色谱2024，Vol.42Issue(9)：866-874,9.DOI:10.3724/SP.J.1123.2023.11014
固相萃取-超高效液相色谱-串联质谱法同时测定水中61种激素
Simultaneous determination of 61 hormones in water by solid phase extraction-ultra performance liquid chromatography-tandem mass spectrometry
摘要
Abstract
Concerns over the emergence of steroid hormones as pollutants in water have grown.Steroid hormone compounds present challenges in the simultaneous detection of total residual hormones owing to their analogous structures and diverse types.In this study,we es-tablished a rapid and high-throughput continuous online method based on solid phase extraction(SPE)coupled with ultra performance liquid chromatography-tandem mass spectrometry(UP-LC-MS/MS)for the simultaneous determination of 61 hormone components,including 48 glu-cocorticoids,1 mineralocorticoid,4 androgens,and 8 progesterones,in water. Various SPE columns were investigated to assess their extraction efficiency for enriching and purifying target compounds in a large sample volume(1 L).An HC-C18 SPE column was select-ed because of its superior performance.Acetonitrile was used as a washing solution during SPE to ensure that the majority of the tested substances achieved recoveries exceeding 70%and effectively avoid interferences from water-soluble components. Various C8 and C18 columns were tested,and the optimal HPLC conditions for hormone re-tention were established.We systematically evaluated different UPLC columns and mobile pha-ses,including methanol-water and acetonitrile-water systems with 0.1%formic acid added to the aqueous phase.The optimized UPLC conditions were as follows:BEH C18 column(100 mm×2.1 mm,1.7 μm);column temperature,40℃;flow rate,0.3 mL/min;injection volume,5 μL;mobile phase A:0.1%formic acid aqueous phase;mobile phase B:acetonitrile.Gradient elution was performed as follows:0-0.5 min,30%B;0.5-15.0 min,30%B-75%B;15.0-18.0 min,75%B-98%B;18.0-19.0 min,98%B;19.0-19.1 min,98%B-30%B;19.1-20.0 min,30%B. Both positive-and negative-ion modes were explored in the UPLC-MS/MS experiment to ob-tain the full scan of the parent ions,and positive mode was finally selected for electrospray ion-ization(ESI).Two product ions exhibiting strong signals and minimal interference were select-ed for quantitative and qualitative ion analyses,using an external standard method for quantifi-cation.MS/MS was performed in positive-ion(ESI+)mode with multiple reaction monitoring(MRM)scanning.The MS/MS parameters were as follows:atomizing gas pressure,379 kPa;curtain air pressure,241 kPa;spray voltage,5 500 V;desolvation temperature,550℃;colli-sion exit voltage(CXP),13 V;intake voltage(EP),10 V;and residence time of each ion pair,0.5 ms.Other instrument settings,such as the collision energy and declustering voltage,were also optimized. The 61 hormones exhibited excellent linear relationships within their corresponding concen-tration ranges,with correlation coefficients greater than 0.99.The method detection limits(MDLs)were in the range of 0.05-1.50 ng/L.The average recoveries of the 61 hormones across three spiked levels ranged from 62.3%to 125.2%,with relative standard deviations(RSDs,n=6)of 1.1%-10.5%. Using this method,we successfully detected 10 hormone components(cortisone,fluticasone propionate,ciclesonide,betamethasone dipropionate,clobetasone butyrate,diflucortolone va-lerate,halobetasol propionate,isoflupredone,difluprednate,and hydroxyprogesterone ca-proate)in various surface water and groundwater samples collected from the Taihu Basin region. The SPE-UPLC-MS/MS method presented in this paper is simple,highly sensitivity,and ex-ceptionally accurate.Thus,it exhibits promising potential for tracing targeted hormone residues in water and will be of great value in monitoring and ensuring water safety.Finally,a regional analysis was conducted on the hormone levels in water,and suggestions were made for the tar-geted treatment of hormone residues in future sewage treatment processes.关键词
超高效液相色谱-串联质谱/固相萃取/激素/水Key words
ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS)/solid phase extraction(SPE)/hormone/water分类
化学化工引用本文复制引用
陈月琴,马明,徐红丹,潘春燕..固相萃取-超高效液相色谱-串联质谱法同时测定水中61种激素[J].色谱,2024,42(9):866-874,9.基金项目
国家自然科学基金青年科学基金项目(82003975) （82003975）
无锡市卫生健康委科研项目面上项目(M202170) （M202170）
无锡市职业教育创新发展专项课题(9202014).National Natural Science Foundation Youth Science Foundation Project(No.82003975) （9202014）
General Research Project of Wuxi Municipal Health Commission(No.M202170) （No.M202170）
Wuxi Vocational Education Innovation and Development Special Project(No.9202014). （No.9202014）
