螺旋霉素在水溶液中的光降解

螺旋霉素(Spiramycin,SPI)是一种广泛存在于水体中的新兴有机污染物.在表层水体,光降解是其主要的降解方式.本实验研究了高压汞灯(250W)、氙灯(1000W)和太阳光照射下SPI在超纯水和天然湖水中的光降解过程,探讨了SPI在水溶液中的光降解动力学及环境因素对其光降解的影响.结果表明,SPI在高压汞灯照射下降解最快,其次是氙灯,太阳光照射下降解最慢,均符合准一级反应动力学.高压汞灯照射下,SPI在纯水中的光降解速率小于天然湖水中,在纯水中SPI发生了直接光降解和自敏化光降解,并以直接光降解为主.SPI的光降解速率常数(k)与其初始浓度(C0)呈负相关;随水体pH增大k增大;NO_3~-对SPI光降解具有促进作用,NO_3~-浓度升高降解速率增大;而HA、NO_2~-对其光降解具有抑制作用,HA、NO_2~-浓度升高抑制率增加.     

羟基多溴联苯醚(OH-PBDEs)小鼠肝脏微粒体体外代谢及对雌激素代谢的影响研究

羟基化多溴联苯醚(OH-PBDEs)是一类具有内分泌干扰效应的酚类化合物,以小鼠肝脏微粒体作为研究对象,考察了OH-PBDEs的体外代谢行为及对雌激素代谢的影响。研究结果发现,4种OH-PBDE均能够代谢,其代谢率大小为6-OH-BDE-996’-OH-BDE-996-OH-BDE-1375’-OH-BDE-99,表明羟基官能团(-OH)与醚键及溴原子处于邻位时,表现出较高的代谢率; 4种OH-PBDE对3种天然雌激素包括雌酮(E1)、17β-雌二醇(E2)、雌三醇(E3)的代谢表现出不同作用,整体来说,对E1和E2代谢随着OH-PBDE浓度的增加抑制作用逐渐增强,对E3代谢则表现出促进作用,但是对人工合成的雌激素17α-炔雌醇(EE2)无明显影响;对E2代谢产物2-羟基雌二醇(2-OH-E2)的生成量定量表征表明,除6-OH-BDE-99促进了2-OH-E2的生成量,其余3种OH-PBDE随实验添加浓度的增加,抑制了2-OH-E2的生成量,这可能与酶介导的不同代谢机制有关。     

三氯生光降解动力学过程及其光降解产物生物毒性评价

光化学降解是药品及个人护理用品(PPCPs)在环境中转化归趋的重要途径之一,同时光解过程对该类化合物的生态毒性产生重要影响。本研究以抗菌药物三氯生为模型化合物,研究在紫外光照射下,三氯生初始浓度、腐殖酸含量、pH、光强对其光降解动力学的复合影响。采用发光细菌、羊角月牙藻2个不同营养级生物的毒性响应变化评价三氯生母体化合物及光降解过程中毒性变化。研究表明:三氯生光降解遵循准一级反应动力学。初始浓度为10μmol·L~(-1)、腐殖酸含量为0 mg·L~(-1),初始p H值为11、光强为0.44 m W·cm-2时,该光化学降解反应体系三氯生有最高的反应速率和降解效率。三氯生光降解过程中产生了对受试生物有较高抑制作用的中间产物,随着光降解时间的延长,光降解中间产物的毒性逐渐降低,在光降解30 min后无显著毒性。     

雌酮的氯化产物及其内分泌干扰作用活性

利用固相萃取-LC/ESI-MS分析测定雌酮及其在氯气消毒过程中产生的副产物,结果表明,雌酮容易和次氯酸发生反应,并检出了包括一氯雌酮、二氯雌酮在内的4种副产物．用酵母双杂交方法对副产物的内分泌干扰活性进行了测试,发现副产物也具有内分泌干扰作用．     

长江水体分散颗粒物对对乙酰氨基酚光降解的影响

研究了药物对乙酰氨基酚在长江水体颗粒物表面的吸附及颗粒分散体系中的光降解规律,探讨了体系pH、颗粒物浓度及加入柠檬酸、草酸、腐殖酸对对乙酰氨基酚光降解的影响.结果表明,对乙酰氨基酚在颗粒物表面的吸附符合Langmuir型吸附等温式,分散颗粒物可以促进对乙酰氨基酚的光降解,光降解符合一级反应动力学规律;pH=9时光降解速率最快;加入草酸、柠檬酸可以加快对乙酰氨基酚的光降解,而腐殖酸则抑制其光降解.     

珠江三角洲两条主要河流沉积物中的典型内分泌干扰物污染状况

为了调查珠江三角洲河流沉积物中典型内分泌干扰物的污染状况,采用超声提取-衍生化-GC/MS法研究了双酚A(BPA)、雌酮(E1)、雌二醇(E2)、己烯雌酚(DES)、17α-乙炔雌二醇(EE2)、雌三醇(E3)等典型内分泌干扰物在珠江广州河段和东江东莞河段表层沉积物中的质量分数水平、分布特征,并对其来源进行了分析。结果显示,BPA在所有样品中均有检出,E1和E2的检出率分别为72%和61%,其质量分数(以干质量计)分别在14.3～429.5 ng.g-1之间(中值为79.5 ng.g-1)、<1.3～10.9ng.g-1之间(中值为3.4 ng.g-1)和<0.9～2.6 ng.g-1之间(中值为1.6 ng.g-1);其余几种雌激素均未被检出。东江东莞河段沉积物中BPA的污染水平整体高于珠江广州河段,而天然雌激素的污染状况则是珠江广州河段更为严重。3种化合物的质量分数总体呈现出沿河口方向降低的分布特征,这可能与沿岸工业废水和生活污水不规则排放以及水动力条件有关。BPA、E1、E2的质量分数均与沉积物总有机碳(TOC)质量分数呈正相关,表明有机质是控制沉积物中内分泌干扰物分布的一个重要因素。     

珠江三角洲两条主要河流沉积物中的典型内分泌干扰物污染状况

为了调查珠江三角洲河流沉积物中典型内分泌干扰物的污染状况,采用超声提取-衍生化-GC/MS法研究了双酚A（BPA）、雌酮（E1）、雌二醇（E2）、己烯雌酚（DES）、17α-乙炔雌二醇（EE2）、雌三醇（E3）等典型内分泌干扰物在珠江广州河段和东江东莞河段表层沉积物中的质量分数水平、分布特征,并对其来源进行了分析。结果显示,BPA在所有样品中均有检出,E1和E2的检出率分别为72%和61%,其质量分数（以干质量计）分别在14.3～429.5 ng.g-1之间（中值为79.5 ng.g-1）、〈1.3～10.9ng.g-1之间（中值为3.4 ng.g-1）和〈0.9～2.6 ng.g-1之间（中值为1.6 ng.g-1）;其余几种雌激素均未被检出。东江东莞河段沉积物中BPA的污染水平整体高于珠江广州河段,而天然雌激素的污染状况则是珠江广州河段更为严重。3种化合物的质量分数总体呈现出沿河口方向降低的分布特征,这可能与沿岸工业废水和生活污水不规则排放以及水动力条件有关。BPA、E1、E2的质量分数均与沉积物总有机碳（TOC）质量分数呈正相关,表明有机质是控制沉积物中内分泌干扰物分布的一个重要因素。     

低分子有机羧酸对累托石悬浮液中双酚A光降解的影响

研究了低分子有机羧酸草酸、柠檬酸对内分泌干扰物双酚A(BPA)在累托石悬浮液中光降解的影响.结果表明,在250W金属卤化物灯(λ≥36nm)照射下,草酸、柠檬酸可以显著提高BPA在累托石悬浮液中的光降解率,反应符合Langmuir-Hinshelwood动力学方程,降解率同时受pH值、累托石用量的影响,矿化实验表明BPA在累托石/低分子羧酸体系中能够深度氧化.     

双酚E在分子识别作用下的光催化降解

研究了经分子识别后的双酚E在TiO2光催化体系中的光降解行为,结果表明:双酚E能与β-环糊精形成稳定的包结物,其包结常数为7.83×103 L·mol-1,经β-环糊精分子识别后双酚E的光催化降解效率可以提高26%,同时研究了双酚E光降解的动力学规律及pH值和β-环糊精浓度对双酚E光降解的影响.β-环糊精对双酚E光催化降解的促进作用源于β-环糊精促进双酚E在TiO2表面的吸附.     

中国天然雌激素排放清单和风险评价

环境雌激素由于其较强的内分泌干扰特性,越来越受到普遍关注。环境雌激素中,人和动物排放的天然类固醇雌激素（E1、E2、EE2、E3）干扰性最强。建立天然雌激素排放清单,对于了解中国环境雌激素的排放状况,以及进一步的污染风险分析与控制,具有重要意义。本研究将天然雌激素的主要排放源按人、猪、牛和家禽分为10种不同类型,根据各...     

Occurrence of estrogenic endocrine disrupting chemicals concern in sewage plant effluent

The purpose of this study was to give a worldwide overview of the concentrations of typical estrogenic endocrine disrupting chemicals （EDCs） in the effluent of sewage plants and then compare the concentra- tion distribution of the estrogenic EDCs in ten countries based on the survey data of the estrogenic EDCs research. The concentrations of three main categories （totally eight kinds） of estrogenic EDCs including steroidal estrogens （estrone （El）, estradiol （E2）, estriol （E3） and 17a- ethynylestradiol （EE2））, phenolic compounds （nonylphe- nol （NP） and bisphenol A （BPA）） and phthalate esters （dibutyl phthalate （DBP） and dibutyl phthalate （2- ethylhexyl） phthalate （DEHP）） in the effluents of sewage plants reported in major international journals over the past decade were collected. The statistics showed that the concentration distributions of eight kinds of EDCs were in the range of ng·L^-1 to μg·L^-1. The concentrations of steroidal estrogens mainly ranged within 50.00 ng. L-1, and the median concentrations of El, E2, E3 and EE2 were 11.00, 3.68, 4.90 and 1.00 ng·L^-1, respectively. Phenolic compounds and phthalate esters were found at pg. L-1 level （some individual values were at the high level of 40.00 μg·L^-1）. The median concentrations of BPA, NP, DBP and DEHP were 0.06, 0.55, 0.07 and 0.88 μg·L^-1, respectively. The concentrations of phenolic compounds and phthalate esters in the effluents were higher than that of steroids estrogens. The analysis of the concentration in various ten countries showed that steroids estrogens, phenolic compounds and phthalate esters in sewage plant effluents were detected with high concentration in Canada, Spain and China, respectively.     

Occurrence of endocrine disruptor compounds in the estuary of the Iberian Douro River and nearby Porto Coast (NW Portugal)

Previous studies in the Douro River estuary, based on occasional sampling, showed the presence of several estrogenic disrupting chemicals (EDCs). In sequence, we hypothesized that such type of pollution was more likely an enduring issue than an occasional phenomenon, and that it may even affect recreational beaches in each side of the estuarine mouth. Thus to conclude about the continuous influx of EDCs, water samples were taken twice a day, once per a week, from March to May of 2009, at four sites within the estuary and at two sites in the coastline. After solid-phase extraction, the extracts were prepared for GC-MS analysis of 11 reference EDCs. These embraced natural and pharmaceutical estrogens (17β-estradiol, estrone and 17α-ethynylestradiol) and xenoestrogenic industrial pollutants (4-octylphenol, 4-nonylphenol, and their mono and diethoxylates and bisphenol A). Data showed the ubiquitous presence of potentially hazardous amounts of natural estrogens (particularly of estradiol, ca 5.5?ng?L^?1) and persistent organic pollutants such as nonylphenol mono (up to 550?ng?L^?1) and diethoxylate (up to 2000?ng?L^?1). It was concluded that the targeted area is continuously polluted by the assayed EDCs, and as a consequence, conditions exist for endocrine disturbance in the biota by chronic exposure to EDCs.     

Presence of estrogenic endocrine disruptors in three European estuaries in Northwest Iberian Peninsula (Portugal)

Abstract

Estrone, 17β-estradiol, 17α-ethynylestradiol, alkylphenols and alkylphenol ethoxylates, are endocrine disruptor compounds. In Portugal, the report of male fish feminization in Minho, Ave and Mondego River estuaries made pertinent their evaluation in surface water samples. Data, got by specific enzyme-linked immunosorbent assays, showed that estrogens concentrations were lower in Minho than in Ave or Mondego estuaries: [Estrone]?>?[17β-estradiol]?>?[17α-ethynylestradiol] (p?<?0.05). Converting estrogen concentrations in 17α-ethynylestradiol equivalents, the contribution of estrogens was 1.3?ng/L, 3.5?ng/L, and 2.4?ng/L, respectively, for Minho, Ave, and Mondego estuaries stressing out a high risk for local aquatic species. The concentrations of alkylphenols and alkylphenol ethoxylates were lower at both Minho and Mondego estuaries ≈600?ng/L and 2700?ng/L, respectively than at the Ave, ≈1070?ng/L and 4855?ng/L (p?<?0.05). In conclusion, this study reports the first systematic data about the presence of the targeted endocrine disruptor compounds in the Minho River estuary and, in parallel, provides new information about their concentrations in two other habitats previously monitored. This study also shows that in Ave and Mondego estuaries the concentrations of industrial estrogens were still excessive, whereas the load of the pure estrogens has decreased significantly facing previous surveys.     

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.     

城市污水中典型卤代苯酚分布及其光降解行为研究

卤代苯酚(HPs)是一类广泛存在于水体中的污染物,其在污水处理厂出水中的存在及迁移转化会产生一定的健康和生态风险。探究卤代苯酚在环境中的转化行为非常重要。光降解反应是酚类物质在水体中迁移转化的重要途径,实际水体中的有机质等对卤代苯酚的光降解会产生一定的影响。对大连市区6家污水处理厂出水中卤代苯酚的污染状况进行了调查,结果显示在所有出水中总HPs的浓度范围为77.2~168.6 ng·L-1。在所有检出的卤代苯酚中,五氯酚和2,6-二氯酚浓度较高,且检出频率均为100%,检出浓度范围分别为10.8~166.7 ng·L-1和0.1~72.2 ng·L-1。在模拟太阳光照射条件下,选取2种氯酚和2种溴酚研究它们在污水样品与纯水中光降解行为,从卤原子取代的程度和种类两方面对不同卤代苯酚光降解的规律进行类比,分析了其光降解特性。此外,对比分析了不同污水厂出水的对同种卤代苯酚降解速率的影响,发现出水的p H值、溶解性有机质等因素,都可能影响卤代苯酚的光降解。     

Investigation of the effects of humic acid and H 2 O 2 on the photocatalytic degradation of atrazine assisted by microwave

A solution of atrazine in a TiO₂ suspension, an endocrine disruptor in natural water, was tentatively treated by microwave-assisted photocatalytic technique. The effects of mannitol, oxygen, humic acid, and hydrogen dioxide on the photodegradation rate were explored. The results could be deduced as follows: the photocatalytic degradation of atrazine fits the pseudo-first-order kinetic well with k = 0.0328 s⁻¹, and ·OH was identified as the dominant reactant. Photodegradation of atrazine was hindered in the presence of humic acid, and the retardation effect increased as the concentration of humic acid increased. H₂O₂ displayed a significant negative influence on atrazine photocatalysis efficiency. Based on intermediates identified with gas chromatography-mass spectrometry (GC-MS) and Liquid chromatography-mass spectrometry (LC-MS/MS) techniques, the main degradation routes of atrazine are proposed.     

Factors influencing the photodegradation of N-nitrosodimethylamine in drinking water

In order to provide basic data for practical application, photodegradation experiment of N-nitrosodimethylamine (NDMA) in aqueous solution was carried out with a low-pressure Hg lamp. Effects of the initial concentration of NDMA, solution pH, dissolved oxygen, and the presence of humic acid on NDMA photodegradation were investigated. NDMA at various initial concentrations selected in this study was almost completely photodegraded by UV irradiation within 20 min, except that at 1.07 mmol/L, NDMA could be photodegraded almost completely in the acidic and neutral solutions, while the removal efficiency decreased remarkably in the alkaline solution. Dissolved oxygen enhanced the NDMA photodegradation, and the presence of humic acid inhibited the degradation of NDMA. Depending on the initial concentration of NDMA, NDMA photodegradation by UV obeyed the pseudo-first-order kinetics. Dimethylamine, nitrite, and nitrate were detected as the photodegradation products of NDMA. ¹O₂ was found to be the reactive oxygen species present in the NDMA photodegradation process by UV, based on the inhibiting experiments using tert-butanol and sodium azide.     

Investigation of the effects of humic acid and H<Subscript>2</Subscript>O<Subscript>2</Subscript> on the photocatalytic degradation of atrazine assisted by microwave

A solution of atrazine in a TiO₂ suspension, an endocrine disruptor in natural water, was tentatively treated by microwave-assisted photocatalytic technique. The effects of mannitol, oxygen, humic acid, and hydrogen dioxide on the photodegradation rate were explored. The results could be deduced as follows: the photocatalytic degradation of atrazine fits the pseudo-first-order kinetic well with k = 0.0328 s^?1, and ·OH was identified as the dominant reactant. Photodegradation of atrazine was hindered in the presence of humic acid, and the retardation effect increased as the concentration of humic acid increased. H₂O₂ displayed a significant negative influence on atrazine photocatalysis efficiency. Based on intermediates identified with gas chromatography-mass spectrometry (GC-MS) and Liquid chromatography-mass spectrometry (LC-MS/MS) techniques, the main degradation routes of atrazine are proposed.     

Photosensitivity sources of dissolved organic matter from wastewater treatment plants and their mediation effect on 17α-ethinylestradiol photodegradation

● EE2 photodegradation behavior in the presence of four WWTPs’ DOM was explored. ● The ³DOM* played a major role in the EE2 photodegradation mediated by WWTPs’ DOM. ● The A²/O process DOM contained more aromatic and oxygen-containing substances. ● Possible photosensitivity sources of DOM in the A²/O process were proposed. Dissolved organic matter (DOM) from each treatment process of wastewater treatment plants (WWTPs) contains abundant photosensitive substances, which could significantly affect the photodegradation of 17α-ethinylestradiol (EE2). Nevertheless, information about EE2 photodegradation behavior mediated by DOM from diverse WWTPs and the photosensitivity sources of such DOM are inadequate. This study explored the photodegradation behavior of EE2 mediated by four typical WWTPs’ DOM solutions and investigated the photosensitivity sources of DOM in the anaerobic-anoxic-oxic (A²/O) process. The parallel factor analysis identified three varying fluorescing components of these DOM, tryptophan-like substances or protein-like substances, microbial humus-like substances, and humic-like components. The photodegradation rate constants of EE2 were positively associated with the humification degree of DOM (P < 0.05). The triplet state substances were responsible for the degradation of EE2. DOM extracted from the A²/O process, especially in the secondary treatment process had the fastest EE2 photodegradation rate compared to that of the other three processes. Four types of components (water-soluble organic matter (WSOM), extracellular polymeric substance, humic acid, and fulvic acid) were separated from the A²/O process DOM. WSOM had the highest promotion effect on EE2 photodegradation. Fulvic acid-like components and humic acid-like organic compounds in WSOM were speculated to be important photosensitivity substances that can generate triplet state substances. This research explored the physicochemical properties and photosensitive sources of DOM in WWTPs, and explained the fate of estrogens photodegradation in natural waters.     

Quantification of 17 endocrine disruptor compounds and their spatial and seasonal distribution in the Iberian Ave River and its coastline

The Ave River flows through the most urbanized and industrialized Porto district areas. Despite ovotestis was recently reported in male fish from the estuary, no data exist on the water levels of natural and pharmaceutical estrogens (17β-estradiol, estrone, and 17α-ethynylestradiol), xenoestrogenic industrial pollutants (4-octylphenol, 4-nonylphenol and their mono and diethoxylates, and bisphenol A), phytoestrogens (formononetin, biochanin A, daidzein, and genistein), and sitosterol. Absence of analyses applies to the river, estuary, and nearby coastline. Those compounds mimic the action of endogenous estradiol, being well-recognized endocrine disrupters (EDCs). To conclude about suspected influxes of estrogenic EDCs into the river and coastline, water samples were taken at eight sites every two months, during one year (2010), at low tide. Data showed ubiquitous presence of potentially hazardous amounts of estrogens (particularly ethynylestradiol, up to 10 ng L^?1), nonylphenol (up to 250 ng L^?1), and sitosterol (up to 6 μg L^?1), which helps explaining the ovotestis emergence in local fish. Also, because physicochemical parameters used in water quality evaluation, such as pH, dissolved oxygen, nitrates, and nitrites levels, were within legal limits – suggesting good quality – our study supports that assessment of human and environmental risks by targeting surface waters requires integrating EDCs monitoring in routine analyses.