雌激素和孕激素在松花江水体及给水处理单元的分布规律

发布时间：2018-03-22 15:14

本文选题：松花江　切入点：雌激素　出处：《哈尔滨工业大学》2014年硕士论文　论文类型：学位论文

【摘要】：雌激素和孕激素是重要的内分泌干扰物，这类物质在环境中极其微量的存在都有可能对生态系统及人类健康造成潜在危害。研究这类物质在松花江哈尔滨段的分布情况，能够帮助全面了解松花江的水质状况，为相关研究和决策提供数据支持。本文利用在线固相萃取技术，建立了水中雌激素和孕激素类物质的UPLC-MS/MS分析方法，该方法对各雌激素和孕激素的检测限为0.1~1.0ng/L，满足痕量分析的要求。通过对松花江哈尔滨段的水体进行采样分析，发现该江段内雌激素E1、E2、E3和EE2的浓度范围分别为ND~25.5ng/L、 ND~9ng/L、 ND~19.5ng/L和ND~8.7ng/L，孕激素CPA、LNG的浓度范围分别为ND~12.7ng/L、ND~3.4ng/L，孕激素GES在所有水样中未检出。雌激素和孕激素总浓度在该江段内呈现江南高于江北，下游高于上游，冰雪消融期和丰水期高于枯水期的规律。在人类活动比较集中的采样点以及河沟汇入口下游的采样点，雌激素和孕激素的浓度有所增加。通过对比E1和E2的浓度之比，推测水中雌激素的存在与人类的活动有很大关系。生态风险评价表明，松花江哈尔滨段的水体中E1、E2、E3和LNG的存在具有一定的生态风险，需要采取相关措施。雌激素活性分析同样表明，该江段内大部分采样点的EEQ值高于预测无影响浓度，需要采取相关措施加以控制。考察了水厂常规处理工艺以及给水深度处理中试系统对水中雌、孕激素类污染物质的去除效果。结果表明，常规水处理单元对水中雌、孕激素的去除效果不佳。混凝沉淀单元对雌、孕激素的去除率不到40%，过滤对雌、孕激素的去除率不到20%，且两个单元都出现了出水浓度高于进水的情况。臭氧对雌、孕激素有很好的去除效果，且臭氧对雌、孕激素的去除效果与臭氧投量有关，也与雌、孕激素初始浓度有关。臭氧投量为1.5~3.0mg/L时，雌激素和孕激素的去除率为90%~97%。雌激素和孕激素初始浓度较低时，去除率略有下降。通过对臭氧氧化产物进行分析，发现臭氧并没有将目标污染物完全矿化。生物活性炭单元和超滤单元单独使用时对水中雌、孕激素的去除率低于臭氧单元。其中生物活性炭单元对E2和E3的去除率在70%左右，对E1和EE2的去除率不到20%，超滤单元对各雌激素和孕激素的去除率在65%~85%之间。高级氧化—吸附—超滤膜过滤组合工艺对雌激素和孕激素具有很好的去除效果，出水中基本没有检出雌激素和孕激素，说明该工艺能很好地保证出水水质。
[Abstract]:Estrogen and progesterone are important endocrine disruptors, and the presence of these substances in the environment may cause potential harm to ecosystem and human health. Can help to understand the water quality of Songhua River, and provide data support for related research and decision. An on-line solid phase extraction (SPE) method for the determination of estrogen and progesterone in water by UPLC-MS/MS has been developed. The detection limit of each estrogen and progesterone is 0.1 ~ 1.0ng / L, which meets the requirements of trace analysis. By sampling and analyzing the water body in Harbin section of Songhua River, It was found that the concentration range of estrogen E _ (1) E _ (2) E _ (2) E _ (3) and E _ (2) E _ (3) and E _ (2) E _ (3) and E _ (2) E _ (3) and E _ (2) E _ (2) E _ (3) and E _ (2) E _ (3) and E _ (2) E _ (3) and E _ (2) E _ (3) and E _ (2) E _ (3) and E _ (2) E _ (3) and E _ (2) E _ (2) E _ (3) and E _ (2) E _ (2) E _ (3) and E _ (2) N. The regularity that the downstream is higher than the upstream, and the ice and snow melting period and the high water season are higher than the dry season. The concentrations of estrogen and progesterone have been increased. By comparing the concentration of E1 and E2, it is inferred that the existence of estrogen in water is closely related to human activities. The ecological risk assessment shows that the existence of E1C E2E3 and LNG in Harbin section of Songhua River has certain ecological risks, and some relevant measures should be taken. The analysis of estrogenic activity also shows that E1C E2E3 and E2E3 in Harbin reach of Songhua River have some ecological risks. The EEQ value of most sampling points in this section is higher than that of predicted unaffected concentration, and relevant measures should be taken to control it. The removal efficiency of female and progesterone pollutants in water by conventional treatment process and advanced water treatment system was investigated. The removal rate of progesterone in coagulation sedimentation unit was less than 40% for female, and less than 20% for female in filtration, and the effluent concentration was higher than that in influent in both units. Ozone has a good effect on the removal of estrogen and progesterone, and the removal effect of ozone on estrogen and progesterone is related to the amount of ozone, and also to the initial concentration of estrogen and progesterone. The removal rate of estrogen and progesterone is 90%. When the initial concentration of estrogen and progesterone is low, the removal rate decreases slightly. Through the analysis of ozonation products, it is found that ozone does not completely mineralize the target pollutant. The removal rate of progesterone in water by biological activated carbon unit and ultrafiltration unit alone was lower than that of ozone unit, and the removal rate of E2 and E3 by biological activated carbon unit was about 70%. The removal rate of E1 and EE2 was less than 20%, and the removal rate of estrogen and progesterone by ultrafiltration unit was between 65% and 85%. Estrogen and progesterone were not detected in the effluent, indicating that the process can ensure the quality of the effluent.
【学位授予单位】：哈尔滨工业大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：TU991.2;X143

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