环境内分泌干扰物分析方法的研究与进展

本文对近5年来国内外环境内分泌干扰物的研究进展进行了综述,包括环境内分泌干扰物的分类、样品前处理技术、检测技术等,并对环境内分泌干扰物分析的发展进行了总结和展望,引用文献286篇。     

环境水体中酚类EDCs前处理技术及分析方法研究进展

环境内分泌干扰物(EDCs)是指干扰生物体内保持自身平衡和调节发育过程中天然激素的合成、分泌、运输、代谢、结合、反应、消除等生物过程的外源性化学物质,这类物质的存在会干扰人类和野生动物的内分泌系统,带来生殖障碍、发育异常、免疫功能减弱等问题。EDCs,尤其是使用最为广泛的酚类EDCs,在水环境中的污染特征研究已是当前科学界和公众共同关注的热点问题之一。环境样品基质非常复杂,使得痕量酚类EDCs的分析检测难度较大。该文对近年来环境水体中酚类EDCs的分析方法进行了综述,分别对样品前处理与检测分析技术进行了介绍,其中前处理技术包括样品萃取、样品净化和样品衍生化,检测分析技术包括化学分析和仪器分析。最后对酚类分析方法进行了展望。     

磁性氧化石墨烯的制备及其在环境水样中7种内分泌干扰物检测中的应用

制备了十二胺修饰的磁性氧化石墨烯纳米材料并将其用于磁固相萃取。在对磁固相萃取材料合成与萃取条件以及液相色谱分离等条件进行优化的基础上,建立了磁固相萃取与高效液相色谱-紫外检测对环境水样中7种内分泌干扰物的分析方法。该方法对雌酮、雌二醇、雌三醇、双酚A、17α-乙炔基雌二醇、己烷雌酚和雄烯二酮7种内分泌干扰物的检出限在0.10~0.23 nmol/L之间。将该方法分别应用于废水样品和湖水样品的加标回收试验,回收率在73.9%~112.9%和74.9%~114.7%之间。该方法操作简便,分析成本较低,可为环境水体中内分泌干扰物的分析提供技术支持。     

环境和生物样品中铂族金属的分析研究进展

评述了近年来环境和生物样品中痕量铂族金属的分析研究进展，重点介绍了样品的预处理和分离富集技术以及检测手段等。     

分子印迹聚合物用于环境内分泌干扰物的检测与去除

环境内分泌干扰物对人体健康和生态环境具有严重危害,发展高效的环境内分泌干扰物检测方法与去除技术具有重要意义。由于拥有高度的吸附选择性、较大的吸附容量和良好的可重复利用性,分子印迹聚合物在环境内分泌干扰物的检测与去除方面得到了诸多应用。本文介绍了分子印迹聚合物的制备方法及性能特点,综述了近年来基于分子印迹聚合物的固相萃取技术和传感器技术在环境内分泌干扰物的灵敏、特异性检测中的应用,以及基于分子印迹聚合物的吸附技术与其他方法的联用技术用于环境内分泌干扰物的选择性高效去除,并分析了分子印迹聚合物在合成和使用方面存在的问题,展望了其应用前景。     

效应引导的污染物分析与识别方法

识别环境样品中主要贡献污染物有助于确定环境风险的来源,是环境治理的前提。单一的化学分析和生物学检测方法常常遗漏主要贡献污染物的信息。效应引导的污染物识别(effected-directed analysis, EDA)是以生物检测引导组分分离、化学分析与污染物鉴定的实用方法,是环境风险评价以及环境样品中主要贡献污染物筛查与识别的有力手段。该方法已成功用于环境中遗传毒物、内分泌干扰物和芳香烃受体效应污染物等污染物的鉴定,为特定污染地区贡献污染物及其来源的确定提供了宝贵的基础数据。本文综述了EDA中所应用的样品提取、分离策略、生物效应检测以及贡献化合物的识别方法,总结了近年来以EDA为手段在环境中识别的效应污染物并对目前EDA应用所存在的问题与未来的发展趋势进行了分析。     

环境及生物样品中铂分析研究的进展

介绍了近年来环境及生物样品中铂分析研究的进展。特别是对大气尘埃及土壤中铂的分布，转移规律以及植物和动物样品中不同化学形态铂的分离，分析方法及分析结果作了着重介绍。     

冷冻干燥技术在环境水样有机新污染物前处理中的应用进展

有机新污染物是一类在先进分析技术帮助下新鉴定的、现有法规未管制的、人为源的有机污染物。有机新污染物主要包括药品与个人护理、农药、全氟化合物、内分泌干扰物等,其会产生内分泌干扰效应、诱发抗性基因传播,还对人类和野生生物的生存与发展构成潜在威胁,因此检测环境样品中的有机新污染物浓度对生态环境和人体健康具有重大意义。由于环境样品中的有机新污染物浓度较低,为了达到检测仪器的检测要求,通常需要对环境样品进行前处理,包括样品的净化和浓缩。冷冻干燥技术是一种在真空干燥条件下通过升华方式去除水分的前处理技术,主要包括样品冷冻、初级干燥和再干燥3个阶段,常用于食品和药品行业。在药品行业中,冷冻干燥技术能维持药品的生物活性和化学活性,保持药品的物理化学特性。近年来,冷冻干燥技术逐步用于环境水样中有机新污染物的前处理。其主要的操作步骤包括水样预处理、冷冻干燥、洗脱、吹干、过滤、定容和上机检测。冷冻干燥技术具有操作简单、低成本、样品处理体积少、样品易保存和处理过程中样品损失少等优点,具有广泛应用于环境样品中有机新污染物监测的潜力。该文综述了环境样品中有机新污染物常见的种类,并重点介绍冷冻干燥技术的原理及其在环境样品前处理过程中的应用,提出了冷冻干燥技术在环境分析中的应用前景,为环境样品中有机新污染物的监测提供了参考。     

卵黄蛋白原的分离测定及其在环境内分泌干扰物质筛选中的应用

环境内分泌干扰物的存在直接威胁野生动物的生存和人类的健康，对其作用机制及筛选方法的研究，已经成为环境科学研究的热点领域。近年来，卵黄蛋白原作为环境内分泌干扰物的“生物标志物”，得到了较深入的研究。本文讨论了卵黄蛋白原的分离测定方法及其在内分泌干扰物筛选中应用的最新进展，为建立更有效的卵黄蛋白分离测定方法及发展新的环境内分泌干扰物筛选技术提供参考。     

环境样品中痕量邻苯二甲酸酯的分离与测定

本文研究了以小粒径（１０－４０μ）硅胶柱色谱分离富集、反相高效相色谱分析测定大气颗粒物、土主植物样品中痕量邻苯二甲酸酯的方法，方法操作简单，回收率高，空白值低，利用该方法分析了部分环境样品中邻苯二甲酯酯含量。     

Application of chemometric methods to the investigation of main microcontaminant sources of endocrine disruptors in coastal and harbour waters and sediments

Identification, resolution and distribution of main microcontaminant sources of endocrine disruptors in Spanish harbours, coastal waters and sediments are investigated using chemometric methods. We investigated eighteen different endocrine disruptor chemical compounds, including non-ionic surfactants, their degradation products and linear alkylbenzene sulfonates, found in a total number of 74 samples (35 water samples and 39 sediment samples) over a period of 16 months from March 1999 to July 2000, and in 32 different geographical sites along the Spanish Mediterranean Coast (e.g. Barcelona, Tarragona, Almeria Harbour, Malaga and the Bay of Cadiz). Main environmental contamination sources of these endocrine disruptor compounds were investigated and interpreted according to their chemical composition and according to their resolved geographical distribution profiles.An erratum to this article can be found at     

“Orange alert”: A fluorescent detector for bisphenol A in water environments

Due to the prevalent use of polycarbonate plastics and epoxy resins in packaging materials and paints for ships, there has been a widespread global contamination of environmental water sources with bisphenol A (BPA). BPA, an endocrine disruptor, has been found to cause tremendous health problems. Therefore, there is an urgent need for detecting BPA in a convenient and sensitive manner to ensure water safety. Herein, we develop a fluorescent turn-on BPA probe, named Bisphenol Orange (BPO), which could conveniently detect BPA in a wide variety of real water samples including sea water, drain water and drinking water. BPO shows superior selectivity toward BPA and up to 70-fold increase in fluorescence emission at 580 nm when mixed with BPA in water. Mechanistic studies suggest a plausible water-dependent formation of hydrophobic BPA clusters which favorably trap and restrict the rotation of BPO and recover its inherent fluorescence.     

Characterization of paint samples used in drinking water reservoirs: identification of endocrine disruptor compounds

Several migration tests are performed from various epoxy paint samples that, according to the regulation, can be used in food reservoirs such as drinking water reservoirs. The level of the organic compounds capable of producing migrations to water with special attention to endocrine disruptor compounds (EDCs) are identified and estimated by closed loop-stripping analysis (CLSA) and liquid-liquid extraction (LLE) methods coupled with gas chromatography (GC)-mass spectrometry (MS). Bisphenol A, a strong endocrine disruptor, is found in all migration experiments. Its concentration level reaches between 0.02 and 0.03 mg/cm2. The higher concentration corresponds with benzylic alcohol, which is used as a solvent and curing agent in epoxy paint. Other EDCs identified in the migration tests are phthalates, 4-nonylphenol, and t-butylphenol. The main non-EDCs identified are solvents, antioxidants, and rubber-like compounds. No great differences are found in the use of metallic plates or concrete slabs for migration experiments; only additional compounds related with the pretreatment of the concrete wall have been identified, too. In the study of a drinking water sample the same organic compounds identified in the migration test is not seen. This is probably because of the dynamic situation in a drinking water reservoir. Finally, a GC profile of a direct epoxy paint analysis is shown. The main peak identified is bisphenol A diglycidyl ether, monomer, and an active principle of the polymerization of epoxy resins based on bisphenol A. In addition, we report the recoveries of a selected group of EDCs using CLSA and LLE methods coupled with GC-MS.     

Novel modes of capillary electrophoresis for the determination of endocrine disrupting chemicals

The synthesis and usage of a wide range of organic chemicals has increased dramatically over the last five decades. These compounds sometimes termed endocrine disrupting chemicals include agricultural pesticides, industrial solvents, dyes, plasticisers, detergents and heat exchangers. Concerns have been raised about the potential adverse effects of these compounds on humans and wildlife species. Our objectives are to develop a method to identify, using novel capillary electrophoretic techniques, the endocrine disrupting compounds that are reported to be present in environmental samples. The CE modes, capillary zone electrophoresis, micellar electrokinetic chromatography (MEKC), cyclodextrin-modified MEKC (CD-MEKC) and electroosmotic flow-suppressed CD-MEKC were investigated for the determination of a range of endocrine disrupting chemical compounds. This paper shows some initial results obtained.     

汞的环境生化分析进展

汞是一种毒性很大的环境内分泌干扰物,全球环境中存在各种形式的汞已经严重地威胁着人类的健康.因此,发展高灵敏度、高选择性检测汞的分析新方法对环境监测和临床医学研究具有十分重要的意义.对近年来环境中汞的生化分析方法进展作了综述,引用文献61篇.     

Molecularly imprinted polymer film grafted from porous silica for efficient enrichment of steroid hormones in water samples

Steroid hormones as endocrine disrupting compounds can interfere with the functioning of hormonal systems of organisms and thus affect the health and reproduction of humans and wildlife. Unfortunately, these types of harmful endocrine disrupting compounds have been found in a variety of environmental samples at very low concentrations. Therefore, a simple, fast, and efficient method for enrichment of water samples is needed. A molecularly imprinted solid‐phase extraction combined with high performance liquid chromatography coupled with diode array detection was developed for the determination of six steroid hormones, such as estrone, 17‐β‐estradiol, estriol, 17‐α‐ethinylestradiol, progesterone, and testosterone in water samples. The recoveries obtained in the proposed method were in the range of 78.7–101.3%. Matrix effect below 20% suggests that the quantitative and qualitative results of the analysis were not significantly affected by the matrix. The results show that molecularly imprinted polymers based on spherical silica gel had the potential to be a highly innovative and selective sorbent. The proposed method was proved to be applicable for molecularly imprinted solid‐phase extraction in selective and reliable extraction and enrichment of steroid hormones in environmental water samples.     

分子烙印固相萃取技术在环境样品分析中的应用

分子烙印固相萃取技术克服了传统固相萃取技术选择性差的缺陷,实现了对复杂样品中特定分析对象或杂质的选择性提取,从而大大提高了分析测试的精度和准确性,并降低了检测限。该文对分子烙印聚合物(MIPs)作为固相萃取填料从复杂的环境样品中分离、富集和纯化微量及痕量的目标化合物进行了综述,涉及的目标化合物包括杀虫剂、除草剂、兽药等各类农药残留以及重金属离子和某些生物毒素等。     

Liquid chromatographic separation of the enantiomers of trans-chlordane, cis-chlordane, heptachlor, heptachlor epoxide and alpha-hexachlorocyclohexane with application to small-scale preparative separation

Analytical high-performance liquid chromatographic separations of the individual enantiomers of five polychlorinated compounds were obtained on polysaccharide stereoselective HPLC columns. The enantiomers of the pesticides trans-chlordane, cis-chlordane and heptachlor were separated on CHIRALCEL OD using a hexane mobile phase. The enantiomers of the heptachlor metabolite, heptachlor epoxide, were separated on CHIRALPAK AD using a methanol mobile phase. The enantiomers of alpha-hexachlorocyclohexane (alpha-HCH), were separated on CHIRALCEL OJ using a hexane/2-propanol mobile phase. Similar chromatographic conditions using preparative columns were used to isolate approximately 250 mg of each of the individual enantiomers. The purified individual enantiomers have been submitted for testing of their endocrine disruptor (ED) activity.     

The Metal–Organic Framework MIL‐53(Al) Constructed from Multiple Metal Sources: Alumina,Aluminum Hydroxide,and Boehmite

Three aluminum compounds, namely alumina, aluminum hydroxide, and boehmite, are probed as the metal sources for the hydrothermal synthesis of a typical metal–organic framework MIL‐53(Al). The process exhibits enhanced synthetic efficiency without the generation of strongly acidic byproducts. The time‐course monitoring of conversion from different aluminum sources into MIL‐53(Al) is achieved by multiple characterization that reveals a similar but differentiated crystallinity, porosity, and morphology relative to typical MIL‐53(Al) prepared from water‐soluble aluminum salts. Moreover, the prepared MIL‐53(Al) constructed with the three insoluble aluminum sources exhibit an improved thermal stability of up to nearly 600 °C and enhanced yields. Alumina and boehmite are more preferable than aluminum hydroxide in terms of product porosity, yield, and reaction time. The adsorption performances of a typical environmental endocrine disruptor, dimethyl phthalate, on the prepared MIL‐53(Al) samples are also investigated. The improved structural stability of MIL‐53(Al) prepared from these alternative aluminum sources enables double‐enhanced adsorption performance (up to 206 mg g^?1) relative to the conventionally obtained MIL‐53(Al).     

固相萃取-反相高效液相色谱法测定水中的邻苯二甲酸酯

建立了固相萃取-反相高效液相色谱法检测水中3种邻苯二甲酸酯类物质邻苯二甲酸二甲酯、邻苯二甲酸二(2-乙基己基)酯、邻苯二甲酸二正辛酯的方法. 考察了固相萃取柱、洗脱溶剂、洗脱体积、上样速度以及洗脱速度对萃取效率的影响. 通过综合分析, 选定SupelcleanLC-18 SPE Tube固相萃取柱, 甲醇为洗脱剂, 洗脱体积2 mL, 上样速度为4 mL/min, 洗脱速度为1 mL/min. 在此萃取条件下, 萃取回收率在83.4%～121.2%之间. 邻苯二甲酸二甲酯、邻苯二甲酸二(2-乙基己基)酯、邻苯二甲酸二正辛酯质量浓度在2～100 mg/L之间均为线性. 经萃取后, 方法的最低检出限分别为邻苯二甲酸二甲酯0.06 μg/L, 邻苯二甲酸二(2-乙基己基)酯0.16 μg/L, 邻苯二甲酸二正辛酯0.08 μg/L. 方法的精密度在10%～15%之间. 应用该方法测定自来水中酞酸酯类化合物的含量, 加标回收率为83.6%～110.2%.