固相萃取-微乳液相色谱法测定环境水体中的3种酚类化合物

建立了固相萃取-微乳液相色谱法同时测定环境水体中的苯酚、双酚A (BPA)、2,4-二氯苯酚3种酚类化合物的检测方法。水样加酸酸化后,经C18固相萃取小柱富集净化,用微乳液相色谱法测定3种目标物的含量。在Inertsil C18色谱柱(150 mm×4.6 mm, 5 μm)上以微乳(3.0%十二烷基硫酸钠(SDS)-6.0%正丁醇-0.8%正庚烷-90.2%(水+0.5%HAc))和乙腈作为流动相进行梯度洗脱,流速1.0 mL/min,检测波长280 nm。结果表明,苯酚、双酚A、2,4-二氯苯酚的检出限(S/N=3)依次为0.74、8.0、8.0 μg/L,线性范围在0.1~10 mg/L范围内,相关系数(r)均大于0.999。将3种酚类化合物定量加到空白水样中,苯酚、双酚A、2,4-二氯苯酚的加标回收率分别为82.7%、87.8%、82.6%,其RSD均小于5%(n=6)。对环境水样的酚类化合物分析也取得了良好的加标回收率,其值均在85.7%~113.2%之间。结果表明,该方法准确可靠、灵敏度高,适用于环境水体中酚类化合物的检测。     

包装材料中的酚类环境雌激素的测定-固相微萃取/气相色谱质谱法

建立了固相微萃取-气相色谱质谱法(SPME/GCMS)快速测定包装材料中的烷基酚、双酚A的分析方法,以CH2Cl2为提取溶剂,采用快速溶剂萃取法萃取包装材料中的酚类物质,萃取物经N,O双(三甲基硅烷基)三氟乙酰胺(BSTFA)衍生化后,用PDMS/DVB纤维萃取,利用GC-MS对包装材料中4-叔-丁基酚、4-叔-辛基酚、4-辛基酚、4-壬基酚、双酚A 5种目标物进行定性定量分析。结果表明,酚类物质主要存在于聚碳酸酯材料中,检测4-叔-辛基酚、4-辛基酚和双酚A的质量分数分别为82.44、60.28和78.35μg/kg。     

超高效液相色谱–串联质谱法测定食品接触材料中烷基酚物质迁移量

建立了超高效液相色谱-串联质谱法测定食品接触材料中双酚A、四溴双酚A、壬基酚和辛基酚迁移量的方法。样品经蒸馏水、3%乙酸溶液、10%乙醇溶液、20%乙醇溶液、50%乙醇溶液和异辛烷6种食品模拟物浸泡处理,浸泡液经C18色谱柱分离,以多反应监测(MRM)模式进行定性和定量。检测结果表明:在水基、酸性、酒精类食品模拟物中,双酚A、四溴双酚A、壬基酚、辛基酚的质量浓度均在0.001~0.50μg/mL范围内与其质谱响应值具有良好的线性关系,相关系数均不小于0.9995,方法检出限为0.01~0.25μg/kg,定量限为0.03~0.83μg/kg;在油基食品模拟物中,双酚A、四溴双酚A、壬基酚、辛基酚的线性范围均为0.01~0.50μg/mL,相关系数均不小于0.9989,方法检出限为0.10~2.50μg/kg,定量限为0.33~8.32μg/kg。双酚A、四溴双酚A、壬基酚、辛基酚的加标回收率为87.2%~101.2%,相对标准偏差为1.5%~3.4%(n=6)。该法样品处理步骤简单,准确度高,灵敏度好,可用于食品接触材料中烷基酚类化合物的检测。     

连续流动液膜萃取中液膜有机溶剂的选择

以具有不同极性的环境内分泌干扰物双酚A、辛基酚和壬基酚为模型化合物，对连续流动液膜萃取中用作液膜的有机溶剂进行了选择；结果表明，不同极性的有机溶剂对于极性不同的化合物的萃取效率明显不同。     

BSTFA-GC-MS联用技术分析测定痕量酚类内分泌干扰物

采用N,O-双三甲基硅基三氟乙酰胺-气相色谱-质谱分析化学手段,建立了壬基酚二氧乙烯醚(nonylphenol-di-ethoxylate,NP2EO)、壬基酚单氧乙烯醚(nonylphenol-mono-ethoxylate,NP1EO)、4-壬基酚(4-nonylphenol,4-NP)、双酚A(bisphenol A,BPA)、枯烯基酚(4-cumylphenol,4-CP)和4-t-辛基酚(4-t-octylphenol,4-t-OP)六种典型酚类内分泌干扰物(endocrine disrupting chemicals,EDCs)高效、可靠的分析方法。酚类EDCs衍生化条件是以N,O-双三甲基硅基三氟乙酰胺为衍生化试剂,在70℃条件下反应50 min。该方法简化了操作、改善了色谱峰形,检出限较低,具有很好的重现性,相对标准偏差(RSDs)小于1%。运用该方法对某污水处理厂进水中的酚类EDCs进行了分析检测,验证了该方法能够很好的应用于环境样品中痕量酚类EDCs的定量分析,具有较大地实用价值。     

液相色谱-串联质谱法同时测定玩具中5种酚类内分泌干扰物

采用液相色谱-串联质谱法测定玩具中5种酚类内分泌干扰物(即双酚A、对叔辛基酚、邻正壬基酚、对正辛基酚及对正壬基酚的含量)。ABS塑料玩具样品以四氢呋喃为提取溶剂,超声辅助溶解,用甲醇沉淀塑料基质;布绒玩具样品用甲醇作为提取溶剂,超声提取。提取液采用Waters XBridge C_(18)色谱柱分离,以不同比例的甲醇和0.1%(体积分数)氨水溶液的混合液作为流动相进行梯度洗脱,洗脱液供质谱分析,质谱测定中选择电喷雾负离子源和多反应监测模式。5种化合物的质量浓度在一定范围内与峰面积呈线性关系,上述5种酚类化合物的测定下限(10S/N)分别为1.0,1.0,1.0,0.5,0.5μg·kg~(-1)。加标回收率在87.4%~105%之间,测定值的相对标准偏差(n=6)均小于9.1%。     

[Bmim]BF4-NaH2PO4双水相萃取-高效液相色谱法测定水中痕量氯酚类内分泌干扰物

利用离子液体双水相萃取-高效液相色谱(HPLC)法测定了水中痕量氯酚类内分泌干扰物.以2,4-二氯酚(2,4-DCP)、2,6-二氯酚(2,6-DCP)和对氯苯酚(4-CP)为目标分析物,考察了影响离子液体双水相萃取率的主要因素,如分相盐的浓度、水相pH值、萃取时间及离子液体加人量.当NaH2PO4的浓度为0.5 g/...     

衍生化分散液液微萃取与气相色谱-质谱联用测定水中的烷基酚

烷基酚(Alkylphenols,APs)类化合物是一类典型的环境内分泌干扰物,主要包括辛基酚(Octylphenol,OP)和壬基酚(Nonylphenol,NP)的不同异构体~([1,2]).研究表明,珠江三角洲的河流水体及表层沉积物已经受到烷基酚类化合物的污染~([3,4]),其对水生生态系统和食物链的带来的影响和危害将不可忽视~([5]).     

酚类环境雌激素的分析研究进展

环境中分布或残留的化学物质对人类和野生动物的内分泌系统的不良影响已引起广泛关注。在已发现的数十种环境内分泌干扰物中，壬基苯酚、辛基苯酚、双酚A和2，4－二氯酚等以其相似的结构特征和类雌激素活性逐渐被划分为一类新的分析研究对象，称为酚类环境雌激素。本文综述了这些物质的主要来源和分布及其分析测定的研究进展，重点评述了一些新的分析技术如基体固相分散萃取法（MSPD）、分子印迹聚合物法（MIP）、荧光分子传感法（FMS）和生物识别－化学分析联用法等在上述物质的分析测定中的应用。比较了GC－MS和LC－MS等手段用于分析此类物质的优势和各自的局限性，并展望了这一领域未来的研究发展趋势。本文引用文献共54篇。     

分散液液微萃取-衍生化高效液相色谱-荧光检测法测定环境水样中4种酚类内分泌干扰物

为实现小体积环境水样中酚类化合物的准确、快速、高灵敏测定,通过分散液液微萃取(DLLME)和荧光衍生化的结合,建立了高效液相色谱-荧光检测(HPLC-FLD)双酚A、壬基酚、辛基酚和对特辛基酚的分析方法。考察并优化了DLLME和衍生化条件,结果表明,最优的DLLME条件为萃取剂氯仿用量70μL,分散剂乙腈用量400μL,漩涡振荡3 min,高速离心2 min。以2-[2-(7 H-二苯并[a,g]咔唑-乙氧基)]-乙基氯甲酸酯(DBCEC-Cl)为柱前衍生试剂,在pH10.5的Na2CO3-NaHCO3缓冲液/乙腈溶液、50℃下衍生反应3 min得到稳定的衍生产物,于10min内实现了4种酚衍生物的分离。方法的检出限为0.9~1.6 ng/L,定量限为3.8~7.1 ng/L,具有良好的线性、精密度和回收率,与以往报道的方法相比具有一定的优势和实用性,可用于造纸厂废水、湖水、生活废水、自来水中4种酚类内分泌干扰物的测定。     

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     

Determination of endocrine disruptors in water after derivatization with N-methyl-N-(tert.-butyldimethyltrifluoroacetamide) using gas chromatography with mass spectrometric detection

The combined gas chromatographic determination of a number of hydroxyl-group containing endocrine disruptors, including 4-octylphenol, 4-nonylphenol, 2,4-dichlorophenol, pentachlorophenol, 4-tert.-butylbenzoic acid, bisphenol-A, 17beta-estradiol and 17alpha-ethynylestradiol, was investigated. Derivatization, required for sensitive determination of these compounds, was carried out using N-methyl-N-(tert.-butyldimethyltrifluoroacetamide). A number of parameters affecting the derivatization reaction, like temperature, time, matrix, solvent, and amount of reagent were studied in detail. Quantitative yields were obtained for real-life extracts after optimization, but the hormones were only mono-substituted. Both solid-phase extraction (SPE) and liquid-liquid extraction were studied as extraction methods, with emphasis on SPE material and effect of pH. Recoveries and RSD for analysis of surface water samples were 58-106 and 6-16% (n=4), respectively, when using SPE, and 109-117 and 6-14% (n=6) when using liquid-liquid extraction. The method developed allows routine analysis of surface water for traces of endocrine disruptors. The limits of detection of were 4-6 ng/l but higher for the hormones.     

Characteristics of phenol and chlorinated phenols sorption onto surfactant-modified bentonite

Surfactant-modified bentonite was synthesized by replacing adsorbed Na+ with long-chain alkyl quaternary ammonium cation, hexadecyltrimethylammonium bromide (HDTMAB). The sorption isotherms of phenol, p-chlorophenol, and 2,4-dichlorophenol were modeled according to the Langmuir and Freundlich equations. The Langmuir isotherm was found to describe the equilibrium adsorption data well. The mechanisms and characteristics of sorption of these ionizable organic contaminants onto surfactant-modified bentonite from water were investigated systematically and described quantitatively. The sorption properties are affected by the treatment conditions, such as amount of organobentonite, and the properties of organic compounds. Results indicated that adsorption of phenols from water was in proportion to their hydrophobicities, which increased with chlorine addition (phenol相似文献   

Analytical methodologies for determining the occurrence of endocrine disrupting chemicals in sewage treatment plants and natural waters

In this study, a method for assessing the occurrence of trace amounts of 12 representative estrogenic compounds in sewage and surface waters was developed. The selected substances were the phytoestrogens daidzein, genistein and biochanin A, the alkylphenols bisphenol A and 4-nonylphenol, the natural hormones 17β-estradiol, estrone, estriol and the synthetic hormone 17α-ethynylestradiol and the mycoestrogens zearalenone and two of its metabolites (α-zearalanol and β-zearalanol). The procedure consists in solid phase extraction (SPE) performed with OASIS cartridges followed by liquid chromatography coupled with tandem mass spectrometry (LC-MS-MS). Recoveries were all above 80% for each analyzed aqueous matrices. The developed method was applied to verify the occurrence of endocrine disrupters in environmental samples of sewage influents and effluents of an Italian STP. Phytoestrogens were present in effluents at concentrations ranging from 3 to 83 ng/l, whereas the levels detected for alkylphenols were in the range 13-36 ng/l for bisphenol A and up to 1 μg/l for nonylphenol. Estrogens and zeranols were determined at levels below 30 ng/l. Analysis of a river (Tiber) receiving effluent waters revealed high quantities of bisphenol A (15-29 ng/l) and nonylphenol (up to 1.2 μg/l), whereas the presence of all the other compounds were at levels of few ng/l.     

Determination of endocrine disruptors in environmental waters using poly(acrylamide-vinylpyridine) monolithic capillary for in-tube solid-phase microextraction coupled to high-performance liquid chromatography with fluorescence detection

A method for the determination of endocrine disruptors, bisphenol A and 17alpha-ethinylestradiol, in environmental water samples was developed using in-tube solid-phase microextraction followed by liquid chromatography and fluorescence detection. A poly(acrylamide-vinylpyridine) monolithic capillary column was applied as the extraction media in view of its greater phase ratio than open-tubular capillaries and thus higher extraction efficiency. After optimizing the extraction conditions, bisphenol A and 17alpha-ethinylestradiol were extracted directly from water samples in a wide dynamic linear range of 0.5-1000 ng mL(-1), with the detection limits obtained as 0.064 and 0.12 ng mL(-1), respectively. The precision of the method was satisfactory with the intraday and interday RSD values smaller than 7.2%. Environmental water samples of different sources were successfully analyzed with the presented method and the monolithic capillary was proved to be robust and reusable in analyzing real water samples.     

Isotope dilution gas chromatography with mass spectrometry for the analysis of 4‐octyl phenol, 4‐nonylphenol,and bisphenol A in vegetable oils

By the combination of solid‐phase extraction as well as isotope dilution gas chromatography with mass spectrometry, a sensitive and reliable method for the determination of endocrine‐disrupting chemicals including bisphenol A, 4‐octylphenol, and 4‐nonylphenol in vegetable oils was established. The application of a silica/N‐(n‐propyl)ethylenediamine mixed solid‐phase extraction cartridge achieved relatively low matrix effects for bisphenol A, 4‐octylphenol, and 4‐nonylphenol in vegetable oils. Experiments were designed to evaluate the effects of derivatization, and the extraction parameters were optimized. The estimated limits of detection and quantification for bisphenol A, 4‐octylphenol, and 4‐nonylphenol were 0.83 and 2.5 μg/kg, respectively. In a spiked experiment in vegetable oils, the recovery of the added bisphenol A was 97.5–110.3%, recovery of the added 4‐octylphenol was 64.4–87.4%, and that of 4‐nonylphenol was 68.2–89.3%. This sensitive method was then applied to real vegetable oil samples from Zhejiang Province of China, and none of the target compounds were detected.     

Use of polymeric sorbents for the off-line preconcentration of priority pollutant phenols from water for high-performance liquid chromatographic analysis

The use of porous polymeric minicolumns for the determination of phenols from the U.S. Environmental Priority Pollutant List was studied. For the off-line preconcentration of priority pollutant phenols from water by solid-phase extraction, minicolumns packed with 1,4-di(methacryloyloxymethyl)naphthalene-divinylbenzene copolymer and Amberlite XAD-4 were used. In order to compare the sorption properties of these polymeric sorbents, the recoveries and breakthrough volumes of phenol, p-nitrophenol, 2,4-dinitrophenol, o-chlorophenol, o-nitrophenol, 2,4-dimethylphenol, 4-chloro-m-cresol, 4,6-dinitro-o-cresol, 2,4-dichlorophenol, 2,4,6-trichlorophenol and pentachlorophenol were studied.     

Determination of Endocrine Disruptors in Environmental Water by Single-Drop Microextraction and High-Performance Liquid Chromatography

Using single-drop microextraction followed by high performance liquid chromatography, an effective method for the rapid extraction for endocrine disruptors, including estrogens and alkylphenols, was developed. Factors that influenced the extraction efficiency, such as hydrogen bonding, hydrophobic property, polarity, and van der Waals forces, were evaluated in detail. The results indicated that bisphenol A and estrogens were extracted effectively by the solvents with hydrogen bond acceptors and higher polarity; alkylphenols preferred solvents that could supply strong van der Waals forces or possessed π-π stacking structures and superior hydrophobicity. The optimum extraction conditions were determined, including extraction time, pH, and salt effects. Under the optimized conditions, high extraction factors (≥147) were achieved. Limits of detection for the endocrine disruptors were between 0.33 and 0.67 µg L^?1. The method strategy is well suited for the determination of trace levels of endocrine disruptors in environmental water.