饮用水中内分泌干扰物双酚A的臭氧氧化降解研究

采用臭氧氧化工艺对饮用水中内分泌干扰物双酚A特性进行了研究.研究表明:在原水浓度为1.0mg/L左右,臭氧总投加量为1.0、1.5和2.0mg/L条件下,30min BPA去除率可达70%、82%和90%.通过考察不同臭氧投加量、不同本底条件、不同BPA初始浓度和不同臭氧投加时间对BPA臭氧氧化的影响,分析得出臭氧投加量对BPA的降解占主导地位,而臭氧接触时间对去除效果的影响很小;采用紫外波长扫描确定在臭氧降解BPA的同时生成了在UV₂₅₄上有吸收的产物.通过考察臭氧氧化双酚A过程中UV₂₅₄的变化,提出低臭氧投加量下BPA不能完全被氧化,而采用缩短臭氧投加时间、加大臭氧投加量以及提高水中余臭氧浓度等方法,有利于水中BPA的完全降解.     

水中腐殖酸对高级氧化联用技术去除内分泌干扰物（DMP）的影响

使用腐殖酸模拟本底天然有机物进行试验,采用UV-H₂O₂、O₃、UV-O₃3种高级氧化工艺,研究了水中腐殖酸对3种高级氧化联用技术去除饮用水中内分泌干扰物(DMP)的影响.结果表明,UV-H₂O₂联用工艺氧化DMP的过程符合伪一级反应动力学,水中腐殖酸的存在对UV-H₂O₂联用工艺氧化DMP的影响非常大,伪一级反应的速率常数与本底TOC值的关系式为K=0.162 0[TOC]₀^{-0.817 1};同时水中腐殖酸对UV-O₃联用工艺氧化DMP的效果影响比较大,而总体上腐殖酸对O₃氧化DMP的去除影响不大.从效果分析知,在一定浓度腐殖酸本底条件下单独O₃氧化和UV-O₃联用工艺对DMP的氧化均以O₃分子对DMP的氧化起主导作用,当腐殖酸浓度变小,UV-O₃联用工艺体系中.OH自由基氧化DMP的重要性增大.水中腐殖酸对3种高级氧化工艺的影响程度顺序依次为:UV-H₂O₂>UV-O₃>O₃.     

再生水中内分泌干扰物质的存在及处理现状

随着污水回用大力开展,人们与再生水的接触机会增加,必须保障再生水的水质安全.资料调研发现,作为再生水水源的污水处理厂出水中含有多种内分泌干扰物质,活性炭吸附、超滤、高级氧化技术及膜技术可有效去除再生水中的内分泌干扰物质,但鉴于经济和管理上的困难,目前仍不能全面推广.中国常用的澄清(混凝沉淀)/过滤工艺不能有效去除污水处理厂二级出水中的内分泌十扰物质,这对接触人群的健康产生潜在威胁,对生物种群也有一定的影响.生物处理方法未来有可能成为去除内分泌干扰物质很有前途的方法.     

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.     

Integral assessment of estrogenic potentials of sediment-associated samples

GOAL, SCOPE AND BACKGROUND: Exogenic endocrine-active substances are also called 'Endocrine Disrupting Chemicals' (EDC). They imitate or hinder the function of natural endogenic hormones or disturb the synthesis or the metabolism of hormones or of hormone receptors. The Enzyme-Linked Receptor Assay (ELRA) can detect estrogenic and anti-estrogenic effects at the level of receptor binding and is a useful tool for the integrative detection of contaminant effects. Although the test system has been used repeatedly in sediment assessments, the questions have remained concerning how it responds to variations in the physico-chemical matrix. For some bioassays, the salinity of the sample is a critical factor. This is especially relevant when testing wastewater samples or when sediment-associated samples in the tidal reaches of rivers are tested. Sediments in the tidal reaches of rivers change their salinity several times a day. Against this background, it would be beneficial to have a test procedure of known salinity tolerance. On account of this, the salinity tolerance of the ELRA was tested, assessed with reference substances at several salinity levels, and compared with the E-Screen method and a Yeast Estrogen Screen (YES), which are also frequently applied in environmental testing. The aim of this paper was to explore when the salinity limits within these test procedures are applicable. The trials should reveal the working range to be expected, characterize the salinity-dependent variations in sensitivity of the test, and provide options for methodological adjustments to improve the stability against increased salinity. METHODS: The ELRA was carried out with the human Estrogen Receptor alpha. (ER) using the same principle like a competitive immunoassay based on ligand-protein interaction. However, an essential difference is the use of a physiologically relevant receptor instead of an antibody as a linking protein. The ELRA measures the competition of sample estrogens and anti-estrogens against estradiol supplied as a BSA-coating conjugate for the binding site of dissolved ER. Estradiol or xeno-estrogen binding is quantified by a biotynilated anti-ER antibody and the subsequent measurement of peroxidase activity by a streptavidin-POD-biotin complex. The E-Screen was performed with the human breast cancer cell line MCF-7, which expresses the estrogen receptor constitutively. Cell proliferation depends on binding of estrogens or xeno-estrogens with the receptor. After incubation, estrogen-dependent cell growth was measured by sulforhodamin B staining. The YES was performed with a recombinant yeast strain, transfected with a receptor and a reporter plasmid bearing the estrogen receptor and a vitellogenin gene fused with the reporter gene lacZ. Estrogen or xeno-estrogen-dependent gene induction was measured indirectly by LacZ activity. The salinity levels were simulated in varying concentrations with NaCl from 0 to 40 per thousand or Artificial Sea Water (ASW) from 0 to 32 per thousand. RESULTS: The study characterized the factor 'salinity' for the prospective application fields of the ELRA. With reference substances such as 17-beta-estradiol, the ELRA showed classical sigmoidal concentration-effect relations in a range from 0.05 to 100 microg/l under physiological conditions. After a methodological adjustment to compensate decreasing receptor-binding affinity of estrogens and xeno-estrogens at higher salinity levels, the ELRA became applicable under salinity conditions up to concentrations of 20.5 per thousand. In tests, the ELRA reached under the influence of salinity a mean limit of detection of 0.062 microg/l 17-beta-estradiol. The mean relative inter-test error was around 11%. Above concentrations of 20.5 per thousand there is a risk of false negative assessment. Compared with the E-Screen method using the MCF7 cell line and the yeast estrogen test system (YES), the ELRA shows a lower sensitivity to 17-beta-estradiol. In the E-Screen, the cell proliferation was strongly reduced by sodium chloride induced cytotoxicity. In comparison with the E-Screen, the salinity tolerance of the YES and YAS methods is significantly higher. DISCUSSION: Despite adaption, total salinity tolerance could not be achieved with the ELRA. Freshwater samples were generally appraisable. Higher salinity levels above 20.5 per thousand would tend towards false negative results. The low inter-test error of 11% makes the ELRA suitable for the detection of estrogenic and anti-estrogenic potentials of single substances, substance mixtures, and of environmental samples. CONCLUSIONS: The ELRA is very fast and reproducible, it can be used for high-throughput screening in a microplate format at low cost, it is robust to microbial contamination, and is less susceptible to cytotoxic interferences than cell culture methods. RECOMMENDATIONS AND PERSPECTIVES: In their established form, the YES and the E-Screen methods are not applicable for liquid phase testing at higher salinity conditions. The salinity-adapted test version of the ELRA described here shows a broader working range for samples. Native water samples of more or less brackish origin or high-salinity effluent samples are testable. Results of tests with sediment associated samples of different salinity will be subject of a forthcoming publication.     

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.     

环境内分泌干扰物污染控制、削减措施及风险管理方法探讨

环境内分泌干扰物（EDCs）是一类广泛存在于环境中，能干扰正常内分泌功能的天然或人工合成的化合物，严重地威胁着生态环境及人类健康。简要介绍了环境内分泌干扰物的危害性及污染现状，分析探讨了对环境内分泌干扰物的控制、削减对策，并就如何加强生态风险管理谈了看法。     

4-壬基酚臭氧氧化中雌激素活性变化的影响因素

采用有效的重组基因酵母检测方法,研究了不同影响因素下水中典型内分泌干扰物4-壬基酚(4-NP)在臭氧氧化过程中雌激素活性的变化规律.结果表明,臭氧能迅速氧化4-NP,并有效地去除其雌激素活性;臭氧氧化过程中,水中高臭氧浓度、低pH值、低悬浮物含量、低·OH抑制剂浓度以及适量的腐殖酸浓度均有利于降低4-NP的雌激素活性.     

塑料包装物中邻苯二甲酸酯的分布统计分析

选取36种日用塑料包装物作为研究对象,采用方差分析和多重比较检验等统计方法,对其所含6种优先控制污染物—邻苯二甲酸酯(PAEs)的分布特点进行统计分析.结果表明,仅有2.78%的塑料样品没有PAEs被检出,50%的样品含有2种或2种以上PAEs;其中邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二(2-乙基)己酯(DEHP)分布最为广泛,存在于97.22%的样品中.塑料包装袋的来源、色彩与其ΣPAEs具有较高的关联性,菜市场包装袋的ΣPAEs显著高于超市塑料包装袋和一次性塑料包装袋的ΣPAEs;彩色塑料包装袋中ΣPAEs高于非彩色塑料包装袋;在材质中加入颜料的塑料包装袋其ΣPAEs明显高于表面彩绘的塑料包装袋.     

内分泌扰乱化学物质生物筛选技术研究进展

内分泌扰乱化学物质是环境科学领域研究的热点之一,已报道的内分泌扰乱化学物质达100种左右,但环境中大量的具有内分泌扰乱作用的化学物质还没有被认定.因此开展内分泌扰乱化学物质的筛选是当前的首要任务.笔者综述了国外内分泌扰乱化学物质的活体和离体生物筛选技术最新进展,并展望了国内外内分泌扰乱化学物质生物筛选技术研究的发展趋势.