-hole voltage, collision energy and separation and elution mobile phase program were optimized. Finally, ESI-) mode was selected. Acetic acid adduct was used as the parent ion, and the flow of methanol / 0.1% acetic acid solution was equal as the final condition.By investigating the results of standard sample recovery, the key links of solid-phase extraction (SPE) pretreatment were optimized, including extraction column, purification column and elution solvent selection.It was found that for surface water samples, hydrophilic and lipophilic equilibrium (HLB) column was used as extraction column and acetonitrile / ethyl acetate (1: 1, volume ratio) as elution solvent.The results showed that the recovery rate of the method was between 65 and 108%, and the relative standard deviation was less than 15. The detection limit of the method was only 10 ng/L for cortisone acetate and 10 ng/L for hydrocortisone acetate. The method was simple and convenient.Economic, efficient, can meet the requirements of daily testing.Using the established method to study the status of glucocorticoid pollution in the Qinghe River in Beijing, 8 kinds of glucocorticoids were detected in the concentration range of 0.20 ng / L (dexamethasone, 476 ng / L) (hydrocortisone acetate, triamcinolone acetonide, triamcinolone acetonide, triamcinolone acetonide, triamcinolone acetonide, triamcinolone acetonide).Hydrocortisone acetate and clobetasol propionate were detected for the first time, and compared with the status of glucocorticoid pollution at home and abroad, it was found that the contamination of glucocorticoid in water was relatively serious.It was found that the concentration level of glucocorticoid was the middle and lower reaches of Qinghe River, and the distribution density and land use type of coastal population were the main reasons for the distribution of glucocorticoid.
【学位授予单位】：南京师范大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：X832

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