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。     

复合污染体系中溶解性有机质对雌二醇降解的影响

针对天然水体常见的重金属-有机污染物复合污染问题,探讨水体中普遍存在的溶解性有机质(DOM)对有机污染物降解的影响.采集黄河花园口断面水样,模拟天然水体中DOM质量浓度变化,研究了17β-雌二醇(E2)单一污染体系和Cu(Ⅱ)-E2复合污染体系中DOM对E2降解的影响,用环境扫描电镜、傅里叶变换红外光谱和X射线光电子能谱等手段分析了Cu(Ⅱ)-E2复合污染体系中DOM与Cu(Ⅱ)的作用机理.结果表明:在E2单一污染体系中,DOM明显促进E2降解,E2降解速率常数由0.062 d-1提高到0.430 d-1;在Cu(Ⅱ)-E2复合污染体系中,DOM与Cu(Ⅱ)络合,改变了Cu(Ⅱ)的沉淀形态,降低了Cu(Ⅱ)对微生物的抑制作用,因此,E2降解速率常数由0.006d-1提高到0.030 d-1.     

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.     

我国天然水体中环境雌激素的污染现状及其生态效应研究进展

作为一种新兴的环境污染物,环境中的雌激素存在于各种介质中,并且已经被证实对生物存在危害。结合国内外的研究成果,综述了不同种类的环境雌激素在我国天然水体中污染现状以及环境雌激素对人类、水生生物和微生物的生态效应。在此基础上,对我国未来开展环境雌激素相关研究和如何应对环境雌激素污染问题进行了展望。     

环境雌激素对水生动物的影响研究进展

水环境是环境雌激素的最大储存库。环境雌激素通过食物的传递进入动物体内，类似于雌激素的功能。环境雌激素可导致水生动物性别特征丧失和后代不能繁殖；可引起水蚤性别比例失调，蜕皮率下降，导致软体动物性畸形和超雌性化现象；导致鲤鱼等生殖器畸形，引起鱼类种群生存力和资源量下降。壬酚(NP)、双酚A(BPA)和E2在河水、水生附着生物和底栖生物之间的生物积累与放大倍数在18～1200倍之间，环境激素通过食物链的生物放大作用比通过水体的传递对鱼类等水生生物的危害更大，并且在河流等的枯水期对水生动物的影响更大。文章讨论了环境雌激素的降解与研究前景。     

辽东湾海水中甾体雌激素的检测及生态风险评价

建立了SPE-丹酰化衍生-UPLC-MS/MS海水中雌激素的高灵敏度分析方法,对辽东湾海水中甾体雌激素的浓度水平及分布进行了调查并对其潜在的生态风险进行了评估.结果表明:辽东湾海水样品中检出雌酮,17β-雌二醇,17α-雌二醇,雌三醇和17α-乙炔基雌二醇的浓度分别为(0.714±0.407),(0.089±0.077),(0.009±0.011),(0.008±0.008),(0.001±0.003)ng/L.雌激素浓度在大辽河入海口区域最高,双台子河入海口次之,大凌河及小凌河入海口区域最低.辽东湾海水中的17β-雌二醇等当量浓度(EEQ-E2β)为0.562±0.327ng/L,导致野生梭鱼雌雄同体发生的概率约为0.83%,不足以解释该海域野生梭鱼雌雄同体的高发生率.为了有效管理该海域的环境安全,有必要对原因物质进行进一步解析.     

3种环境雌激素检测和筛选方法的比较

介绍了进行环境雌激素检测和筛选的3种方法:鱼类卵黄蛋白原诱导实验法、重组基因酵母检测法和酵母双杂交法,着重介绍了这3种方法的基本原理、具体操作、适用条件及应用现状.卵黄蛋白原诱导实验是根据正常雄性体内不会含有卵黄蛋白原,环境雌激素能刺激卵生动物肝细胞产生卵黄蛋白原,可通过测定动物体内合成的卵黄蛋白原含量来评价其活性.重组基因酵母法是根据环境雌激素能刺激转化酵母的报告基因表达,以表达的β-半乳糖苷酶的量为依据来判断雌激素活性的大小.酵母双杂交法是在重组基因酵母法的基础上,引入了辅激活蛋白,通过检测雌激素受体和辅激活蛋白之间的相互作用来评价环境雌激素的活性.这3种方法均具有灵敏、简便、快速、经济的优点,同时既可以定性检测又可以定量检测,是目前进行环境中雌激素类物质安全检测与监测的重要手段.     

Endocrine disruptors in the Leça River and nearby Porto Coast (NW Portugal): presence of estrogenic compounds and hypoxic conditions

The Leça River and two beaches close to the north and south margins of the estuary, nowadays an important seaport harbor, show signs of contamination. However, the chemical nature of that contamination is uncertain. Therefore, this study checked for the presence of 11 endocrine disrupting compounds (EDCs) of animal (17β-estradiol and estrone), pharmaceutical (17α-ethynylestradiol), and industrial (alkylphenols, alkylphenol ethoxylates, and bisphenol A) origins in water samples collected from six points at the river gradient and at two sites in the coastline (Atlantic Ocean). Along with the EDCs, evaluated by gas chromatography – mass spectroscopy (GC-MS) during spring, summer, and autumn, physico-chemical parameters were also assessed and particular attention was given to dissolved oxygen (DO) levels. Data showed the presence of high amounts of estrogens (up to 10?ng?L^?1 for estrone) and industrial compounds (up to 2?µg?L^?1 for the nonylphenol ethoxylates) at both river and seacoast. Along with this, clear signs of hypoxia were found in the river (DO??1 at several sampling sites). Taking into account these issues, it was concluded that there are local conditions for the occurrence of endocrine disruption in aquatic animals.     

结合态雌激素的检测方法及污染现状

结合态雌激素是天然雌激素物质的一种重要赋存形态,在环境中可水解为自由态,产生内分泌干扰效应,因此具有潜在的环境风险,并且会影响天然雌激素污染调查和毒性评估的准确性.本文详细探讨了结合态雌激素特定的化学结构对其检测、转化及环境风险等方面的影响,对比分析了目前常用的几类检测方法的优缺点,并初步总结了其在污水处理设施和环境水体中的污染浓度及归趋,以期为我国开展相关研究工作提供参考.     

超高效液相色谱法对塑料玩具中16种环境雌激素的同时测定

含有环境雌激素的塑料玩具及儿童用品有可能被小孩放进口中,如果放置的时间足够长,就会导致雌激素的溶出量超过安全水平,危害儿童的肝脏和肾脏,也可引起儿童性早熟。采用超高效液相色谱法,对塑料玩具中16种环境雌激素类化合物进行检测,建立了超高效液相色谱法同时测定塑料玩具中16种环境雌激素的方法。采用超生萃取法进行提取,使用乙醇作为提取溶剂,在前处理过程中对样品进行无水硫酸钠脱水处理,使杂质显著降低;以乙腈-水为流动相,考察了5种具有不同选择性的UPLC色谱柱对16种环境雌激素的分离效果,结果表明,16种环境雌激素在ACQUITY UPLC BEH C18色谱柱上获得了最为理想的分离效果。该方法的回收率为93.6%～98.8%,RSD为0.5%～2.3%,检出限达0.11～0.76 ng。采用本方法对市售的28种儿童塑料玩具进行了检测,检出的环境雌激素有DEHP、DCHP、DMP、DNOP,其它未检出,其中DEHP、DCHP和DMP检出率相对较高,分别占32.8%、24.5%、19.5%,DNOP则最小,检出率为10.4%。此方法简便、易行、分离度较好,可作为测定塑料玩具中增塑剂环境雌激素类化合物的方法。