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.     

内蒙古自治区实施排污权交易的探索

探索和建立排污权交易制度,实现稀缺环境资源的有偿使用,提高环境资源的配置效率,对于内蒙古自治区建立长效减排机制、改善环境质量有着非常现实的意义。本文在借鉴国内外排污权和碳交易理论和经验的基础上,分析内蒙古自治区排污权交易制度设计和实践特点,提出进一步完善和活跃内蒙古自治区排污权交易市场的对策建议。     

排污权交易应用于农业面源污染控制研究

当前农业面源污染已经成为我国水环境污染的主要根源,文中通过对农业非点源污染现状的调查和对治理污染的手段和措施的分析,结合排污权交易的优势和特点,探讨排污权交易体系引入农业非点源污染控制系统的可行性,相比较于大型工业点源,农业面源污染减排成本较低的状况为排污权交易提供了有利条件。在分析面源污染具有涉及个体多、发生不确定性强、减排结果监测困难等特征的基础上,提出了工业点源与农业面源排污权交易的总体框架。同时针对农业面源排污权交易中可能存在的一些问题进行了初步探讨,提出解决思路,期待着为今后相关研究抛砖引玉。     

流动注射在线UV消解测定环境水体中的总氮研究

采用San++流动分析仪在线UV消解测定环境水体中的总氮,样品浓度在0.00~5.0 mg/L与峰高有良好的线性关系(r=0.999 6)。进行了标准样品考核和实际水样的流动注射法和国标方法的比对分析。实验结果表明:采用流动注射在线消解测定水中TN,其标样测定值均在保证值范围内,相对标准偏差小于3%;两种方法测定实际水样的结果无显著性差异且具有很好的一致性,加标回收实验的回收率在90.0%~97.7%之间,能满足地表水及排放废水中TN监测要求。     

固定污染源排气中颗粒物测定的质量保证

固定污染源排气中颗粒物的监测是一个复杂的过程,它综合了实验室分析、现场采样及生产工艺等因素,是环保管理部门监控、考核企业污染物是否排放达标的重要因子之一。本文从滤筒的选择、实验室称量、采样仪器、采样点位置、运行工况等几方面提出了固定污染源排气中颗粒物测定中应注意的问题,并对实验室湿度和滤筒烘烤温度对滤筒称重的影响进行了测定,得出实验室的湿度应控制在两次称量土5％范围之内,同时应根据排气筒类型不同,选择不同的温度烘烤滤筒,否则会直接影响滤筒称量的准确度。只有做好固定污染源排气中颗粒物监测过程中各个环节的质量控制,才能获得科学、准确的监测数据。     

我国环境空气中颗粒物达标统计要求研究

基于世界卫生组织(WHO)和美国制定颗粒物达标统计要求的原则,利用我国120个城市2005~2012年可吸入颗粒物(PM10)的实际监测数据,通过统计回归法、比例反推法和控制图法对我国不同地理区划城市的颗粒物达标统计要求进行了分析研究.结果表明,当我国城市PM10浓度达到年均值标准时,大多数城市PM10日均值的达标率均在95.0%以上,平均为97.1%;其中华北、西北地区城市的平均达标率为96.3%,东北地区城市平均达标率为96.6%,华东、中南地区城市平均达标率为97.2%,西南地区城市平均达标率为98.1%.当我国PM10达标统计要求等于97百分位数时,日均值标准和年均值标准的控制力度基本匹配,当达标统计要求高于97百分位数时,日均值标准成为控制性标准,反之年均值标准成为控制性标准.综合考虑我国城市PM10浓度统计特征、百分位数的稳健性和对人体健康的保护性等各方面因素,我国宜选择95百分位数作为我国目前的PM10和PM2.5的日均值达标统计要求.     

青海三江源地区退化草地土壤全氮的时空分异特征

在第二次土壤普查和2009、2010年实地采样的基础上,运用地统计学和GIS技术研究了青海三江源地区1980～2010年退化草地0～10 cm、10～30 cm、30～50 cm全氮的时空分异特征.结果表明,进行特异值处理后,两期的土壤全氮的均值都表现出从表层到底层下降的趋势.从同一土层对比来看:2010年的土壤全氮的含量平均值及变异系数比1980年低.经对数转换后两期数据符合正态分布,经过半方差函数模型的拟合得出,两期同一层次上的块金效应2010年都比1980年小,表示三江源地区各分层上全氮的空间分布的自相关性在加强,结构性因素对土壤全氮的空间分布起着越来越重要的作用.普通克里格插值结果表明,30年来三江源地区土壤全氮的含量变化存在地区差异,南部、中部、东部以递减为主,西部的部分地区以增加为主.     

家用洗衣机微生物污染状况研究

在生活中,洗衣水往往是被人们所忽略的污染源。为了人们更加健康的生活更加健康的洗衣,本文对家用洗衣机内外筒以及洗衣水中细菌总数和大肠菌群数进行了取样测定,结果表明,各种样品的细菌总数结果很相近,并且远远超出了公共用品中其它公共用品卫生的标准,即细菌总数评价指标不大于300 cfu/25cm2;洗衣机内外筒的细菌总数结果相近。最后,本文通过分析其造成的污染状况,从而引导人们养成科学的洗衣习惯。     

穗花狐尾藻生长及酚类物质含量对光照强度的响应研究

沉水植物穗花狐尾藻(Myriophyllum spicatum)能产生对水华蓝藻生长有抑制效应的酚类活性物质。为了揭示光照强度对穗花狐尾藻的生长及其体内酚类物质含量的影响,文章研究了不同光照强度下穗花狐尾藻的生物量及其顶端组织与茎中的可溶性糖、可溶性蛋白、总酚的含量以及与酚类代谢相关酶——苯丙氨酸裂解酶(Phenylalanine ammonia-lyase,PAL)的活性,结果表明:穗花狐尾藻生物量随着光照强度的减弱而显著降低;高光照强度和中等光照强度下,顶端组织中可溶性蛋白、总酚含量和PAL酶活都明显高于茎中各指标;茎中的总酚含量、PAL酶活性在低光照强度下显著高于高光照强度和中等光照强度下。     

浅水湖泊水动力过程对藻型湖区水体生物光学特性的影响

基于2010年7月底至8月初对太湖藻型湖区梅梁湾沿岸带水域不同风速条件下水下光场的原位连续高频观测,通过对水下辐照度、光束衰减系数、吸收系数、相关理化参数及气象水文参数的测定与分析,揭示了该区域水体的生物光学特性变化及其与水动力过程的关系.结果表明,总颗粒物吸收系数ap(440)、非色素颗粒物吸收系数ad(440)、浮游植物吸收系数aph(440)及有色可溶性有机物吸收系数aCDOM(440)在小风(30 min内平均风速<3 m.s-1)、中风(3 m.s-1<风速<5 m.s-1)和大风(风速>5 m.s-1)作用下分别为3.97、3.97、6.58 m-1;1.69、2.17、4.20 m-1;2.28、1.80、1.33 m-1;1.05、1.04、1.08 m-1,其中变幅最大的为非色素颗粒物,CDOM吸收系数在不同风速条件下差别不大.水体各组分在PAR波段积分值的贡献率的变化规律为:小风速下浮游植物吸收系数的贡献最大(达42.5%),随着风速的增大,CDOM、浮游植物、纯水吸收系数的贡献率均有降低的趋势,而非色素颗粒物的贡献率则显著增大,分别为33.0%、41.7%、52.0%.PAR漫射衰减系数与10min平均风速呈显著线性相关,风速引起的沉积物再悬浮对PAR漫射衰减系数的影响显著,从小风到大风,PAR漫射衰减系数增加了80.0%,对应真光层深度降低了42.2%.PAR漫射衰减系数、750 nm波长处的光束衰减系数、总悬浮物浓度与风速、波高、波切应力均存在显著正相关,其中又以PAR漫射衰减系数的相关性最为显著.高频观测结果揭示了浅水湖泊藻型湖区水动力过程通过引起沉积物再悬浮、浮游植物的混合及迁移显著改变水体生物光学特性短期变化.