集约化奶牛场沼液沼灌区类固醇雌激素定量分析  

Detection and variation of steroidal estrogens in intensive dairy farm marsh irrigation areas

作　　者：余薇薇 孙尉哲 杜邦昊 杨威 蒋晖 唐川东[2] 杨硕 谢明原 唐竟竞 Yu Weiwei;Sun Weizhe;Du Banghao;Yang Wei;Jiang Hui;Tang Chuandong;Yang Shuo;Xie Mingyuan;Tang Jingjing(School of River and Ocean Engineering,Chongqing Jiaotong University,Key Laboratory of Hydraulic and Waterway Engineering of the Ministry of Education,Chongqing 400074,China;Western Branch of China Academy of Urban Planning and Design,Chongqing 401121,China)

机构地区：[1]重庆交通大学河海学院水利水运工程教育部重点实验室,重庆400074 [2]中国城市规划设计研究院西部分院,重庆401121

出　　处：《农业工程学报》2021年第5期241-247,共7页Transactions of the Chinese Society of Agricultural Engineering

基　　金：国家自然科学基金项目(51608079);重庆市研究生教育教学改革研究项目(yig182028);重庆市大学生创新创业训练(S202010618007);重庆市教委科学技术研究项目(KJ1600541);重庆市基础研究与前沿探索项目(cstc2018jcyjAX0322)。

摘　　要：随着集约化奶牛场的发展,其产生的类固醇雌激素已成为新的环境污染源,因此建立沼液及土壤复杂组分中类固醇雌激素定量分析方法,考察不同季节类固醇雌激素含量变化十分必要。该研究对奶牛场沼灌区的沼液及土壤中5种类固醇雌激素(雌酮、17α-雌二醇、17β-雌二醇、雌三醇、雌酮硫酸钠)建立了固相萃取-液相色谱串联两级质谱(SPE-LC-MS/MS)分析方法。针对沼液及土壤复杂基质特点,分别建立二者样品前处理方法,处理后样品采用电喷雾离子源负离子模式多反应监测分析。结果表明,检测方法线性关系良好,检出限为0.09~0.39ng/L,定量限为0.24~1.18 ng/L,回收率范围为74.56%~91.84%,该法可有效用于沼液及土壤中痕量雌激素的检测。通过对沼液、沼灌区土壤样品检测发现,雌酮、17α-雌二醇与17β-雌二醇检出频率及浓度较高,而雌三醇与雌酮硫酸钠检出频率及浓度较低。同时得到沼液出水及土壤纵深雌激素的含量分布,厌氧池出水中各物质浓度雌酮>17β-雌二醇>17α-雌二醇>雌酮硫酸钠>雌三醇;好氧池出水中17β-雌二醇>17α-雌二醇>雌酮>雌酮硫酸钠>雌三醇;不同纵深土壤中均为17β-雌二醇>雌酮>17α-雌二醇>雌酮硫酸钠,未检测出雌三醇;沼液中雌激素浓度随季节温度变化,土壤中随季节性降低。试验结果为研究复杂基质中雌激素检测和分布提供一定理论依据和数据支撑。Steroidal estrogen production has become an emerging source of environmental pollution,due to the huge demand for meat products as the rapid development of intensive farms.Therefore,it is necessary to establish quantitative analysis for steroidal estrogens in complex fractions of digestate and soil,in order to explore the changes of steroidal estrogens in different seasons.In this study,a solid phase extraction-liquid chromatography tandem mass spectrometry(SPE-LC-MS/MS)was developed for the analysis of five steroidal estrogens(estrone,17α-estradiol,17β-estradiol,estriol,and sodium estrone sulfate)in digestate and soil from the methane irrigation area of dairy farms.Sample pretreatments were made on the complex matrix characteristics of methane and soil.The treated samples were analyzed by multi-response monitoring in the negative ion mode with an electrospray ionization source.The results showed that there was good linearity of the assay,where the detection limits were 0.09-0.39 ng/L,the quantification limits were 0.24-1.18 ng/L,and the recoveries ranged from 74.56%to 91.84%.This technology was effectively used for the determination of trace estrogens in methane and soil.The frequency and concentration of estrone,17α-estradiol,and 17β-estradiol were higher in the methane irrigation area soil samples from dairy farms,while the frequency and concentration of estriol and sodium estrone sulfate were lower.The average concentrations of estrone and 17α-estradiol increased from summer to winter,indicating a weak degradation of estrogens,due to the lower temperature and lower activity of anaerobic bacteria.The concentration of 17β-E2 showed a decreasing trend,indicating that 17β-E2 was more easily converted under anaerobic conditions.In the anaerobic tank effluent,the concentration of each substance was ranked in order:estrone,17β-estradiol,17α-estradiol,estrone sodium sulfate>estriol in the anaerobic pond effluent,whereas,in the aerobic pond effluent:17β-estradiol,17α-estradiol,estrone,estrone sodium sulfate

关 键 词：沼液 土壤 液质联用 沼灌区类固醇雌激素 固相萃取 复杂基质 

分 类 号：X713[环境科学与工程—环境工程]