Simultaneous determination of alkylphenol ethoxylates and their biotransformation products by liquid chromatography/electrospray ionisation tandem mass spectrometry

Reversed-phase LC-MS/MS is used to determine major estrogenic alkylphenol ethoxylates (APEOs) and their biotransformation products. It allows the simultaneous analysis of eight APEOs, alkylphenoxy carboxylates (APECs) and alkylphenols (APs) in sewage treatment plant (STP) effluents in the same extract after solid-phase enrichment on polymeric Oasis HLB. As precursor ions, [APEO + NH4]+, [APEC - H]- and [AP - H]- were monitored. Instrumental limits of detection (LOD) were 2-600 pg, corresponding to sample concentrations of 0.04-12 ng l(-1), without correction for overall method recoveries. Matrix-induced signal suppression during electrospray ionisation (ESI) and extraction as well as overall method recoveries were assessed and the suitability of deuterated surrogates as internal standards was evaluated.     

Express detection of nonylphenol in water samples by fluorescence polarization immunoassay

The development of express method for detection of endocrine-disrupting chemicals (EDC) such as alkylphenols is required for ecological monitoring. Several attempts have been made to produce antibodies against 4-nonylphenol (NP) in recent years. This work describes the production of new antibodies against NP and also summarizes the characterization of antibodies obtained earlier. Three approaches used to produce alkylphenol-specific antibodies are compared; these are based on: 1. omega-(4-hydroxyphenyl)nonanoic or omega-(4-hydroxyphenyl)heptanoic acid NP derivatives designed to mimic the linear NP isomer; 2. 4-aminophenol, which potentially mimics various substituted phenolic compounds with different side-chain structures at position 4 of the benzene ring; and 3. a mixture of branched NP isomers, conjugated to the carrier protein via a benzene ring by the Mannich reaction, and expected to be the closest mimic of NP structure by preserving its natural alkyl moiety.Fluorescence polarization immunoassays based on different combinations of antibody and labeled antigen for screening detection of NP were developed and structural aspects of assay sensitivity and specificity were investigated. The assays based on the antisera raised against omega-(4-hydroxyphenyl)nonanoic acid and NP conjugate via Mannich reaction are capable of express detection of NP with detection limit of 7 microg mL(-1 )and assay dynamic range of 18-300 microg mL(-1).     

Determination of nonylphenol and octylphenol in paper by microwave-assisted extraction coupled to headspace solid-phase microextraction and gas chromatography-mass spectrometry

A novel and simple method for the determination of active endocrine disrupter compounds (octylphenol OP, and nonylphenol NP) in paper using microwave-assisted extraction (MAE) and headspace solid-phase microextraction, coupled with gas chromatography-mass spectrometry has been developed. Parameters affecting the efficiency in the MAE process such as exposure time and extraction solvent were studied in order to determine operating conditions. The optimised method was linear over the range studied (1.25-125 microg kg(-1) for OP and 9.50-950 microg kg(-1) for NP) and showed good level of precision, with a RSD lower than 10% and detection limits at 0.10 and 4.56 microg kg(-1) for OP and NP, respectively. The results obtained from six different types of paper revealed the presence of the target compounds in all samples analysed, at levels ranging between 3 and 211 microg kg(-1).     

Development and validation of a method for the determination of trace alkylphenols and phthalates in the atmosphere

An analytical method has been developed for the simultaneous extraction and determination of trace tertiary octylphenol (t-OP), technical nonylphenol isomers (NP), nonylphenol monoethoxylate isomers (NP1EO) and seven phthalates in the atmosphere using gas chromatography-mass spectrometry (GC-MS). High volume samples were collected using a high-volume pump equipped with a PUF/XAD-2 column for air and glass fiber filter for particles. The detection limits of the method for alkylphenols (APs) and the phthalates ranged from 0.0006 to 0.034 ng m⁻³ in air. The recoveries of t-OP, NP, NP1EO and the phthalates for the entire procedure were satisfactory (>69%). The method was successfully applied to the determination of the analytes in the atmosphere samples collected over land and the ocean. The concentrations of t-OP, NP, NP1EO showed decline trends from land to the open sea, and the phthalates present over land and the North Sea were comparable. It is suggested that the atmosphere is a significant pathway for the transport of alkylphenols and the phthalates in the environment.     

Extraction of Nonylphenol and Nonylphenol Ethoxylates from River Sediments: Comparison of Different Extraction Techniques

Summary Five different extraction techniques (Soxhlet, automated Randall, accelerated solvent extraction, microwave-assisted solvent extraction and extraction with a surfactant solution) have been evaluated for the determination of nonylphenol (NP) and nonylphenol ethoxylates (NPEO) in river sediments. All the techniques were applied to the same three samples collected from northern Italian rivers. The analyses were performed with two RP columns, with different stationary reversed phases—a classical C₁₈ phase and a hexyl–phenyl phase. The recoveries and reproducibility of the different extraction techniques were comparable and all the methods gave reliable results. The variance of the results was dominated by the variance in sample homogeneity, sample preparation, and chromatographic analysis. A choice between the methods can be made on the basis of the cost and safety of each technique. Preliminary results obtained from use of a water-based extraction method with a surfactant solution (Tween-80), and its application to analysis of sediment and of worm tissue, are also presented.Presented at: Chemical Analysis and Risk Assessment of Emerging Contaminants, Barcelona, Spain, November 28–30, 2002     

Determination of 4-nonylphenol and 4-tert.-octylphenol in water samples by stir bar sorptive extraction and thermal desorption-gas chromatography-mass spectrometry

A simple and highly sensitive method called thermal desorption (TD)-gas chromatography-mass spectrometry (GC-MS), which is used for the determination of trace amounts of 4-nonylphenol (NP) and 4-tert.-octylphenol (OP) in water samples, is described. NP and OP in samples are extracted from water samples and concentrated by the stir bar sorptive extraction (SBSE) technique. A stir bar coated with polydimethylsiloxane (PDMS) is added to a 2.0 ml water sample and stirring is carried out for 60 min at room temperature (25 °C) in a headspace vial. Then the extract is high sensitively analyzed by TD-GC-MS without any derivatization step. The optimum SBSE conditions are realized at an extraction time of 60 min. The detection limits are 0.02 ng ml⁻¹ for NP and 0.002 ng ml⁻¹ for OP. The method shows good linearity over the concentration range of 0.1-10 ng ml⁻¹ for NP and 0.01-10 ng ml⁻¹ for OP, and the correlation coefficients are higher than 0.999. The average recoveries of NP and OP are higher than 97% (R.S.D.: 3.6-6.2%) with correction using the added surrogate standards, 4-(1-methyl) octylphenol-d₅ and deuterium 4-tert.-octylphenol. This simple, accurate, sensitive and selective analytical method may be used in the determination of trace amounts of NP and OP in tap and river water samples.     

固相萃取-高效液相色谱-荧光检测法同时测定水中的壬基酚和双酚A

利用C18固相萃取柱富集和净化水样,采用高效液相色谱分离、荧光检测建立了水中的壬基酚（NP）和双酚A（BPA）的测定方法,并成功用于污水处理厂各处理单元出水的测定。不同加标水平的NP和BPA的回收率为95．3％～98．6％．其相对标准偏差为2、5％～3．7％。     

环境样品中壬基酚及相关化合物的分离富集与测定

对近 2 0年来环境样品中壬基酚及其相关化合物分析方法的研究进展进行了综合评述 ,重点讨论了样品前处理方法、柱分离和测定技术     

The model of alkylphenol micelles bound to respective antibodies on the solid surface

The model of binding of micelles of nonylphenol molecules to respective antibodies immobilized on the solid surface is proposed. The actual dimensions of micelles obtained from AFM measurements were used in modelling and allowed to predict the shape of the micelle. An account of non-spherical shape of micelles and their simultaneous binding to several antibodies allows estimation of the micelle binding energy.     

超高交联树脂对壬基酚聚氧乙烯醚的吸附机理(英文)

研究了壬基酚聚氧乙烯醚(NPEO-10)在3种具有不同比表面积和孔径大小的超高交联树脂上的吸附行为与机理.3种超高交联树脂对壬基酚聚氧乙烯醚的吸附量受它们的比表面积和孔径大小以及溶液温度的影响.壬基酚聚氧乙烯醚在3种超高交联树脂上的吸附等温线可以用Langmuir和双Langmuir模型很好地拟合,而用Freundlich模型拟合则效果不好,但这些拟合曲线都具有相似的形状.热力学分析表明吸附过程主要表现为吸附质分子的疏水部分和吸附剂表面的作用以及吸附质分子在其表面形成胶束状的聚集体,即分散的、单层及双层聚集体的混合分布.吸附动力学曲线中的两个平台也证明了吸附过程存在单层和双层聚集体.脱附研究为实现超高交联树脂吸附分离水溶液中的壬基酚聚氧乙烯醚提供了合适的操作条件.