UV体系中3种微量类固醇雌激素的竞争降解及同趋转化

采用UV体系(UV、UV/H2O2和UV/H2O2/TiO2)降解水中同时存在的3种微量类固醇雌激素雌酮(E1)、17-β雌二醇(E2)和17-α乙炔基雌二醇(EE2),结果表明,降解过程均符合一级反应动力学,通过不同UV系统对比发现,关键因素对混合污染降解的影响顺序为H2O2>光强>TiO2.E1光解特性良好,在混合基质中可优势降解;E2和EE2直接光解效果较差,优劣顺序受到光强的影响,光强升高EE2略占优势.H2O2和催化剂TiO2的投加可提高3种物质的降解效果及降解速率常数,但竞争条件下E2和EE2的去除率提高有限.E1,E2和EE2的光化学降解过程具有相似的转化趋势,均可生成与E1结构类似的副产物.     

Effect of Light on Biodegradation of Estrone, 17β‐Estradiol,and 17α‐Ethinylestradiol in Stream Sediment

Biodegradation of [A‐ring ¹⁴C] Estrone (E1), 17β‐estradiol (E2), and 17α‐ethinylestradiol (EE2) to ¹⁴CO₂ was investigated under light and dark conditions in microcosms containing epilithon or sediment collected from Boulder Creek, Colorado. Mineralization of the estrogen A‐ring was observed in all sediment treatments, but not epilithon treatments. No difference in net mineralization between light and dark treatments was observed for ¹⁴C‐E2. Net mineralization of ¹⁴C‐E1 and ¹⁴C‐EE2 was enhanced in light treatments. Extents of ¹⁴CO₂ accumulation and rates of mineralization were significantly greater for E2 than E1 under dark conditions, but were comparable under light conditions. These results indicate substantial differences in the uptake and metabolism of E1 and E2 in the environment and suggest biorecalcitrance of E1 relative to E2 in light‐limited environments. The extent of ¹⁴CO₂ accumulation and rate of mineralization for EE2 in dark treatments were less than half of that observed for E2 and generally lower than for E1, consistent with previous reports of EE2 biorecalcitrance. However, ¹⁴CO₂ accumulation and rates of mineralization were comparable for EE2, E2, and E1 under light conditions. These results indicate photoactivation and/or phototransformation/photodegradation processes can substantially enhance heterotrophic biodegradation of estrogens in sunlit environments and may play an important role in estrogen transport and attenuation.     

基于响应面法优化污水中雌酮的固相萃取条件

为提高污水样品中雌酮(E1)的固相萃取回收率,应用响应面法(RSM)对影响固相萃取的关键参数进行了优化,建立了固相萃取回收率的二次多项式模型,分析了模型有效性和因子交互作用,确定了最佳固相萃取条件;并对实际污水处理厂进、出水样品中的E1进行了固相萃取和浓度检测。结果表明,影响E1固相萃取回收率的因素重要性依次为:洗脱体积>进样速率>洗脱速率。最佳固相萃取条件为:洗脱体积11.15 mL;进样速率10.62mL/min;洗脱速率4.15 mL/min;在此条件下,预测回收率最大可达81.82%。分别采用SBR、氧化沟和A2/O工艺的3座污水处理厂进水E1浓度分别为36.8⁸9.0、24.189.0、24.1²8.4和27.828.4和27.8⁵8.1 ng/L,对应去除率分别为62.8%58.1 ng/L,对应去除率分别为62.8%⁷7.0%、49.3%77.0%、49.3%⁶3.6%和56.1%63.6%和56.1%⁷4.9%。3种污水处理工艺对E1均有一定的去除能力,但出水中残余E1仍远超过预测无效应浓度。     

畜禽粪便改良土壤中E1和E2自然降解的影响因素

研究了E1(雌酮)和E2(17β-雌二醇)在牛粪、猪粪和鸡粪改良土壤自然降解过程中灭菌、光照和温度的影响以及泰乐菌素与吐温80的复合影响. 对比灭菌和未灭菌环境中E1和E2的降解效果表明,灭菌能显著抑制E1的降解,而对E2的降解影响不显著;对比光照和黑暗环境中E1和E2的降解可知,光照对二者的影响不大;在前2种条件下,E1和E2的降解效果(以去除率计)不受粪便类型的影响. 在0～35 ℃,雌激素E1和E2的去除率随温度的升高呈增大趋势,其中E1在牛粪改良土壤中的去除率由1.21%增至58.04%,E2的去除率由1.24%增至48.93%;环境中共存的吐温80能促进E1和E2的降解,当泰乐菌素与吐温80共存时,可有效促进E2的降解.      

Simultaneous analysis of free and sulfo-conjugated steroid estrogens in artificial urine solution and agricultural soils by high-performance liquid chromatography

A simple and robust analytical method was developed to simultaneously detect and quantify 17β-estradiol (E2), estrone (E1), 17β-estradiol-3-sulphate (E2-3S), and estrone-3-sulphate (E1-3S) in aqueous solutions (calcium chloride and artificial urine solutions) and agricultural soils using high performance liquid chromatography and UV detection. The standards for all four compounds were linear in the range of 0.01 to 1.0 μg mL^?1 (n = 6) and 1.0 to 20 μg mL^?1 (n = 6), respectively, with correlation coefficients > 0.999. The on-column limits of detection at an injection volume of 50 μL and S/N (signal: noise) ratio of 3 were: 9.0 ng mL^?1, 10 ng mL^?1, 5.0 ng mL^?1, and 7.0 ng mL^?1 for E2-3S, E1-3S, E2 and E1, respectively. The limit of detection and quantification in artificial urine solution and CaCl₂ solution was 1.0 ng mL^?1 for all four compounds. Method detection limits for the compounds in the 3 soils ranged from 2 to 2.4 ng g^?1 (E2-3S and E1-3S), and 1.0 to 2.9 ng g^?1 (E2 and E1), respectively.     

污水中基于酶活性分析的硫酸雌酮雌激素效应

在污水处理厂尾水中,雌酮（E1）和硫酸雌酮（E1-3-S）分别是赋存浓度最高的自由态雌激素和结合态雌激素.E1-3-S难以被生物降解且雌激素效应有限,但环境条件适宜时可在芳基硫酸酯酶（AryS）作用下通过水解释放出具有雌激素效应的E1.本论文提出了一种利用AryS活性值和E1-3-S酶促水解动力学参数计算E1-3-S半寿期的方法.根据现场取样分析得到了重庆市某污水处理厂生物处理构筑物内混合液,合流制管道溢流口与尾水受纳水体底泥中在冬、春、夏3个季节的AryS活性值,其均值分别为417.41~941.14,91.55~179.42,28.11~59.64μg对硝基酚/（g·h）.在20℃的实验室条件下,E1-3-S的酶促水解遵循一级动力学模式（P<0.01）,且水解速率K_d与AryS活性呈线性正相关（R²=0.9774）.根据春季的AryS活性数据和实验室条件下E1-3-S水解速率与酶活性的线性回归方程推算,得到了在污水处理厂生物构筑物内、合流制管网溢流口和污水厂尾水排放点附近水体中E1-3-S在对应环境温度条件下通过酶促水解的半寿期分别为33.5,153.0,410.0h.该方法可用于评估硫酸型结合态雌激素在水环境中的雌激素效应释放风险.     

Enzymatic treatment of estrogens and estrogen glucuronide

Natural and synthetic estrogens from sewage treatment systems are suspected to influence the reproductive health of the animals in the rivers.In this article we investigated the enzymatic treatment of three estrogens (estrone,17β-estradiol,and 17α-ethynyletstradiol) by a fungal laccase which oxidize phenolic compounds with dissolved oxygen.The elimination of the estrogenic activities by enzymatic oxidation was demonstrated by medaka vitellogenin assay.In addition,we developed an enzymatic treatment system comprised of β-D-glucuronidase and the laccase for 17β-estradiol 3-(β-D-glucuronide) degradation.The two enzymes eliminated 17β-estradiol 3-(β-D-glucuronide) and the intermediate,17β-estradiol,efficiently.     

漆酶催化氧化雌酮的研究

以空气中氧气为氧化剂,用漆酶催化水中的雌酮,分别研究反应体系的PH值、温度、漆酶浓度、底物浓度对雌酮去除率的影响。结果表明：pH值4—5范围内,pH=4．5时,雌酮的去除率最高,40min后可达91％;适宜温度范围为22．5℃～27．5℃,反应的最适温度为25℃,40min后可达93％;适量增加漆酶浓度可提高反应速度和去除效率,但过量的漆酶会造成酶分子对E1的包裹而降低催化效率;漆酶在较宽的底物浓度范围内对雌酮都有催化效果。