正相高效液相色谱法分析壬基环己醇聚氧乙烯醚中残留壬基环己醇

壬基环己醇聚氧乙烯醚(NCEO_n)是非环境友好型壬基酚聚氧乙烯醚(NPEO_n)潜在的升级换代产品。 本文采用正相高效液相色谱法(NP HPLC)测定产品中残存壬基环己醇(NC),用Weilbull法测定其中聚乙二醇(PEG)含量,用电喷雾电离质谱法评价聚氧乙烯(PEO)多分散指数(PDI),以此鉴定NCEO_n的品质。 为了建立快速分析NCEO_n产品中NC含量的方法,以满足跟踪检测的需求,本文筛选了反相HPLC和NP HPLC两类5种方法,并进行比较和初步条件优化,确定了用Inertsil NH₂色谱柱和示差折光检测器以及乙酸乙酯为洗脱液的NP HPLC法定量分析NC,方法的回收率为91.77%～107.6%,相对标准偏差为4.46%,最低检测限为9.8 μg/mL。 经测定,NCEO₇和NCEO₉产品中NC的残留量分别为0.158%和0.139%,PEG质量分数为7.1%和7.3%,PDI为85.0%和88.6%,证实NCEO_n产品具有NC残留量少、PEG含量低和产品PEO窄分布特征,具有在化妆品或个人洗护用品等民用产品中替代NPEO_n的潜能。     

“拟双子”阴离子表面活性剂在癸烷/水界面的分子动力学模拟

采用全原子分子动力学模拟方法研究了壬基酚取代的系列烷基磺酸盐表面活性剂在癸烷/水界面的微观聚集行为,通过分析界面厚度、界面生成能和界面张力以及表面活性剂分子与水分子之间的径向分布函数和配位数,讨论了不同磺烷基链长度对壬基酚基取代烷基磺酸盐表面活性剂界面性质的影响.结果表明,磺烷基链长为12时,表面活性剂的界面张力最低,界面厚度和界面生成能最大.     

Synthesis of Ionic Liquids Containing the Hydroxyl Functionality for Extracting Nonylphenol and Octylphenol in Water

A new series of task-specific ionic liquids (TSILs) containing hydroxyl groups was prepared and applied for extracting 4-nonylphenol (4-NP) and 4-tert-octylphenol (4-t-OP) in water. These new TSILs showed much greater extraction efficiencies for 4-NP and 4-t-OP than the common typical ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate ([C₄mim][PF₆]) and 1-hexyl-3-methylimidazolium hexafluorophosphate ([C₆mim][PF₆]).

新型毛细管内固相萃取-气相色谱法检测纺织品中烷基酚类物质

建立了毛细管内固相萃取(SPE)-气相色谱(GC)检测纺织品中壬基酚和辛基酚含量的分析方法。通过比较4种性质不同固相萃取剂的萃取效果,筛选出对烷基酚(APs)类物质萃取效果最佳的固相萃取剂,将其作为填充物质制作毛细管内固相萃取柱,将毛细管内固相萃取法与气相色谱联用进行分析检测。最佳固相萃取剂为Abselut NEXUS,毛细管内固相萃取最佳条件为:1.2 μL甲醇和1.2 μL超纯水活化,1.2 μL甲醇洗脱,上样速率是0.4 μL/min。该法在较低浓度范围内呈现良好的线性相关性,对烷基酚的富集倍数约为100倍,对辛基酚和壬基酚的检出限分别为3.7 μg/L和4.5 μg/L,加标回收率分别为85.6%~98.2%和83.8%~95.7%,结果表明,此法能够简捷、迅速、有效地检测出纺织品中残留的烷基酚类物质。     

固相萃取-气相色谱-质谱-选择离子法测定纺织助剂中壬基酚

建立了纺织助剂中壬基酚的提取与含量测定方法.样品通过固相萃取、衍生化后,利用气相色谱/质谱-选择离子定量分析方法,对各类助剂中的壬基酚(NP)进行了定量检测.针对不同类型助剂,通过实验对前处理方法进行了优化.各类助剂的加标回收率在90%以上,相对偏差小于4%,方法的最低检出限为0.2 mg.L-1.该方法适用于水性,油性,乳液型等绝大部分纺织助剂,具有广泛性和实用性.     

水体中壬基酚光降解机理研究

在模拟太阳光条件下, 通过测定光解过程中壬基酚(NP)残留率和中间产物, 考察了溶解氧(DO), H₂O₂, NO₃^-及Cl^-对水体中NP光解的影响, 并推测了降解途径. 结果表明: DO浓度越低NP降解越慢, 产物有4-壬基-邻苯二酚、壬醇、壬醛和壬酸, 其中以壬酸为主, 推测NP在 O₂^·-作用下, 生成邻酚, 再发生共轭加成. H₂O₂, NO₃^-的添加显著加快NP降解速率, 产物有碳链缩短(2～8碳)的酚、4-壬基-邻苯二酚、壬醇、壬醛、壬酸, 其中以壬醛为主, H₂O₂, NO₃^-在光照下生成·OH, ·OH进攻NP电子云较集中的位置, NO₃^-吸收光同时产生·NO₂, 检测到2-硝基-4-壬基酚. 在H₂O₂存在下, Cl^-的添加对NP降解先促进后抑制, 并检测到壬酰氯, 推测·OH与Cl^-共存, 形成Cl₂^-参与反应, 氯代产物的前驱体可能是壬醛.     

Effect of Surfactant Type and Concentration on Surfactant Migration,Surface Tension,and Adhesion of Latex Films

The effect of surfactant type and concentration on the migration behavior of surfactant in a latex film was investigated. Two types of surfactant, including an anionic (sodium lauryl sulfate, SLS) and a non-ionic (nonylphenol ethoxylate, average number of ethylene oxide units = 40, NP-40) surfactant, were used in an emulsion polymerization of methyl methacrylate butyl acrylate copolymer (MMA–BA). The total amount of surfactant was varied in three levels, i.e., 1.5, 3, and 4.5 wt%, and the surfactants were used both pure and in a mixture state. The surfactant migration to the film–air (F–A) and film–substrate (F–S) interfaces of the latex films was determined by using an attenuated total reflection-Fourier transform infrared (ATR-FTIR) method. In addition, the adhesion of the latex films to glass substrates was measured by a pull-off test. The results showed that the migration of anionic surfactant to the interfaces was greater than the non-ionic one. It was also found that the use of non-ionic surfactant along with anionic surfactant could decrease the migration of the anionic surfactant to the interfaces.     

沉积物中壬基苯酚类雌性激素化合物的加速溶剂提取方法研究

为了同时提取和检测沉积物中的雌性激素化合物对壬基苯酚(NP)、对壬基苯酚一乙氧醚(NP1EO)和对壬基苯酚二乙氧醚(NP2EO),对加速溶剂提取体系的各种条件和对壬基苯酚类化合物的硅烷基化反应条件等进行了优化。在丙酮和丙酮-二氯甲烷混合液(丙酮含量≥60%)介质中,这些化合物的硅烷基化反应很快达到反应终点。加速溶剂提取体系的最佳提取条件是120℃、8.4MPa、两次循环提取;最佳提取溶剂是二氯甲烷。与索氏提取和酸化悬浮液液提取比较,明显提高了提取率、重现性和准确性。平均添标回收率在89.3%~95.7%之间,相对标准偏差为2.3%~13.4%。本方法对壬基苯酚、对壬基苯酚一乙氧醚和对壬基苯酚二乙氧醚化合物的检出限分别为10、30、35ng/gdw(干重)。     

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 Hormones and Non-ionic Surfactant Degradation Products in Small-Volume Aqueous Samples from Soil Columns Using LC-ESI-MS-MS and GC-MS

The leaching of two estrogens, 17β-estradiol and estrone, and two degradation products of non-ionic surfactants, octylphenol and nonylphenol, through a soil column were studied to estimate their transport behavior. Different concentration methods (lyophilization, solid phase extraction, and liquid–liquid extraction) were evaluated for analyzing these compounds in small effluent fractions (30–50 mL) collected. Liquid chromatography-mass spectrometry (LC-MS-MS) and gas chromatography-mass spectrometry (GC-MS) were employed for quantitative analysis of these compounds. After comparison, the lyophilization-LC-MS-MS method was found to be best suited for the analysis of the two estrogen hormones and the liquid–liquid extraction-GC-MS method best for the analysis of the two phenols in small samples in the soil column study. Because of their high sorption capacity, these compounds were mostly sorbed in the upper part of the soil column and were difficult to detect in column effluent.