分散液-液微萃取/高效液相色谱法测定水样中的痕量双酚A

建立了分散液-液微萃取与高效液相色谱联用技术测定水样中痕量双酚A(BPA)的方法. 通过对实验条件的筛选及优化, 得到最佳条件: 22.5 μL氯苯作萃取剂、0.5 mL丙酮作分散剂、0 min静止萃取时间、调节pH 3.2左右、10%离子强度及9 mL水样体积. 此条件下方法的线性范围为0.5~100 μg/L(R2=0.9941), 检出限为0.10 μg/L. 在BPA质量浓度为1 μg/L条件下, 方法回收率为87.8%~111.0%, 相对标准偏差8.3%(n=5), 富集倍数范围1905~2527. 对添加不同BPA浓度的自来水、地表水及回用中水进行分析, 回收率分别为(108±11.1)%, (107±13.2)%及(81.2±6.2)%(n=3). 在既定的色谱条件下, BPA的测定不受乙炔基雌二醇、雌二醇、雌三醇、雌酮和壬基酚等雌激素的干扰.     

Determination of Estrogens in Water Samples by Ionic Liquid-Based Dispersive Liquid-Liquid Microextraction Combined with High Performance Liquid Chromatography

Using 1-hexyl-3-methylimidazolium hexafluorophosphate ([C₆MIM][PF₆]) ionic liquid as extraction solvent, five estrogens including estrone (E₁), 17β-estradiol (E₂), estriol (E₃), 17α -ethynylestradiol (EE₂), and diethylstilbestrol (DES) in water samples were determined by dispersive liquid-liquid microextraction (DLLME) followed by high performance liquid chromatography with a photodiode array detector and a fluorescence detector (HPLC-DAD-FLD). The extraction procedure was induced by the formation of cloudy solution, which was composed of fine drops of [C₆MIM][PF₆] dispersed entirely into the sample solution with the help of a disperser solvent (acetone). Parameters including both extraction and disperser solvents and their volumes, extraction and centrifugal time, sample pH, and salt effect were investigated and optimized. Under the optimized conditions, 110–349 fold enrichment factors of analytes were obtained. The calibration curves were linear in the concentration range of 0.2–100 µg L^?1 for E₂, E₃, and EE₂ detected with FLD, and 1–100 µg L^?1 for E₁ and DES detected with DAD. The correlation coefficient of the calibration curve was between 0.9990 and 0.9997. The limits of detection (LOD, S/N = 3) for the five estrogens were in the range of 0.08–0.5 µg L^?1. The relative standard deviations (RSD) for six replication experiments at the concentration of 5.0 µg L^?1 were ≤5.7%. The proposed method was applied to the analysis of three water samples from different sources (river water, waste water, and sea water). The relative recoveries of spiked water samples are satisfied with 89.3–102.4% and 88.7–105.2% at two different concentration levels of 5.0 and 50.0 µg L^?1, respectively.     

分散液液微萃取-柱前衍生-高效液相色谱法测定水样中双酚A

建立了分散液液微萃取-柱前衍生-高效液相色谱法测定水样中双酚A的分析方法.通过交互正交试验和混合型优化实验设计对影响因素(萃取剂体积、分散剂类型及其体积、水样体积、pH值及离子强度)进行了优化.优化后的分散液液微萃取条件为:60 μL萃取剂,0.4 mL分散剂(甲醇),pH 4.0;优化后的柱前衍生化条件:0.1 mL 2.0 g/L衍生剂(对硝基苯甲酰氯)、衍生化时间30 min;方法的线性范围:0.002～0.2 mg/L(r=0.9997),检出限0.007 μg/L(S/N=3);不同浓度双酚A的萃取率为59.0%～63.0%,相对标准偏差(RSD)2.5%～9.2%(n=5);水样中双酚A的加标率为86.5%～107.1%,RSD为4.0%～11.9%(n=5),其它雌激素(雌酮、雌二醇、雌三醇和17α-乙炔基雌二醇)对双酚A的测定无干扰.本方法可以对水环境中的痕量BPA进行检测,具有操作简便、快速等优点.     

超声辅助分散液液微萃取-高效液相色谱法快速测定水样中的6种农药

为实现小体积环境水祥中不同农药的准确、快速、高灵敏测定,通过研究萃取剂、分散剂的种类、体积、盐浓度及超声时间对萃取效率的影响,结合分散液液微萃取与超声萃取技术,并与高效液相色谱联用,建立了快速测定环境水样中的吡虫啉、水胺硫磷、辛硫磷、毒死蜱、哒螨灵和阿维菌素6种农药的方法.在优化的萃取条件下,检测6种农药的线性范围为10～ 600 μg/L,检出限(S/N=3)为0.8～3.1 μg/L,相对标准偏差为4.7％～11.3％,富集倍数可达到58～187倍.本方法具有良好的线性、精密度和回收率,并具有较好的实用性.     

分散液液微萃取-气相色谱法测定水样中甲拌磷农药

建立了基于分散液液微萃取(DLLME)的新型样品前处理方法,并采用气相色谱/氢火焰离子化检测器对水样中痕量的甲拌磷农药进行了测定。考察了影响分散液液微萃取的因素包括萃取溶剂、分散剂、样品体积、萃取温度和离心速度等。在最佳实验条件下,对甲拌磷的富集倍数达到300倍;检出限为0.001μL/L;方法的线性范围为0.01~10μL/L,R2为0.9986;相对标准偏差为6.65%;回收率为104%。将分散液液微萃取法与单滴液相微萃取和离子液体-液相微萃取方法进行了对比,结果表明,分散液液微萃取技术具有操作简单、快捷(前处理时间小于5 min)、富集效果好、回收率高等优点。同时预言,将离子液体与分散液液微萃取结合,将会产生更加满意的结果。     

分散固相萃取-超声辅助分散液液微萃取/高效液相色谱法测定土壤中溴氰菊酯残留

建立了以分散固相萃取-超声辅助分散液液微萃取为样品前处理技术,结合高效液相色谱法(HPLC)测定土壤中溴氰菊酯。样品用甲醇∶水(1∶4,V/V)提取,经布氏漏斗减压抽滤,滤液经N-丙基乙二胺(PSA)、C18、石墨炭黑粉(GCB)净化后,用氯仿萃取,超声,离心后沉积相进行HPLC测定。对分散固相萃取吸附剂的选择及影响分散液液微萃取的因素进行了优化,在最优条件下,溴氰菊酯的富集倍数达到565倍,线性范围为0.005~2.5mg/kg,线性相关系数为0.9998,检出限为0.001mg/kg,平均加标回收率为70.3%~94.5%,相对标准偏差为2.5%~4.7%。该方法具有简便快速、准确灵敏、萃取效率高等特点,可用于土壤中溴氰菊酯残留检测。     

离子液体分散液液微萃取/高效液相色谱法测定环境水样中7种萘二酚

建立了测定环境水样中7种萘二酚的离子液体分散液液微萃取/高效液相色谱(IL-DLLME-HPLC)分析方法。以1-丁基-3-甲基咪唑六氟磷酸盐([C4MIM][PF6])为萃取剂,水样体积为8.0 m L,研究了萃取剂用量、水相p H值、萃取时间及盐添加量对7种萘二酚萃取效率的影响。获得最佳萃取条件为:[C4MIM][PF6]体积为150μL,水相p H值为5.0~7.0,涡旋萃取时间为3 min,氯化钠添加量为0.20 g/m L。在优化条件下,7种萘二酚在一定质量浓度范围内线性关系良好,相关系数均不小于0.997 7;方法富集倍数为57倍,方法检出限(S/N=3)为0.3~1.0μg/L;阴性环境水样中3个加标水平的平均回收率为83.5%~103%,相对标准偏差(n=6)为1.1%~3.8%。该方法快速简单、准确灵敏、环保,适用于环境水样中痕量萘二酚的富集检测。     

分散液液微萃取-高效液相色谱法测定环境水样中2,4-二氯酚

建立了简便、快速、有效的分散液液微萃取-高效液相色谱法测定环境水样中2,4-二氯酚的分析方法。对萃取剂、分散剂的种类和体积、萃取时间、离心时间、盐浓度等影响萃取效率的因素进行了优化。方法的线性范围为1～500μg/L(r=0.9997),相对标准偏差(RSD)为3.8%(n=6),检出限为0.19μg/L。该法适用于环境水样中的痕量2,4-二氯酚的检测。     

Determination of Trace Bisphenol A in Leachate by Solid Phase Microextraction Coupled with High Performance Liquid Chromatography

Abstract

A rapid determination method for trace bisphenol A in leachate by solid phase microextraction (SPME) coupled with high performance liquid chromatography (HPLC) was developed. The experimental condition of SPME, such as select operation, solid phase microextraction fibers, pH, extraction time, extraction temperature, desorption time, desorption solution, mode, and the analytical conditions of HPLC were optimized. As compared with the graph that was produced by HPLC alone, the graph by only HPLC couldn't analyze bisphenol A and compared to the results of three solid‐phase microextraction fibers. The linear range was between 0.0128 mg/L and 0.192 mg/L in this method, and the correlative coefficient was 0.9975. Limits of detection, repeatability, and reproducibility were also determined. The limit of detection of this method was 3.25 µg/L (3σ, n=11). The relative standard deviation (RSD, n=3) was 4.4%. The method was used for the determination of trace bisphenol A in leachate of Qingshan landfill and leachate of Liufang landfill. The recoveries were between 94.5% and 103.3%. This method is fast, convenient, sensitive, solvent free, and suitable for the determination of trace bisphenol A in leachate.     

悬浮固化分散液相微萃取-高效液相色谱/串联质谱法测定环境水样品中6种雌激素

本文建立了悬浮固化分散液相微萃取(DLLME-SFO)高效液相色谱-串联质谱法(HPLC-MS/MS)测定环境水样品中壬基雌酚、双酚A、己烯雌酚、雌酮、雌二醇、炔雌醇6种雌激素的分析方法。萃取的最优条件为:以90μL 1-十二醇为萃取剂,250μL0.025mol/L Triton X-100为分散剂,调节pH至7.0,超声3min,在室温条件下萃取环境水样中的雌激素残留。最优条件下,该方法在三个浓度水平下的平均加标回收率为93.4%~108.6%,相对标准偏差为1.3%~8.7%,检出限为0.001~0.05μg/L。将该方法应用于环境水样中雌激素残留分析,获得了较好的回收率。     

三相中空纤维膜液相微萃取-高效液相色谱法测定水中痕量双酚A

建立了三相中空纤维膜液相微萃取-高效液相色谱(HF-LPME-HPLC)方法,用于分析测定水中痕量双酚A的含量.设计了三相中空纤维膜液相微萃取系统,优化的HP-LPME最佳萃取条件为:萃取剂为正辛醇,接受相NaOH浓度为0.09 mol/L,样品溶液pH=4.0,NaC1加入量为30 g/L,搅拌速度为900 r/min,萃取时间为60 min.萃取后取20 μL接受相进行色谱分析.在最佳萃取条件下,方法的线性范围为0.5～200 μg/L(r＞ 0.999),检出限(信噪比为3)为0.2 μg/L;富集因子为241;方法RSD＜3.2％ (n=3).在实际环境水样中添加5,20和50μg/L的双酚A标准物质,加标平均回收率为92.8％～101.9％.表明本方法可用于水中痕量双酚A的快速准确测定.     

超声辅助离子液体分散液相微萃取-高效液相色谱法测定废水中雌激素的研究

将离子液体、分散液相微萃取与超声萃取技术结合,采用疏水性离子液体1-丁基-3-甲基咪唑六氟磷酸盐([C4 MIM][PF6])为萃取剂,建立了超声辅助离子液体分散液相微萃取-高效液相色谱法分析废水中3种雌激素物质(己烯雌酚、双烯雌酚、己烷雌酚)方法.试验采用50μL的离子液体,考察了溶液体积、溶液pH值、超声时间、静置时间、离心时间等因素对富集效果的影响.最佳的萃取条件为:溶液体积为6 mL,甲醇体积0.3 mL,溶液pH值为2.0,超声时间6min,静置时间30min,离心时间10 min.在优化的萃取条件下,3种雌激素的富集倍数可达到96.8～112.4倍;方法的线性范围为0.5-100.0μg/L;检出限为0.25～0.50μ/L.对浓度为5.0μg/L的3种物质测定6次的相对标准偏差为9.2%～10.8%.     

Determination of Trihalomethanes in Drinking Water by Dispersive Liquid–Liquid Microextraction then Gas Chromatography with Electron-Capture Detection

Dispersive liquid–liquid microextraction (DLLME) has been used for preconcentration of trihalomethanes (THMs) in drinking water. In DLLME an appropriate mixture of an extraction solvent (20.0 μL carbon disulfide) and a disperser solvent (0.50 mL acetone) was used to form a cloudy solution from a 5.00-mL aqueous sample containing the analytes. After phase separation by centrifugation the enriched analytes in the settled phase (6.5 ± 0.3 μL) were determined by gas chromatography with electron-capture detection (GC–ECD). Different experimental conditions, for example type and volume of extraction solvent, type and volume of disperser solvent, extraction time, and use of salt, were investigated. After optimization of the conditions the enrichment factor ranged from 116 to 355 and the limit of detection from 0.005 to 0.040 μg L⁻¹. The linear range was 0.01–50 μg L⁻¹ (more than three orders of magnitude). Relative standard deviations (RSDs) for 2.00 μg L⁻¹ THMs in water, with internal standard, were in the range 1.3–5.9% (n = 5); without internal standard they were in the range 3.7–8.6% (n = 5). The method was successfully used for extraction and determination of THMs in drinking water. The results showed that total concentrations of THMs in drinking water from two areas of Tehran, Iran, were approximately 10.9 and 14.1 μg L⁻¹. Relative recoveries from samples of drinking water spiked at levels of 2.00 and 5.00 μg L⁻¹ were 95.0–107.8 and 92.2–100.9%, respectively. Comparison of this method with other methods indicates DLLME is a very simple and rapid (less than 2 min) method which requires a small volume of sample (5 mL).     

反相液相色谱法测定双酚A和苯酚

双酚A[4,4′-双(4-羟苯基)丙烷]是生产环氧树脂、聚碳酸酯、巨砜和改性酚醛树脂等高聚物的重要原料,此外,还大量用来制造涂料、粘合剂、橡胶防老化剂和农药杀菌剂等。 合成双酚A的主要原料是苯酚,因此,来反应的苯酚单体就成了双酚A产品中的主要杂质,为了随时掌握苯酚的转化率、监控产品质量,需要建立一种快速、灵敏、简便、准确地测     

分散液液微萃取-上浮溶剂固化/高效液相色谱法测定沉积物中的十溴联苯醚

建立了沉积物中痕量十溴联苯醚的分散液液微萃取-上浮溶剂固化-高效液相色谱-紫外法(DLLME-SFO-HPLC-UV)。以正交试验数据为训练样本,采用BP(Back propagation)神经网络模型优化了分散液液微萃取-上浮溶剂固化条件:分散剂为1.00mL甲醇、萃取剂为35.0μL十二醇、NaCl质量浓度为10.00%、萃取时间10min和pH=5,其萃取率(ER)可达62.22%。方法的线性范围为3.5～1400ng/g(r=0.9960),检出限(LOD)和定量限(LOQ)分别为2.3pg/g(S/N=2)和5.6pg/g(S/N=5),实际样品的加标回收率为97.7%～104.2%。本方法集萃取、富集、分离步骤于一体,简化了沉积物中十溴联苯醚的前处理过程。     

温控离子液体分散液液微萃取结合高效液相色谱法检测脐橙中染色剂残留

建立了QuEChERS-温控离子液体分散液液微萃取结合高效液相色谱法快速检测脐橙中5种染色剂残留的分析方法。QuEChERS前处理步骤:样品用乙腈快速提取,NaCl和无水MgSO4除水后,经N-丙基乙二胺净化。温控离子液体分散液液微萃取步骤:QuEChERS前处理的净化液(1 mL)为分散剂,1-辛基-3-甲基咪唑六氟磷酸盐离子液体(60μL)为萃取剂,55℃水浴12 min,将目标物富集。用高效液相色谱-紫外检测器分析,检出样品用超高效液相色谱-串联质谱确证。在0.01和0.05 mg/kg的添加水平下,5种染色剂的平均回收率为70.3%~93.6%,相对标准偏差为3.5%~9.2%,定量限为1.1~2.8μg/kg。     

分散液液微萃取-气相色谱法快速测定水中15种硝基苯类物质

建立了分散液液微萃取-气相色谱电子捕获检测器测定水中15种硝基苯类物质的方法.筛选出了具有高密度且能够适用于电子捕获检测器的萃取剂.优化了色谱条件,对萃取剂种类及用量、分散剂种类及用量、萃取时间、萃取温度等条件进行了优化.DB-35毛细管柱对15种硝基苯类物质具有最好的分离效果.使用程序升温,初始80℃ 保持2 min,以5℃/min速率升温至180℃,可以在22 min内完成分离.以100μL氯苯作为萃取剂、400μL甲醇作为分散剂,对5.00 mL水样在室温下进行萃取,仅需30 s即可达到萃取平衡,15种目标物的萃取率均可达到90%以上,富集倍数达到45.0~48.8.离心分离,取下层沉积相进行气相色谱测定,使用电子捕获检测器检测,方法的定量限为0.03~0.15μg/L,线性范围为0.20~50.0μg/L,相关系数不低于0.998.方法的相对标准偏差在3.3%~8.9%之间,加标回收率在86.0%~103.5%之间.     

涡旋辅助分散液液微萃取-悬浮固化/高效液相色谱法测定水样中7种萘二酚

建立了水样中7种萘二酚的涡旋辅助分散液液微萃取-悬浮固化/高效液相色谱(VA-DLLMESFO/HPLC)测定方法。以乙醚-十二醇为二元微萃取剂,通过涡旋分散方式协同萃取水样中的目标化合物,采用C18色谱柱分离,HPLC测定。优化了萃取剂及用量、萃取时间、氯化钠用量等条件。最佳萃取条件为:萃取剂为100μL乙醚和50μL十二醇,氯化钠用量为0.2 g/m L,涡旋萃取3 min。在优化条件下,7种萘二酚在一定质量浓度范围内线性关系良好,相关系数均大于0.997,方法检出限(S/N=3)为1.7~6.0μg/L;3个加标水平下的平均回收率为82.1%~106.0%,日内相对标准偏差(RSD,n=5)为1.2%~4.1%;中间添加水平的日间RSD(n=5)为2.5%~5.7%。该方法前处理简单,涡旋分散大大提高了物质传质速率,增大了萃取效率,缩短了萃取时间,是一种适用于水样中萘二酚类物质富集检测的绿色方法。     

功能化离子液体/离子液体分散液-液微萃取测定水中苯氧羧酸类除草剂

建立了功能化离子液体/离子液体分散液-液微萃取(FIL/IL-DLLME)测定水中4种苯氧羧酸类除草剂的农药残留分析方法.离子液体[C4MIMBF4]有助于难溶于水的[C6HyMIMTf2N]在水相中形成液滴.离子对[LiWf2N]的引入有利于提高功能离子液体对分析物的提取效率,对影响萃取效率的重要因素进行选择和优化,最佳条件为:100 μL[C6HyMIMTf2N])作为提取剂,100 μL[C4MIMBF4]作为分散剂,在30℃下超声5 min,[LiTf2N]浓度为5％和样品溶液的pH=2.在最佳优化条件下,5～500 μg/L范围内线性良好,相关系数为0.9953 ～0.9996;对自来水、河水、田间水进行浓度为10和20 μg/L添加回收实验,回收率为70.2％～107.5％,相对标准偏差RSD＜10％,检出限为0.05 ～0.2 μg/L,得到满意的结果,说明本方法对于实际样本的检测具有可行性.     

中空纤维膜液相微萃取/高效液相色谱法测定水样中4种头孢菌素的含量

基于中空纤维膜液相微萃取/高效液相色谱(HF-LPME/HPLC),建立了水样中痕量头孢唑林(CZO)、头孢呋辛(CXM)、头孢他定(CAZ)和头孢西丁(FOX) 4种头孢菌素残留的检测方法。优化得到最佳萃取条件:萃取溶剂为1-辛基-3-甲基咪唑六氟磷酸盐([Omin]PF_6),辅助萃取溶剂为10%三正辛基氧膦(TOPO),样品溶液pH值为2.5,萃取时间为20 min,萃取温度为30℃,搅拌速率为600 r/min。以Agilent Poroshell 120 EC-C_(18)(100 mm×4.6 mm,2.7μm)为色谱柱,以0.05 mol/L醋酸钠缓冲液(pH 4.0)-乙腈(9∶1,体积比)为流动相,4种头孢菌素可在7 min内完全分离。结果表明4种头孢菌素的线性关系良好,富集倍数为45～78倍,检出限为0.2～0.7 ng/mL,回收率为83.2%～102%,相对标准偏差为2.0%～9.8%。该方法简单高效,检测成本低,溶剂用量少,绿色环保,灵敏度高,对水样中痕量头孢菌素残留的富集能力强。