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。     

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.     

17 β-estradiol and 17 α-ethinylestradiol mineralization in sewage sludge and biosolids

Natural steroid estrogens (e.g., 17 β-estradiol, E2), synthetic steroid estrogens (e.g., 17 α-ethinylestradiol, EE2) and pharmaceutical antibiotics (e.g., ciprofloxacin) are chemicals detected in biosolids and sewage sludges because they partition into the solids fraction during the wastewater treatment process. This research utilized a three-way factorial design (six media × two estrogens × three antibiotic treatments) to quantify cumulative E2 and EE2 mineralization over 133 d (MAX) in a range of sewage sludge and biosolid samples in the presence (4 and 40 mg kg^?1) and absence of ciprofloxacin. The same three-way factorial design was utilized to quantify the impact of the six media, E2 or EE2, and ciprofloxacin on cumulative soil respiration over 133 d (RESP). Minimal ciprofloxacin mineralization was observed (<0.05% over 133 d), but despite its persistence, ciprofloxacin had no significant effect on MAX of E2 or EE2, and, in general, no significant effect on RESP. MAX ranged from 38.38% to 48.44% for E2 but from only 0.72% to 24.27% for EE2 although RESP was relatively similar, ranging from 101.00 to 866.54 mg CO₂ in the presence of E2 and from 69.55 to 893.95 mg CO₂ in the presence of EE2. The sorption-limited bioavailability of EE2, which is inherently resistant to biodegradation due to chemical structure, as MAX and Freundlich sorption coefficients (K_f) were negatively correlated. As such, the K_f values of EE2 were largest in composted biosolids in which EE2 was particularly resistant to microbial degradation as the MAX of EE2 was <3%. In contrast, the MAX of E2 showed a positive association with the K_f values of E2 because some steps in the E2 transformation process have been found to occur in the sorbed phase. The MAX of E2 was significantly greater in the biosolid and composted biosolid media than in any other media, whereas the MAX of E2 decreased in the following order: secondary sewage sludge > primary sewage sludge > biosolid = composted biosolid. This suggests that sewage sludges in municipal lagoons and pre-treatment holding lagoons are a more favorable media for mineralization of EE2, whereas biosolids in post-treatment storage lagoons are a more favorable media for the mineralization of E2. The presence of ciprofloxacin will have no impact on the potential E2 or EE2 mineralization rates in these cases.     

Estrogenic Compounds Downstream From Three Small Cities in Eastern Nebraska: Occurrence and Biological Effect1

Abstract: Recent studies have detected estrogenic compounds in surface waters in North America and Europe. Furthermore, the presence of estrogenic compounds in surface waters has been attributed, in some cases, to the discharge of wastewater treatment plant (WWTP) effluent. The primary objective of the current study was to determine if WWTP effluent contributes estrogens to the surface waters of Nebraska. A second objective of this study was to determine if estrogens were found in concentrations sufficient enough to manifest feminizing effects on fish. These objectives were satisfied by deploying polar organic chemical integrative samplers (POCIS) and caged fathead minnows at eight field sites. Deployment sites included: three reference sites (Pawnee Creek, the Little Blue River, and the Middle Loup River), two sites upstream of the WWTPs at Grand Island and Columbus, and three sites downstream of the WWTPs at Grand Island, Columbus, and Hastings. Following the seven day deployments, POCIS extracts were analyzed for estrone, 17β‐estradiol, estriol and 17α‐ethinylestradiol using liquid chromatography tandem mass spectrometry (LC/MS/MS). 17β‐estradiol was detected in POCIS from six of the eight field sites with the greatest quantities recovered in POCIS deployed downstream from the Grand Island and Hastings WWTPs. Estrone was detected only in the POCIS deployed downstream from the Grand Island and Hastings WWTPs. Estrogenic effects were detected in caged minnows analyzed for the hepatic mRNA expression of two estrogen‐responsive genes, vitellogenin (vg1) and estrogen receptor α (ERα). Fish deployed at the site where the greatest quantities of estrogens were recovered (Hastings) had significantly higher expression of both vg1 and ERα than fish deployed at any of the other sites. These results confirm that WWTP effluent contributes biologically significant levels of estrogens to Nebraska surface waters.     

The arrival and discharge of conjugated estrogens from a range of different sewage treatment plants in the UK

The occurrence of free and conjugated estrogens was examined in a survey of eleven sewage treatment plants (STPs) and their discharge water in the United Kingdom using grab sampling. The STPs included trickling filter with and without tertiary treatment, and activated sludge with tertiary treatment. For three activated sludge plants both influent and effluent samples were compared. For a further 8 STPs only the effluent was examined. The estrone-3-sulphate, estradiol-3-sulphate and estriol-3-sulphate concentrations (up to 20 ng L⁻¹) were typically 5-fold that of the respective free estrogen concentration in the effluents. This represents a substantial additional ‘potential’ estrogen load arriving in the receiving waters. Estrone-3-glucuronide was found at 9 ng L⁻¹, estradiol-3-glucuronide at 7 ng L⁻¹, and estriol-3-glucuronide at 32 ng L⁻¹ in sewage influent. Except on one occasion, no glucuronide conjugates could be found in the effluent. The results suggest in most cases glucuronide conjugates will be completely transformed in sewage treatment whilst sulphate conjugates will only be partially removed.     

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.     

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.     

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。     

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.