高效液相色谱-二极管紫外阵列/荧光串联测定雌激素的方法及污水处理厂对雌激素的去除特性

建立了高效液相色谱-二极管紫外阵列（PDA）/荧光（FLD）串联法测定雌酮（E1）、雌二醇（E2）、乙炔雌二醇（EE2）、雌三醇（E3）和双酚A（BPA）5种典型雌激素的方法，并利用该方法测定了某城市污水处理厂5种雌激素的分布情况及去除特性。研究结果表明，二极管紫外阵列/荧光检测器对 5 种雌激素的检出限在4.30~9.54 μg·L-1之间，定量限在12.90~28.62 μg·L-1之间。5 种雌激素日内精密度的相对标准偏差小于6.86%，日间精密度相对标准偏差小于9.47%；对100、500和1 000 ng·L-13个浓度的 5 种雌激素经富集浓缩后测定的加标回收率在 62.8%~96.0% 之间，方法符合痕量分析要求。利用该方法对城市某污水处理厂雌激素的含量进行测定，结果表明污水处理厂进水中5种雌激素的总浓度为3 073.1 ng·L-1，其中雌三醇（E3）的浓度最大，占 5 种雌激素总量的40.1%。出水中 5 种雌激素的总浓度为124.7 ng·L-1，5 种雌激素的总去除率为 95.9%。不同处理单元对雌激素的去除效率存在明显差异，生物处理单元对 5 种雌激素的去除效果最好，5 种雌激素的去除率在73.6%~96.6%之间；一级处理工艺和消毒工艺对雌激素的去除效果较差。

High performance liquid chromatography coupling with photo-diode array and fluorescence detector for sensitive analysis of environmental endocrine disruptors (EDCs) in wastewater

A sensitive method combining high-performance liquid chromatography and a photo-diode array and fluorescence detector was developed to quantitatively analyze five environmental endocrine disruptors (EDCs): estrone (E1), estradiol (E2), ethinyl estradiol (EE2), estriol (E3), and bisphenol A (BPA). The LOD of the five EDCs ranged from 4.30 μg·L-1 to 9.54 μg·L-1 and the LOQ ranged from 12.90 μg·L-1 to 28.62 μg·L-1. The intra- and interday precision were lower than 6.86% and 9.47%, respectively. The recovery of all compounds varied from 62.8% to 96.0%. This method can meet the requirements of trace analysis. Wastewater samples collected from wastewater treatment plants (WWTP) were tested according to this method. The results indicated that the total concentrations of five EDCs were 3 073.1 ng·L-1 in the influent of the WWTP. Among the five EDCs, the content of E3 was highest, accounting for 40.1% of total EDCs. Throughout the wastewater treatment process, different treatment units exhibited different removal efficiencies for the EDCs. The biological treatment stage appeared to be necessary for the effective removal of EDCs. The removal efficiencies of EDCs ranged from 73.6% to 96.6% in the biological treatment units. The final sedimentation and disinfection for EDC removal were minor.