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中文题名:

 畜禽养殖场粪污废弃物及周边环境介质中类固醇激素的分析检测    

姓名:

 杨明    

学科代码:

 083001    

学科专业:

 环境科学    

学生类型:

 硕士    

学位:

 工学硕士    

学位年度:

 2012    

校区:

 北京校区培养    

学院:

 环境学院    

研究方向:

 有机污染化学    

第一导师姓名:

 李艳霞    

第一导师单位:

 北京师范大学环境学院    

提交日期:

 2012-06-05    

答辩日期:

 2012-05-15    

外文题名:

 Analysis of steroid hormones in animal wastes and environmental matrices around animal farm    

中文摘要:
近年来,我国畜禽养殖业发展迅速,规模化集约化程度不断提高,畜禽粪便、尿液及养殖场污水等粪污废弃物带来的污染也越来越严峻。畜禽粪污废弃物中含有的类固醇激素等污染物,是经畜禽体内代谢或者人工合成激素药物的使用而进入畜禽排泄物中,属于环境内分泌干扰物。目前,由环境内分泌干扰物所导致的雌性化、发育缺陷、生殖障碍乃至群体灭绝等一系列问题已经引起了全世界的高度重视。而类固醇激素具有更强的内分泌干扰作用,其主要来源是人或动物的排泄,但是目前有关畜禽等排泄的类固醇激素研究较少。本论文分析了畜禽养殖场粪污废弃物中可能含有的特征内分泌干扰物,以动物体内分泌的类固醇激素或人工合成的激素类药物为主;本论文建立了一套同时检测畜禽养殖场粪污废弃物包括畜禽粪便、尿液和养殖厂污水三种介质中22种天然和人工合成的激素含量的分析方法,包括超声提取、液液萃取、固相HLB柱富集、氨基柱净化及硅胶柱净化,配备高效液相色谱串联质谱进行检测。采用内标法校准,目标物在畜禽粪便、尿液和养殖厂污水上的回收率基本在70 %~120 %之间,标准偏差低于10 %。方法检出限尿液约在3.7~300 ng/L,污水约为1.17~149 ng/L,粪便约在0.32~16 ng/g,适合环境样品的分析。为了解畜禽养殖场粪污废弃物中类固醇激素对养殖场周围环境的污染,针对北京某规模化奶牛场,分析了该场粪污废弃物及其周围污水、表层沉积物和底泥中类固醇激素的含量。研究发现,其粪污废弃物中常见的激素类污染物有E1、αE2、ADD、TTR、ETTR、ECL、PGT、CRL和ZRL,其在尿液中浓度0~1290 ng/L、污水中4.46~2540 ng/L、粪便中0.41~322 ng/g,均为动物体内分泌或者天然的激素;合成激素药物检出较少,只在污水中检出5~10 ng/L的BET,尿液中检出57~114 ng/L的PRE和PREL。畜禽粪污在排放过程中,其所含有的类固醇激素也随之进入环境,在污水、底泥中均检出相关类固醇激素,最高浓度分别达到113 ng/g、2540 ng/L;E1、ADD、ETTR和PGT等常见的激素污染物在水平迁移过程中,浓度并未显著下降,反而会有升高。E1、αE2和PGT等在养殖场周边排污沟地下1 m内沉积物中全部检出,浓度为20~24217 ng/g,这三种激素在垂直分布上表现相似的规律性,说明这三种激素在环境行为上表现出一定的相似性。但对其他激素,在垂直分布上表现出特殊的规律,还需要进一步深入研究。
外文摘要:
In recent years, with rapid development of Chinese animal industry, it has become more and more important to pay attention to the pollution from animal manure, urine and feedlot wastewater. Steroid hormones, a kind of EDCs in the animal wastes, which are excreted by the animal metabolism or added through the synthetic hormone drugs, have attracted more and more attention all over the world becausue of their feminization, suppression, reproductive disorders and other effects. However, it is still lack of research in China.An analytical procedure to determine 22 hormones in animal wastes was established in this study, using liquid chromatography–tandem mass spectrometry (LC-MS-MS) combining with the processes of ultrasonic extraction (ULE), liquid-liquid extraction (LLE), solid-phase extraction (SPE), silica gel cartridge cleanup, amino column cleanup. Most of the target pollutants got good recoveries between 70 %~120 % and standard deviations below 10 %. The detection limits of the method were 3.7~300 ng/L for urine, 1.17~149 ng/L for feedlot wastewater and 0.32~16 ng/g for manure. The method is suitable for the analysis of the environmental samples.A concentrated dairy farm in Beijing was chosen to sample animal manure, urine, feedlot wastewaters and sediments, and then 22 hormones in the wastes were analyzed applying the above method to understand the situation of hormone residues in animal manure and the transporation of the pollutants in the environment. The results showed that E1、αE2、ADD、TTR、ETTR、ECL、PGT、CRL and ZRL were the common hermones in animal wastes and their concentrations in the urine, feedlot wastewater and solid manure were in the range of 0~1290 ng/L, 4.46~2540 ng/L and 0.41~322 ng/g. Compared to the natural hormones, few synthetic hormones could be detected, except 5~10 ng/L BET in feedlot wastewaters, 57~114 ng/L PRE and PREL in urine samples. These hormones discharged into the environment were all measurable in the wastewater and the deep sediments in the effluent ditch of the dairy farm with the highest content of 2540 ng/L and 113 ng/g, respectively. The concentrations of E1、ADD、ETTR and PGT were not clearly attenuated along the transportation process, on the contrary, the concentrations of these pollutants increased in some sample sites. Three hormones of E1、αE2 and PGT were all detectable and ranged from 20 to 24217 ng/g in the deep sediments below 1 m to the surface, moreover, they showed the simlar vertical distribution features, but other hormones did not display the same feature. Hence, it is strongly suggested the further study on the exposure levels of hormones in amimal wastes, moreover, the environmental behaviors of these pollutants in different environmental matrices.
参考文献总数:

 121    

馆藏号:

 硕083001/1209    

开放日期:

 2012-06-05    

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