深圳河典型内分泌干扰物分布和季节变化规律研究

2011年6月至2012年5月在深圳河沿程采集水样,采用固相萃取一氮吹一衍生化的预处理方法和气相色谱/质谱联用法,对壬基酚(NP)、辛基酚(OP)、双酚A(BPA)、雌酮(E1)、雌二醇(E2)、17α-雌二醇(17α-E2)、雌三醇(E3)、雌炔醇(EE2)等8种内分泌干扰物(EDCs)在深圳河的浓度分布和时空变化规律进行了研究.同时通过主成分分析考察了EDCs与常规水质污染物的关系.结果表明,NP、BPA、E1、E3、EE2在深圳河各河段均有检出,而OP、17α-E2、E2的检出率均低于20％,EDCs主要来源是NP和BPA;深圳河旱季和雨季EDCs的浓度变化大,其中NP浓度表现出旱季高雨季低的规律,旱季浓度是雨季的1.74～5.63倍,但BPA和3种甾醇类雌激素的浓度呈现出了雨季高旱季低的相反变化规律,这应该与污水处理厂雨季污水溢流有关；通过主成分分析发现,BPA与DO存在明显的负相关关系,生物作用可能在BPA去除和甾醇类雌激素转化中起到了重要作用,具体机制还有待进一步研究.     

三种藻类引发水中17α-乙炔基雌二醇的光降解实验研究

研究了普通小球藻、铜绿微囊藻和柱孢鱼腥藻3种藻类引发水中17α-乙炔基雌二醇(EE2)的光降解.结果表明,在250 W高压汞灯(HPML,nm)的照射下,一定藻浓度下,EE2的光降解率可达19%-20%.另外,还研究光强、藻悬浮液浓度和EE2初始浓度等对EE2光降解速率的影响,发现在本实验体系中,光通量大、藻浓度高及EE2初始浓度低有利于提高EE2的光降解速率.     

温度对17α-乙炔雌二醇在SBR工艺中去除效果的影响

17a-乙炔雌二醇(EE2)属于人工合成雌激素,是活性较强的环境内分泌干扰物之一.在污水处理厂中,EE2主要是通过活性污泥的生物降解作用得以去除.影响活性污泥对EE2生物降解的因素很多,温度是影响因素之一.分别采用一级缺氧/好氧(A/O)模式和三级缺氧/好氧(A/O/A/O/A/O)模式运行的SBR工艺.考察了温度对EE2去除的影响.试验发现,随着温度的升高,EE2在水相和泥相中的去除率明显增加,其中在30℃时EE2去除率达到最大,2种运行模式下水相中EE2去除率均达到了96%以上;泥相是EE2生物降解的主要场所;EE2生物降解主要发生在好氧阶段,缺氧阶段EE2生物降解效果不明显.     

A2O工艺中雌激素的行为变化和去除机理

研究了厌氧-缺氧-好氧(A2O)活性污泥工艺对生活污水中天然雌激素雌酮(Estrone,E1)、17β-雌二醇(17β-Estradiol,E2)以及17α-乙炔基雌二醇(17α-Ethynylestradiol,EE2)的去除性能。在对COD、N和P具有良好去除效果的前提下,对E1、E2和EE2的去除率可分别达到92.7%、100%和62.7%。通过对各反应单元内3种雌激素的物料平衡分析,表明A2O工艺对雌激素的去除主要发生在厌氧段和好氧段。以失活污泥作为对照组,好氧硝化过程中雌激素去除的小试实验发现,好氧过程中E1、E2的去除主要依靠生物降解作用,而EE2的去除则主要依赖于活性污泥对其的吸附作用。     

生物炭对双酚A和17α-乙炔基雌二醇在土壤中吸附的影响

研究了添加生物炭对土壤吸附双酚A(BPA)和17α-乙炔基雌二醇(EE2)的影响。结果表明:BPA和EE2在添加生物炭前后的土壤中的等温吸附线都能被Freundlich模型很好地拟合,所有等温吸附线都呈现出非线性(非线性参数n在0.40~0.79之间),且添加生物炭之后吸附参数KF显著增大。根据等温吸附线,在污染物的平衡浓度为0.01 mg·L-1时,添加4%生物炭后,BPA和EE2的土水分配系数(Kd)分别提高了2.6和3.0倍,此时生物炭对土壤吸附BPA和EE2的贡献度分别达到72.5%和88.5%。进一步研究发现,添加生物炭使土-水吸附系统的p H及溶解性有机质浓度(DOC)升高,这对污染物在土壤中的吸附分别表现为一定的抑制和促进作用。添加生物炭对土壤吸附EE2的促进效果优于BPA,这主要是由于EE2比BPA具有更强的疏水性。     

气相色谱—质谱分析5种雌激素类物质的衍生化方法优化

选取5种雌激素类物质雌酮(E1)、雌二醇(E2)、17α-雌二醇(EE2)、雌三醇(E3)、双酚A(BPA)为研究对象,在气相色谱(GC)—质谱(MS)联用分析方法的基础上,对衍生化试剂和衍生化反应条件进行了优化。结果表明,使用含有1%(质量分数)三甲基氯硅烷(TMCS)的N,O-双(三甲基甲硅烷基)-三氟乙酰胺(BSTFA)联合吡啶作为衍生化试剂,加热条件为烘箱70℃加热40min时,衍生化产物单一且灵敏度高。采用此优化方法得到5种物质的平均加标回收率为98.0%~104.3%,相对标准偏差(RSD)为0.4%~12.5%,可为环境中5种雌激素类物质的分析测定提供参考。     

磁性Fe_3O_4/石墨烯纳米复合材料催化降解水中17β-雌二醇

利用化学沉淀法制备磁性四氧化三铁/石墨烯(Fe3O4/GE)纳米复合材料,并将其与H2O2构成非均相Fenton体系用于催化降解水中微量的17β-雌二醇(E2),研究了初始p H值,初始H2O2浓度,催化剂用量对E2降解的影响。结果表明,Fe3O4/GE纳米复合材料在无需外加光源的条件下能够有效催化降解E2。在p H 7.0,E2初始浓度为1 mg/L,初始H2O2浓度为15 mmol/L,Fe3O4/GE投加量为15 mg/L的条件下,反应8 h后可去除92.9%的E2。Fe3O4/GE具有便捷的磁分离特性和稳定的催化活性,经过7次循环使用后对E2的降解效率仍保持在91.5%左右。     

类-Fenton体系对水中17β-雌二醇的光降解

以250W照明金属卤化物灯为光源研究了水中17β雌二醇(E2)在类Fenton体系中的光降解。结果表明,Fe(Ⅲ)/H2O2体系能有效地光降解E2。pH3～6范围内,E2光降解率及反应初始速率随酸度的增大而增大;H2O2初始浓度越大,E2降解率及反应初始速率越大;E2初始浓度越低,E2降解率越高,反应初始速率越低。     

类-Fenton体系对水中17β-雌二醇的光降解

以250W照明金属卤化物灯为光源研究了水中17β-雌二醇（E2）在类-Fenton体系中的光降解。结果表明，Fe（Ⅲ）／H2O2体系能有效地光降解E2。pH3～6范围内，E2光降解率及反应初始速率随酸度的增大而增大；H2O2初始浓度越大，E2降解率及反应初始速率越大；E2初始浓度越低，E2降解率越高，反应初始速率越低。     

A^2O工艺中雌激素的行为变化和去除机理

研究了厌氧-缺氧-好氧（A2O）活性污泥工艺对生活污水中天然雌激素雌酮（Estrone,E1）、17β-雌二醇（17β-Estradiol,E2）以及17α-乙炔基雌二醇（17α-Ethynylestradiol,EE2）的去除性能。在对COD、N和P具有良好去除效果的前提下,对E1、E2和EE2的去除率可分别达到92.7%、100%和62.7%。通过对各反应单元内3种雌激素的物料平衡分析,表明A2O工艺对雌激素的去除主要发生在厌氧段和好氧段。以失活污泥作为对照组,好氧硝化过程中雌激素去除的小试实验发现,好氧过程中E1、E2的去除主要依靠生物降解作用,而EE2的去除则主要依赖于活性污泥对其的吸附作用。     

Quantification of steroid sex hormones using solid-phase extraction followed by liquid chromatography-mass spectrometry.

In this study, the occurrence of trace amounts of natural and synthetic steroid estrogens in the aquatic environment was studied using liquid chromatography coupled with electrospray mass spectrometry, following solid-phase extraction (SPE). The SPE was performed with C18 and NH2 cartridges. The first objective was to develop a reliable method for analyzing steroid estrogens (resulting from human and animal excretions) in different matrices. The method developed was then applied to quantify the occurrence of natural and synthetic hormones (estrone [E1], 17beta-estradiol [betaE2], 17alpha-estradiol [alphaE2], estriol [E3], and 17alpha-ethinylestradiol [EE2]) in environmental samples in surface water and wastewater treatment plant (WWTP) influent and effluent. In the WWTP influents, betaE2, alphaE2, and E3 were identified as ranging up to 72.6 ng/L in WWTP influent and to 16 ng/L in WWTP effluent. Analysis o f surface wa ter sampled upstream from the WWTP revealed the presence of all five estrogens, at levels up to 19.8 ng/L. These concentrations of estrogens pose an issue for large and small communities, because they are higher than the recommended guidelines for estrogen-active compounds and because a lot of communities use surface water as drinking-water sources.     

Oxidation of natural and synthetic hormones by the horseradish peroxidase enzyme in wastewater

Steroid estrogens, including both natural estrogens (e.g., estrone - E1; 17beta-estradiol - E2; and estriol - E3) and synthetic estrogens (e.g., 17alpha-ethinylestradiol - EE2), are known as endocrine-disrupting compounds. The objective of this research was to evaluate the feasibility of the enzymatic oxidation of estrogens and to optimize this process in municipal wastewater contaminated with steroid estrogens using horseradish peroxidase (HRP) and hydrogen peroxide. An initial HRP activity of 0.02 U ml(-1) was sufficient to completely remove EE2 from the synthetic solution, although greater HRP doses (up to 0.06 U ml(-1)) were required to remove E1, E2 and E3. The optimal molar peroxide-to-substrate ratio was determined to be approximately 0.45. Based on the Michaelis-Menten kinetics, the HRP had an increasing reactivity with E1, E3, E2, and EE2, in increasing order. In real activated sludge process effluent, an HRP dose of 8-10 U ml(-1) was required to completely remove all of the studied estrogens, while only 0.032 U ml(-1) of HRP was necessary to treat synthetic water containing the same estrogen concentrations.     

Occurrence of glucocorticogenic activity in various surface waters in The Netherlands

Considering the important role that surface waters serve for drinking water production, it is important to know if these resources are under the impact of contaminants. Apart from environmental pollutants such as pesticides, compounds such as (xeno)estrogens have received al lot of research attention and several large monitoring campaigns have been carried out to assess estrogenic contamination in the aquatic environment. The introduction of novel in vitro bioassays enables researchers to study if – and to what extent – water bodies are under the impact of less-studied (synthetic) hormone active compounds. The aim of the present study was to carry out an assessment on the presence and extent of glucocorticogenic activity in Dutch surface waters that serve as sources for drinking water production. The results show glucocorticogenic activity in the range of <LOD – 2.4 ng dexamethasone equivalents L⁻¹ (dex EQs) in four out of eight surface waters. An exploratory time-series study to obtain a more complete picture of the yearly average of fluctuating glucocorticogenic activities at two sample locations demonstrated glucocorticogenic activities ranging between <LOD – 2.7 ng dex EQs L⁻¹. Although immediate human health effects are unlikely, the environmental presence of glucocorticogenic compounds in the ng L⁻¹ range compels further environmental research and assessment.     

Sorption and desorption of three endocrine disrupters in soils

Sorption of the estrogens estrone (E1), 17beta-estradiol (E2) and 17alpha-ethynylestradiol (EE2) on four soils was examined using batch equilibrium experiments with initial estrogen concentrations ranging from 10 to 1000 ng mL-1. At all concentrations, >85% of the three estrogens sorbed rapidly to a sandy soil. E1 sorbed more strongly to soil than E2 or EE2. Partial oxidation of E2 to E1 was observed in the presence of soils. Autoclaving was more effective at reducing this conversion than inhibition with sodium azide or mercuric chloride, and had little effect on sorption, relative to the chemical microbial inhibitors. Sorption of EE2 was greater for fine-textured than coarse-textured soils, but greater than 90% of EE2 sorbed onto all four soils. The greatest degree of desorption of estrogens from the sandy soil occurred with the lowest initial concentration of 10 ng mL-1 and reached levels >or=80% for E1 and E2. Desorption of EE2 was greater in coarser textured soils than finer-textured soils. Again, relative desorption from all soils was greatest with low initial concentrations. Therefore, at environmentally relevant concentrations, estrogens quickly sorb to soils, and soils have a large capacity to bind estrogens, but these endocrine-disrupting compounds can become easily desorbed and released into the aqueous phase.     

Dissolved organic carbon from sewage sludge and manure can affect estrogen sorption and mineralization in soils

In this study, effects of sewage sludge and manure borne dissolved organic carbon (DOC) on 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) sorption and mineralization processes were investigated in three agricultural soils. Batch equilibrium techniques and equilibrium dialysis methods were used to determine sorption mechanisms between DOC, estrogens and the soil solid phase. It was found that that the presence of organic waste borne DOC decreased estrogen sorption in soils which seems to be controlled by DOC/estrogen complexes in solution and by exchange processes between organic waste derived and soil borne DOC. Incubation studies performed with ¹⁴C-estrogens showed that DOC addition decreased estrogen mineralization, probably due to reduced bioavailability of estrogens associated with DOC. This increased persistence combined with higher mobility could increase the risk of estrogen transport to ground and surface waters.     

Sorption and Desorption of Three Endocrine Disrupters in Soils

Sorption of the estrogens estrone (E1), 17β-estradiol (E2) and 17α-ethynylestradiol (EE2) on four soils was examined using batch equilibrium experiments with initial estrogen concentrations ranging from 10 to 1000 ng mL^?1. At all concentrations, >85% of the three estrogens sorbed rapidly to a sandy soil. E1 sorbed more strongly to soil than E2 or EE2. Partial oxidation of E2 to E1 was observed in the presence of soils. Autoclaving was more effective at reducing this conversion than inhibition with sodium azide or mercuric chloride, and had little effect on sorption, relative to the chemical microbial inhibitors. Sorption of EE2 was greater for fine-textured than coarse-textured soils, but greater than 90% of EE2 sorbed onto all four soils. The greatest degree of desorption of estrogens from the sandy soil occurred with the lowest initial concentration of 10 ng mL^?1 and reached levels ≥80% for E1 and E2. Desorption of EE2 was greater in coarser textured soils than finer-textured soils. Again, relative desorption from all soils was greatest with low initial concentrations. Therefore, at environmentally relevant concentrations, estrogens quickly sorb to soils, and soils have a large capacity to bind estrogens, but these endocrine-disrupting compounds can become easily desorbed and released into the aqueous phase.     

Uptake and elimination,and effect of estrogen-like contaminants in estuarine copepods: an experimental study

Background, aim, and scope  

In recent years, anthropogenic chemicals which can disrupt the hormonal systems of both humans and wildlife have been raised to a major cause of concern. The aim of the present work was to determine the bioconcentration factors of the two major alkylphenols (AP) of the Seine Estuary [4-nonylphenol (4 NP) and nonylphenol acetic acid (NP1EC)] and of the synthetic estrogen, estrogen ethinylestradiol (EE2), in Eurytemora affinis after exposure in a continuous flow-through system under environmental realistic conditions. Moreover, the elimination of these compounds in copepods from the Seine Estuary has been investigated by measuring concentrations after 1 week in clean water in comparison to background levels.