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。     

顶空衍生固相微萃取-气相色谱质谱法测定聚碳酸酯树脂中的环境雌激素

建立了固相微萃取-气相色谱质谱联用测定聚碳酸酯树脂中环境雌激素4-枯基苯酚和双酚A的分析方法。优化了固相微萃取纤维、萃取温度和时间、解吸时间、搅拌速度、pH等萃取条件及衍生化温度和时间、衍生化方式等衍生化条件，并对样品浸泡时间、浸泡温度等进行了研究。方法的线性范围为0．05μg/L～1mg／L，4-枯基苯酚和双酚A的检出限分别为50ng／L和0．5ng／L，相对标准偏差（RSD，n=5）分别为5．2％和1．6％，平均回收率（n=3）在90．50％～107．3％之间，该方法简单、快速、灵敏。     

固相萃取-气相色谱质谱法检测水体中典型有机磷酸酯阻燃剂

建立了固相萃取(SPE)与气相色谱质谱(GC-MS)联用测定自然水体中8种有机磷酸酯阻燃剂(OPFRs)OPFRs的分析方法。通过对GC MS条件与SPE萃取条件的优化,采用Poly-Sery PSD固相萃取小柱对水样进行富集浓缩,用4 mL乙酸乙酯洗脱,以选择离子扫描方式对目标物进行定性和定量分析,并采用内标法定量。本方法在对应OPFRs线性范围内的线性相关系数为0.9937～0.9995;检出限为0.006～0.850 ng/L;定量限为0.015～2.0 ng/L。除磷酸三(2-乙基)己基酯(TEHP)外,其它OPFRs的加标回收率为70.3%～114.3%。TEHP加标10和50 ng/L时,回收率为64.0%～69.3%;加标100 ng/L时回收率为34.3%。将本方法应用于太湖梅梁湾水体中OPFRs分析,其总浓度值为1000～2700 ng/L。     

土壤中10种多溴联苯醚的加速溶剂-固相萃取净化方法优化研究

建立了土壤中10种多溴联苯醚(PBDEs)的加速溶剂萃取-固相萃取净化-气相色谱分析测定方法.采用加速溶剂萃取(ASE)技术对土壤中10种PBDEs进行提取,并对4种萃取体系(正己烷、正己烷-丙酮(4∶1,V/V)、正己烷-丙酮(1∶1,V/V)、正己烷-二氯甲烷(1∶1,V/V))进行优化;采用固相萃取(SPE)技术对样品进行净化,制备了10种不同填料的SPE柱,通过洗脱实验和加标回收率实验对各SPE柱的净化性能进行对比筛选.最终优化条件为正己烷-丙酮(4∶1,V/V)体系提取,酸性硅胶柱净化.在优化条件下,10种PBDEs的回收率为74.4％ ～ 125.2％,相对标准偏差为4.4％ ～ 14.4％,方法检出限为0.04～0.22 ng/mL.本方法简单、快速、净化效果较好、重现性和回收率良好,可用于土壤样品中PBDEs的分析.     

固相萃取-高效液相色谱联用分析蔬菜中5种有机磷

建立了固相萃取(SPE)-高效液相色谱(HPLC)联用测定蔬菜中甲基对硫磷、三唑磷、乙基对硫磷、倍硫磷和辛硫磷的分析方法.采用自制Florisil SPE柱,优化了萃取溶剂、SPE柱填料类型、SPE柱填料用量和SPE淋洗溶剂等前处理条件以及HPLC仪器条件.方法线性范围为0.02~2.00μg/L;检出限介于0.10~0.17μg/g.分析加标实际样品,回收率为76.5%~109.0%,RSD为2.1%~8.0%.方法完全符合蔬菜中痕量有机磷农药残留的快速分析要求.     

气相色谱/质谱法测定水和沉积物中雄激素与孕激素

建立了气相色谱/质谱联用(GC-MS)技术同时测定水和沉积物中雄激素二氢睾酮、睾丸激素、雄烯二酮和孕激素孕酮的分析方法.分别确定了沉积物微波辅助萃取条件(萃取溶剂、萃取温度和萃取时间)和水样固相萃取条件(固相萃取柱、洗脱溶剂和水样pH值).结果表明:微波辅助萃取最优条件是乙酸乙酯为萃取溶剂,在120℃萃取15 min;以Oasis HLB为固相萃取柱,水样调节至pH4,采用乙酸乙酯为洗脱溶剂,固相萃取效果佳.以三甲基碘硅烷为催化剂,N-甲基-N-三甲基硅基三氟乙酰胺为衍生化试剂,将目标化合物分子结构上的羟基和酮基同步衍生化,并确定了衍生化过程的最佳反应温度为40℃,反应时间为20 min,满足了GC-MS分析该类物质的要求.水和沉积物中4种目标化合物检出限分别为0.1 ～ 0.5 ng/L和0.6 ～ 0.8ng/g,定量限分别为0.4 ～ 1.8 ng/L和1.9 ～2.6 ng/g,加标回收率分别为89.3％ ～ 101.4％和77.3％ ～92.1％,相对标准偏差(RSD)均小于9％.采用本方法对洱海水和沉积物样品进行了分析.     

固相萃取富集高效液相色谱法测定烟草及烟草添加剂中的重金属元素

报道用固相萃取富集,高效液相色谱法测定烟草及烟草添加剂中镍、铜、锡、铅、镉、汞的方法。样品用微波消化,消化液中的镍、铜、锡、铅、镉、汞用四-(对甲氧基苯基)-卟啉(T4MPP)柱前衍生．用C18固相萃取小柱萃取富集镍、铜、锡、铅、镉、汞的T4MPP络合物,然后用甲醇和四氢呋喃为流动相梯度洗脱,Waters Xterra^TMRP18色谱柱分离二极管阵列检测器检测。镍、铜、锡、铅、隔、汞的捡出限在2～4ng／L之间,方法相对标准偏差为1．8％～2．4％,加标回收率为96％～103％。     

水环境中多种有机锡化合物的顶空固相微萃取-气相色谱质谱联用测定

为建立水样中多种有机锡化合物的快速灵敏检测方法,采用顶空固相微萃取-气质联用(HS-SPME-GCMS)技术,通过Plackett-Burman法和BoxBehnken设计优化了测定条件参数。衍生化和萃取温度、萃取时间和缓冲液p H是影响有机锡测定值的关键因素,衍生/萃取温度60℃、萃取时间30 min、缓冲液p H 4.6是测定的最佳条件。优化后的方法灵敏度高、选择性好,线性范围1~1000ng/L,回收率在82.3%~104.7%之间,相对标准偏差均小于9%,该方法适用于快速检测水环境中多种有机锡化合物。     

固相微萃取衍生化与GC-MS测定水中痕量路易氏剂的方法研究

采用固相微萃取衍生化和气相色谱．质谱（GC-MS）监测技术，对水中痕量路易氏剂进行了测定，考察了衍生化试剂、萃取纤维、萃取时间等因素对方法灵敏度的影响。测定路易试剂的线性范围为1．1—220ng／mL，检出限为0．0001mg／L，相对标准偏差为3．4％，回收率为93．2％～104．4％。     

人工尿样中芥子气-谷胱甘肽加合物的气相色谱-质谱法检测

该文以气相色谱-质谱法测定人工尿样中的芥子气-谷胱甘肽加合物的β-裂解产物1,1′-磺酰基二(2-甲巯基)乙烷(SBMTE)。采用固相萃取(SPE)及固相支持液-液萃取(SLE)两种方法对尿样中的SBMTE进行富集净化,并对两种方法的影响因素进行了优化。采用中等极性毛细管色谱柱(DB-17MS)分离,以电子轰击源(EI)质谱选择离子模式(SIM)检测,内标法定量。结果表明,以SPE/GC-MS方法检测,SBMTE在1~100μg/L范围内线性关系良好,相关系数r为0.998 4,检出限(LOD)为0.1μg/L,回收率大于90%;以SLE/GC-MS方法检测,SBMTE在2~150μg/L范围内线性关系良好,相关系数r为0.998 8,检出限为0.5μg/L,回收率大于90%。SPE方法适用于直接检测空白尿样中添加SBMTE或芥子气染毒真实尿样还原后样品的进一步净化处理,SLE方法可应用于芥子气染毒后真实尿样的确证检测和溯源性检测。     

Simultaneous determination of endocrine disrupting phenolic compounds and steroids in water by solid-phase extraction-gas chromatography-mass spectrometry

A solid-phase extraction (SPE)-gas chromatography (GC)-mass spectrometry (MS) analytical method for the simultaneous separation and determination of endocrine disrupting chemicals (EDCs) from water samples is described in detail. Important and contrasting EDCs including estrone, 17beta-estradiol, 17beta-ethynylestradiol, 16beta-hydroxyestrone, 4-nonylphenol, bisphenol A and 4-tert-octylphenol were selected as the target compounds. The SPE technique, followed by the derivatisation with bis (trimethylsilyl) trifluoroacetamide was used for the extraction recoveries of target compounds from water samples. A number of parameters that may affect the recovery of EDCs, such as the type of SPE cartridges, eluents, as well as water properties including pH value, and concentration of salts and humic substances were investigated. It is shown that the Oasis cartridges produced the best recoveries of target EDCs while ethyl acetate was efficient in eluting EDCs from SPE cartridges. The recovery of some EDCs was enhanced by the addition of salt, but reduced by the increase in pH value and humic acid concentration. The optimised method was further verified by performing spiking experiments in natural river water and seawater matrices, with good recovery and reproducibility for all the selected compounds. The established method was successfully applied to environmental water samples from East and West Sussex, UK, for the determination of the target EDCs.     

Simultaneous determination of various pharmaceutical compounds in water by solid-phase extraction-liquid chromatography-tandem mass spectrometry

A solid-phase extraction (SPE) followed by liquid chromatography-electrospray ionisation tandem mass spectrometry (LC-ESI-MS-MS) method was developed and validated for simultaneous analysis of 11 pharmaceutical residues (propranolol, sulfamethoxazole, meberverine, thioridazine, carbamazepine, tamoxifen, mecoprop, indomethacine, diclofenac, meclofenamic acid and monensin) in environmental water samples. The collision energy chosen for the multiple reaction monitoring (MRM) experiment was optimised. A number of parameters that may affect the recovery of the pharmaceuticals, such as the type of SPE cartridges, eluents, as well as water properties including pH value, salinity and concentration of colloid and surfactant were investigated. It is shown that the Oasis HLB SPE cartridge produced the best recoveries of the target pharmaceuticals while methanol was efficient in eluting pharmaceuticals from SPE cartridges. The recovery of some target compounds was enhanced with increasing salinity, but reduced by increasing pH value, and unaffected by surfactant concentration (0-10 microg/l). The recovery of most compounds was slightly increased by the presence of colloids (0-10 mg/l), which however caused a reduction in recovery for sulfamethoxazole and meberverine. The optimised method was further verified by performing spiking experiments in river water and seawater matrices, with good recovery and reproducibility for all except two compounds. The established method was successfully applied to environmental water samples from East Sussex, UK, for the determination of the target pharmaceuticals.     

饮用水中9种卤乙酸的超高效液相色谱法测定

建立了固相萃取/超高效液相色谱(SPE/UPLC)测定饮用水中9种痕量卤乙酸(HAAs)的分析方法.对固相萃取和液相色谱等分析条件进行了优化,选择Lichrolut EN固相萃取小柱富集饮用水中的HAAs,三乙胺-磷酸缓冲液和甲醇作为UPLC的流动相.在优化的分析条件下,9种卤乙酸在6min内实现基线分离,所有目标物在一定质量浓度范围内线性良好,相关系数为0.995 7～0.9999;一氯乙酸(MCAA)的检出限为10.85μg/L,其它8种化合物的检出限为0.25～0.70μg/L;除MCAA外,其它目标物在低、中、高3种加标水平的回收率为60%～106%.方法的相对标准偏差(RSD,n=5)为2.0%～5.7%.将此方法应用于我国北方某城市自来水中卤乙酸的测定,5种HAAs被检出.方法灵敏度高、简便快捷,可用于生活饮用水中痕量卤乙酸的测定.     

Automated trace level determination of glyphosate and aminomethyl phosphonic acid in water by on-line anion-exchange solid-phase extraction followed by cation-exchange liquid chromatography and post-column derivatization.

An automated method based on the on-line coupling of anion-exchange solid-phase extraction (SPE) and cation-exchange liquid chromatography followed by post-column derivatization and fluorescence detection has been developed for the trace level determination of glyphosate and its primary conversion product aminomethyl phosphonic acid (AMPA) in water. PRP-X100 poly(styrene-divinylbenzene)-trimethylammonium anion-exchange cartridges (20 x 2 mm, 10 microm) were selected for the SPE of glyphosate and AMPA. The ionic compounds present in the samples strongly influenced the extraction of both analytes; however, when an on-line ion-exchange clean-up step was introduced before sample SPE, the problem was largely solved. By processing 100-ml samples detection limits better than 0.02 microg/l for glyphosate and 0.1 microg/l for AMPA were achieved in river water. Both analytes were unstable in solution and the approach of storing samples on the PRP-X100 SPE cartridges was evaluated for a period of 1 month under three different storage conditions (deep freeze, refrigeration and 20 degrees C).     

Highly sensitive simultaneous determination of sulfonamide antibiotics and one metabolite in environmental waters by liquid chromatography-quadrupole linear ion trap-mass spectrometry

The present work describes the development of a highly sensitive analytical method based on liquid chromatography-quadrupole linear ion trap-mass spectrometry (LC-QqLIT-MS) for the determination of nine sulfonamide antibiotics and one N4-acetylated metabolite in environmental waters (wastewater, surface water and groundwater) and bottled mineral water. Special emphasis was devoted to the elimination of matrix components during solid-phase extraction (SPE) by the evaluation of three different extraction/purification strategies: single cartridges (Oasis HLB and Oasis MCX) and tandem (TD) extraction (combination of both). The method developed proved to be suitable for sulfonamide determination in all kinds of waters tested. The method was shown to be linear in a wide concentration range, with correlation coefficients higher than 0.999 for all compounds except for sulfadimethoxine (R2 0.997). The overall instrumental repeatability was satisfactory, with the exception of the metabolite (RSD 34%). Method limits of detection achieved for sulfonamides were in the range 0.01-1.13 ng L(-1) and for the metabolite 0.08-461 ng L(-1). Recovery rates were estimated at 500 ng L(-1) spike level in the four water matrices selected. The highest recovery achieved in all matrices was that corresponding to the Oasis HLB cartridge. In environmental waters, recovery values obtained were higher than 61% for the surface water and, in general, higher than 90% for groundwater and wastewater. Bottled mineral water exhibited recovery rates higher than 92%, with the exception of sulfamethoxypiridazine (82%) and sulfapyridine (86%) In order to demonstrate the applicability of the developed method, several water samples were analyzed. Results evidenced the requirement for consideration of N4-acetylated metabolites of sulfonamides in environmental residue analysis to avoid the underestimation of removal rates of such pharmaceutical compounds during wastewater treatments.     

Determination of fluorescent whitening agents in environmental waters by solid-phase extraction and ion pair liquid chromatography-tandem mass spectrometry

A comprehensive method for the trace determination of four stilbene-type disulfonate and one distyrylbiphenyl-type fluorescent whitening agents (FWAs) in environmental water samples was developed and validated. Various solid-phase extraction (SPE) cartridges were investigated. The newly developed Oasis WAX (weak mixed-mode anion exchange and reversed-phase sorbent) SPE cartridge provides the optimal sample extraction results. The analytes were then identified and quantitated by liquid chromatography-electrospray ionization tandem mass spectrometry (HPLC-ESI-MS-MS) in negative ionization mode, applying di-n-hexylammonium acetate (DHAA) as the ion-pairing reagent in mobile phase. Limits of quantitation (LOQs) were established between 4 and 18 ng/l in 50 ml of water samples. Intrabatch and interbatch precision with their accuracy at two concentration levels were also investigated. Precision for these five FWAs, as indicated by RSD, proved to be less than 13 and 11%, respectively, for intra- and interbatch. Accuracy, expressed as the mean recovery, was between 68 and 97%. The method was finally applied to environmental water samples, showing the occurrence of five FWAs in both river water and wastewater treatment plant (WWTP) effluent samples.     

Solid-phase extraction of soy isoflavones

An automated method using solid-phase extraction (SPE) for the concentration and clean-up of soy isoflavone extracts is proposed in this work. Using a standardized sample (0.1 g of a freeze dried soybean extract/25 mL of water); eight SPE cartridges with a wide range of sorbents (C18, divinylbenzene and modified divinylbenzene) from different suppliers were evaluated and compared. A large variation on SPE cartridges performance was observed, especially regarding retention and breakthrough volume of isoflavones during sample load and washing steps. The most effective cartridges were the divinylbenzene based cartridges, especially Strata X (from Phenomenex) and HLB oasis (from Waters). Using Strata X cartridges, several extraction parameters, such as sample loading flow (5-15 mL min(-1)), extracting solvent volume (2-6 mL of methanol), pH of the extracting solvent and the necessity of drying the sorbent before elution, were evaluated to provide a fast, specific, quantitative and reproducible SPE method. The optimized method consists of conditioning the cartridge with 10 mL of methanol and 10 mL of water (10 mL min(-1)), loading 25 mL of the standardized extract onto the cartridges (5 mL min(-1)), washing the cartridge with 10 mL of water (10 mL min(-1)) and finally eluting with 4 mL of methanol (10 mL min(-1)). Mean isoflavones recovery was 99.37% and mean intra- and inter-day reproducibility was higher than 98%. The developed sample clean-up/concentration (6.25:1) method takes less than 10 min and can be used in the analysis of isoflavones from soy extracts.     

Determination of phenoxyalkanoic acids and other herbicides at the ng/ml level in water by solid-phase extraction with poly(divinylbenzene-co-N-vinylpyrrolidone) sorbent and high-performance liquid chromatography--diode-array detection

A method for the determination of phenoxyalkanoic acids and other polar compounds in environmental water samples without pH adjustment before extraction has been developed. Recoveries were calculated from 500 ml of milliQ water spiked at the level of 0.5 ng/ml using solid-phase extraction (SPE) and HPLC-DAD. Different SPE materials (RP-C18, ENV+, ENV+-C8, SAX and Oasis HLB) were tested. After method optimization, 15 of the 16 compounds studied could be extracted with recoveries better than 70% on the most suitable copolymeric poly(divinylbenzene-co-N-vinylpyrrolidone) material (Oasis HLB cartridges).