固相萃取-液相色谱-串联质谱法测定水中5种雌激素

建立了固相萃取-液相色谱-串联质谱组合联用技术同时测定地表水、饮用水和污水处理厂出厂水中的5种雌激素(17β-雌二醇、雌三醇、雌酮、17α-炔雌醇、己烯雌酚)的方法。水样经过全自动固相萃取仪富集,以OASIS HLB柱为萃取柱,甲醇为洗脱剂,用液相色谱-串联四极杆质谱联用仪分析定量。分别在0.5~8、5~80μg/L范围内线性良好,相关系数为0.995~0.998。17β-雌二醇、雌三醇、17α-炔雌醇的检出限均为5μg/L,雌酮与己烯雌酚的检出限为0.5μg/L。5种雌激素的纯水加标回收率为63.6%~120.2%,地表水加标回收率为59.8%~91.5%,自来水加标回收率为55.3%~92.1%,精密度为3.7%~10.7%,该方法简单、可靠,可用于水中雌激素类污染物的同时测定。     

邻苯二甲酸丁基苄酯在鼠肝匀浆中的生物降解及代谢产物鉴定

应用HPLC及HPLC MS方法,研究了邻苯二甲酸丁基苄酯在小鼠肝匀浆中的代谢动力学、酶动力学特征并进行了代谢产物鉴定.测得邻苯二甲酸丁基苄酯在雄性小鼠肝匀浆中的t1/2为73.72min,Km为(73.52±24.11)μmol·L-1,Vmax为(2.85±0.62)μmol·g-1·min-1);在小鼠雌性肝匀浆中t1/2为144.37min,Km为(275.02±64.97)μmol·L-1,Vmax为(6.18±2.30)μmol·g-1·min-1).实验鉴定出邻苯二甲酸丁基苄酯在肝脏中的代谢产物为邻苯二甲酸单丁酯及邻苯二甲酸甲丁酯.实验结果表明,邻苯二甲酸丁基苄酯在肝脏中代谢有明显的性别差异.     

How seasonality affects the flow of estrogens and their conjugates in one of Japan's most populous catchments

A detailed study of the free and conjugated estrogen load discharged by the eight major sewage treatment plants into the Yodo River basin, Japan was carried out. Sampling campaigns were focused on the winter and autumn seasons from 2005 to 2008 and the free estrogens estrone(E1), 17β-estradiol(E2), estriol(E3), 17α-ethynylestradiol(EE2) as well as their conjugated (sulfate and glucuronide) forms. For both sewage effluent and river water E2 and E1 concentrations were greatest during the winter period (December-March). This coincides with the period of lowest rainfall and lowest temperatures in Japan. E1 was the dominant estrogenic component in effluent (means of 10-50 ng/L) followed by E2 (means of 0.5-3 ng/L). The estrogen sulfate conjugates were found intermittently in the 0.5-1.7 ng/L concentration range in the sewage effluents. The greatest estrogen exposure was found to be in the Katsura River tributary which exceeded 1 ng/L E2-equivalents during the winter period.     

Al2(SO4)3和FeCl3混凝对红枫湖溶解性有机质的去除及卤代烃控制的影响

以三价阳离子(Al2(SO4)3和FeCl3)为混凝剂,在不同的投加量和水力条件下对贵阳市红枫湖取水口处溶解性有机质(DOM)的去除和卤代烃(THMs)生成势控制变化趋势进行研究。实验结果表明,在不同的混凝条件下,对DOM的去除率在60%左右,随着快速搅拌速率的增加,去除率略有提高;UV254的去除率为85%左右,不同的混凝剂投加量和水力条件对其影响不大。混凝前后DOM的THM生成势降低约60%,二氯一溴甲烷(CHCl2Br)和一氯二溴甲烷(CHClBr2)占THMs的80%以上;对于不同的混凝剂类型,投加量和水力条件均对THMs生成势变化没有明显差异。三维荧光光谱(3D-EEM)结果表明,DOM中腐殖酸部分在混凝过程中有较大去除,红外光谱(FTIR)验证了混凝去除的基团主要为羰基(CO)的类共轭结构。而在强化混凝过程中没有得到较大去除的内源有机质(藻源有机物)可能是混凝后THMs的主要前体物质。因此,传统的混凝工艺主要去除DOM的腐殖酸部分,还需要结合其他的预处理方法对DOM中的其他组分进行有效去除,以控制THMs的生成势,提高饮用水的安全性。     

Determination of phenolic and steroid endocrine disrupting compounds in environmental matrices

BACKGROUND, AIM AND SCOPE: Many pollutants have received significant attention due to their potential estrogenic effect and are classified as endocrine disrupting compounds (EDCs). EDCs comprise many classes of organic compounds. The development or optimization of analytical protocols for the simultaneous determination of EDCs in environmental samples is an analytical challenge because these compounds exhibit different physicochemical characteristics, they occur in the aquatic environment in relatively low concentrations and, furthermore, environmental samples are considered as complex matrices. The aim of this study is the development of analytical methods for the simultaneous determination of phenolic and steroid EDCs in aqueous and solid samples. The target compounds are 4-nonylphenol, 4-octylphenol, their ethoxylate oligomers (mono- and di-ethoxylates of nonylphenol and octylphenol), bisphenol A, the estrogens (estriol, estrone, 17beta-estradiol, 17alpha-estradiol) and the synthetic steroids (mestranol and 17alpha-ethynylestradiol). MATERIALS AND METHODS: Solid phase extraction employing Oasis HLB cartridges and different elution solvents was used for the recovery studies of the target compounds from various types of water samples (ultrapure water, artificial seawater, river water and seawater). Ultrasonic assisted extraction was applied for the recovery of the target EDCs from the solid samples. The recoveries were assessed using various solvents for the extraction and the elution of EDCs from different SPE cartridges used for clean up. Gas chromatography-mass spectrometry after derivatization with N,O-bis(trimethylsilyl)-trifluoroacetamide was employed for the determination of these compounds. RESULTS AND DISCUSSION: The recovery rates of three elution solvents (methanol, acetone and ethylacetate) for the extraction of target EDCs from artificial seawater were assessed after preconcentration on SPE cartridges. Acetone showed better recoveries and was further tested for its extraction efficiency in different water types (river water, seawater). Ultrasonic assisted extraction was used for the recovery of target EDCs from solid matrices. Acetone, methanol, mixture of acetone-methanol (1:1) and ethylacetate were used as extraction solvents. Ethylacetate and the mixture of acetone-methanol (1:1) exhibited better extraction efficiencies. An additional clean up step was necessary for sediment samples. Different SPE cartridges were employed for clean up of the extracts (Oasis HLB, C18, Florisil, silica, combination of silica and alumina). Florisil cartridges were finally used. The proposed methods were further validated on the determination of target EDCs in field collected samples (river water, seawater, wastewater, total suspended solids and sediments) from the major area of Thessaloniki, Greece. CONCLUSIONS: Efficient and accurate integrated methods for the simultaneous determination of alkylphenols (nonylphenol, octylphenol), their ethoxylate oligomers (mono- and di-ethoxylate of nonylphenol and octylphenol), bisphenol A and steroids (estriol, estrone, 17beta-estradiol, 17alpha-estradiol, mestranol and 17alpha-ethynylestradiol) in aqueous and solid samples were developed. The proposed methods were applied for the determination of the target compounds in representative environmental samples in the area of Thessaloniki, Northern Greece. RECOMMENDATIONS AND PERSPECTIVES: This study confirms the occurrence of selected EDCs in inland and marine waters in the area of Thessaloniki, Northern Greece. Since there is no previous data on the occurrence of the target EDCs in the major area, an extended survey is in progress to evaluate the occurrence and fate of these compounds.     

珠江广州河段表层水中雌激素化合物的污染状况

分析了珠江广州河段枯水期表层水中雌激素化合物的污染状况. 结果表明, 在所有样品中均检测出了双酚A(BPA)和雌酮(E1), 其浓度范围分别为97. 8—540. 6ng·l-1(中值为145. 9ng·l-1)和2. 5—8. 2ng·l-1(中值为4. 5ng·l-1); 两种化合物的最高值都出现在前航道的东圃大桥, 最低值则在黄埔水道的黄埔港, 其空间分布主要与沿途生活污水和工业废水的排放有关.     

再生水无计划间接补充饮用水的雌激素健康风险

以城市污水为水源的再生水中含有一定量的雌激素类内分泌干扰物,其在无计划间接补充饮用水过程中存在潜在健康风险.针对再生水经河流补给湖库型水源地的典型场景,研究了再生水中雌酮、雌二醇、17α-乙炔基雌二醇、双酚A、壬基酚和辛基酚在水体中的变化规律,评价了雌激素的健康风险.结果表明,再生水(二级出水)中雌激素类物质的质量浓度多分布在0.1~100 ng·L-1水平;双酚A和壬基酚的浓度较高,可达到1~10μg·L-1水平.再生水间接补充饮用水过程中,雌激素的浓度受到上游来水稀释、河道湖库自然降解和饮用水处理工艺去除等作用的影响.雌酮、雌二醇、双酚A、壬基酚和辛基酚的非致癌风险较小,都低于规定值1.当湖库型水源地的水力停留时间大于30 d时,再生水中17α-乙炔基雌二醇对人体的非致癌风险值大多小于1;当停留时间小于10 d且再生水占饮用水比例达50%以上时,16%~47%样品的17α-乙炔基雌二醇的非致癌风险值大于1,其健康风险需优先关注.     

4种环境雌激素对淡水鱼卵黄蛋白原诱导的混合物效应研究

在个体水平上阐明环境雌激素类化合物对易受影响生物的联合毒性作用,探讨混合污染物联合作用和环境风险评价的研究方法.通过对鲫鱼血清卵黄蛋白原含量的相对变化和暴露浓度的非线性回归分析得出17α-乙炔基雌二醇(EE2)、17β-雌二醇(E2)、双酚A(BPA)、辛基苯酚(OP)及其等毒性混合物产生雌激素效应的剂量-反应关系,应用联合作用指数和相加作用模型研究4种环境雌激素的联合作用.各化合物非线性回归分析结果均以Weibull函数拟合效果最好,决定系数R2≥0.92;效应浓度值及其95%置信限通过自举抽样法得出,其中半效应浓度值EC50及其95%置信区间分别为0.0079(0.0068～0.0100)、0.0987(0.0900～0.1110)、63.50(56.58～70.62)和250.59(228.46～271.99)μg·L-1.4种环境雌激素混合物效应通过相加作用模型预测在全剂量范围内与实验结果相一致,呈现相似联合作用.相加作用模型是在各个浓度反应水平上展示化合物联合作用的性质,是切实可行的联合作用研究方法,而混合物效应通过联合作用指数评价存在许多不确定性.