顶空固相微萃取与气相色谱-电子捕获技术联用检测软木塞中2,4,6-三氯苯甲醚

建立利用顶空固相微萃取与气相色谱电子捕获技术联用分析检测葡萄酒软木塞中2,4,6-三氯苯甲醚含量的方法。该方法测定软木塞中2,4,6-三氯苯甲醚的相关系数（R²）为0.999 9,精密度好（相对标准偏差不大于5.6%）,回收率为101%～108%,检出限为0.20 pg/L、定量限为0.66 pg/L。利用该方法测定了11 种不同类型的软木塞中2,4,6-三氯苯甲醚的含量,证实了所建方法适用于葡萄酒软木塞中痕量2,4,6-三氯苯甲醚含量的测定。     

超高效液相色谱-串联质谱法测定食用猪油中氯酚类物质

目的应用超高效液相色谱-串联质谱技术,建立同时测定食用猪油中2,4,5-三氯苯酚、2,4,5-三氯苯氧乙酸和五氯酚3种物质的方法。方法样品用80%乙腈提取,固相萃取(SPE)和正己烷净化萃取后,以Atlantis?T3(2.1 mm×150 mm,3μm)为分析柱,乙腈-5.0 mmol/L乙酸铵溶液为流动相,以电喷雾离子源在负离子多反应监测模式下进行测定,基质匹配外标法定量。结果 2,4,5-三氯苯酚、2,4,5-三氯苯氧乙酸和五氯酚在2.0～100.0μg/L范围内线性关系良好,相关系数(r)均大于0.999,方法检出限分别为0.09、1.59、0.90μg/kg,定量限分别为0.29、5.28、3.00μg/kg,回收率为71.9%～109.5%,相对标准偏差为0.2%～9.2%(n=6)。结论该方法简便、准确、灵敏度高,适用于食用猪油中2,4,5-三氯苯酚、2,4,5-三氯苯氧乙酸、五氯酚3种物质的高通量检测。     

果蔬汁中含氯杀菌剂的气相色谱分析

以甲苯为萃取剂,甲醇为分散剂,分散液液微萃取果蔬汁中2,4,6-三氯酚、五氯苯甲醚、五氯硝基苯3种含氯杀菌剂,毛细管气相色谱分离/电子捕获检测器测定。试验主要考察了分散剂、萃取剂、盐效应及酸度对目标化合物萃取的影响情况。结果表明,在5.0μg/mL~100.0μg/mL范围内3种组分有良好线性,相关系数大于0.999 3,平均回收率分别为95.3%、96.5%、81.5%,相对标准偏差为5.53%、6.37%、5.94%。     

固相萃取-气相色谱-串联质谱法测定淡水鱼鱼肉中的五氯酚

目的建立采用固相萃取-气相色谱-串联质谱联用为基础的淡水鱼鱼肉中五氯酚的测定方法。方法淡水鱼鱼肉经粉碎后,液液萃取,MAX柱净化,乙酸酐-吡啶溶液衍生成五氯苯乙酸酯,气相色谱-串联质谱仪进行定性和定量分析。结果在1、5、20μg/kg 3个水平下的回收率范围为85.6%~98.4%,相对标准偏差小于10%,方法的定量限为0.85μg/kg(S/N=10),检出限为0.26μg/kg(S/N=3)。结论该方法具有良好的回收率及稳定性,适用淡水鱼鱼肉中五氯酚的测定。     

顶空固相微萃取联合气相色谱-质谱检测葡萄酒中2,4,6-三氯苯甲醚

利用响应面法优化采用顶空固相微萃取联合气相色谱-质谱技术检测葡萄酒中2,4,6-三氯苯甲醚（2,4,6-trichloroanisole,TCA）。对萃取头进行了选择,并优化固相微萃取参数：样品体积、萃取温度、平衡时间和萃取时间等对TCA萃取效果的影响。结果表明,用聚二甲基硅氧烷/二乙烯基苯（65 μm）萃取头进行TCA萃取的最佳条件：样品9.8 mL、2 g NaCl、33 ℃平衡10 min、萃取90 min进行气相色谱-质谱分析,以TCA-d5为内标物进行定量。该方法的相关系数R2为0.999 9,重复性的相对标准偏差为1.03%,加标回收率范围在95.7%～106.1%之间,检出限和定量限分别为0.3 ng/L和1 ng/L。检测7 种市售葡萄酒产品的TCA含量在0～7.6 ng/L之间,干白葡萄酒中TCA含量低于干红葡萄酒。该方法操作简单、可靠,适用于葡萄酒中TCA的测定。     

超声波辅助-顶空固相微萃取-气相色谱法测定葡萄酒中痕量2,4,6-三氯苯甲醚

建立了超声波-顶空固相微萃取-气相色谱检测葡萄酒中的痕量木塞污染物——2,4,6-三氯苯甲醚（TCA）的方法。试验结果表明,该方法有良好的线性关系,相关系数为0.999 89,方法定量限为0.5 ng/L,相对标准偏差RSD在1.98%～5.32%之间,加标回收率为89.0%～103.2%。该方法操作简便、快速、准确度高、重现性好,适用于普通实验室对葡萄酒中痕量TCA残留的检测。     

气相色谱-质谱法测定食品用纸制品中五氯酚含量

目的建立气相色谱-质谱法测定食品用纸制品中五氯酚含量的分析方法,了解食品用纸制品中五氯酚的残留状况。方法纸制品试样加入2,4,6-三溴酚内标后,经液-液萃取, SLC柱净化,乙酸酐-吡啶溶液衍生后,采用气相色谱-质谱法测定,内标法定量。结果在50~1000ng范围内,相关系数均>0.9995。方法的检出限为0.008mg/kg,定量限为0.025mg/kg。加标回收率为89.3%~109.8%,相对标准偏差(relativestandard deviations, RSDs)分别为3.2%、8.6%和4.4%。106份市售纸制品中, 8份样品检出五氯酚,阳性率为7.5%,含量范围为0.011~0.045 mg/kg,阳性样品五氯酚含量的平均值为0.027 mg/kg。结论该方法灵敏度较高,精密度好,适用于纸制品中五氯酚的准确定量检测。检测数据表明,食品用纸制品中五氯酚风险较小。     

超声波辅助-顶空固相微萃取-气相色谱法测定软木塞中痕量2,4,6-三氯苯甲醚

通过对软木塞样品提取过程的优化,建立了超声波法辅助顶空固相微萃取-气相色谱仪检测软木塞中痕量2,4,6-三氯苯甲醚(TCA)的方法。试验结果表明,该方法的线性范围0.5 ng/L~80.0 ng/L,R2为0.999 8,线性关系良好。方法检出限为0.2 ng/g,方法定量限为0.5 ng/g,精密度(RSD)在1.35%~5.47%之间,加标回收率为81.5%~97.8%。该方法操作简便、快速、易操作、准确度高、重现性好,适用于普通实验室对软木塞中痕量2,4,6-三氯苯甲醚残留的检测。     

葡萄酒和软木塞中2,4,6-三氯苯甲醚检测方法的研究进展

本文介绍了葡萄酒和软木塞中2,4,6-三氯苯甲醚（2,4,6-trichloroanisole,TCA）的来源及影响,分析了2,4,6-三氯苯甲醚的检测难点,总结了目前检测2,4,6-三氯苯甲醚方法的总体趋势及现状。按照前处理方法的原理分类,介绍了前处理方法的定义、特点,并概述和讨论了前处理方法在萃取葡萄酒和软木塞中2,4,6-三氯苯甲醚中的应用;根据仪器检测方法的不同特点,总结和讨论了仪器检测方法在分析检测葡萄酒和软木塞中2,4,6-三氯苯甲醚的应用。前处理方法和仪器检测方法相结合,达到了浓缩和检测葡萄酒和软木塞中2,4,6-三氯苯甲醚的目的。     

顶空固相微萃取气相色谱法测定水产品中五氯酚残留量

应用气相色谱法与顶空固相微萃取样品预处理技术相结合的方法,测定水产品中五氯酚(PCP)。选用20 m L顶空瓶,其中预置1 mol/L盐酸溶液0.7 m L及氯化钠4.0 g,加入1.0 g样品用1 mol/L氢氧化钠溶液定容10 m L,立即封盖。插入85μm聚丙烯酸醋萃取头于65℃平衡35 min后的顶空瓶萃取15 min,随之进入色谱仪解吸3 min并测定。测定中采用HP-5毛细管柱和程序升温(40℃~280℃)条件,并用载气流量为3 m L/min。测得五氯酚(PCP)的方法定量限为0.15μg/kg,标准曲线的相关系数为0.995,样品低、中、高三种浓度的加标后回收率为96.3%~112.6%,相对标准偏差(n=6)为3.3%~4.5%。该法快速、准确、绿色、无污染的检测出水产品中五氯酚的残留量的方法技术,并应用于日常监测与检测中,最终杜绝食品安全隐患问题。     

Determination of geosmin and 2,4,6-trichloroanisole in white and red Austrian wines by headspace SPME-GC/MS and comparison with sensory analysis

This paper describes the development and application of a fast and simple headspace solid phase microextraction GC–MS method for simultaneous determination of geosmin and 2,4,6-trichloroanisole (2,4,6-TCA), two main contributors to off-flavors in wine. The compounds were adsorbed onto a polydimethoxysiloxane (PDMS) fiber at 35 °C for 40 min without prior equilibration, thermally desorbed and analyzed by GC–MS in the selected ion monitoring mode. The parameters for adsorption onto and desorption from the fiber were optimized. This method was applied to analysis of 118 Austrian white and red wines, which were also characterized by sensory analysis. Geosmin was above the limit of detection (0.5 ng/L) in 110 wines (93%) and additionally quantified (>2 ng/L) in 65 wines (55%). It could be detected in wines of each off-flavor (moldy, corky, damp, musty, rotten, woody, grassy) in concentrations up to 16.7 ng/L and even in 90% of the sensorially faultless wines (up to 6.5 ng/L). On the other hand, 2,4,6-trichloroanisole was detected only in 24 wines (20% of all investigated wines) and above the limit of quantitation (2 ng/L) only in 5 wines (4%) sensorially classified as corky; corky and moldy plus other defects; or faultless in concentrations up to 14.3 ng/L. These results show that geosmin is more prevalent than 2,4,6-TCA and that chemical analysis is required especially when other wine characteristic flavors cover beginning off-flavors.     

Matrix effect during the application of a rapid method using HS-SPME followed by GC–ECD for the analysis of 2,4,6-TCA in wine and cork soaks

An off-flavor in wine known as ‘cork taint’ is of concern in the wine and cork industry. Cork taint imparts a musty flavor to the wine and is primarily due to the presence of 2,4,6-trichloroanisole [2,4,6-TCA] in cork stoppers. During this study, an instrumental method for 2,4,6-TCA analysis was developed and evaluated using headspace solid-phase microextraction (HS-SPME) and gas chromatography coupled with an electron capture detector (GC–ECD). 2,3,6-Trichlorotoluene [2,3,6-TCT] was assayed as the internal standard. The method was developed in synthetic wine and was applied in commercial wine samples, as well as in cork soaks obtained by the extraction of TCA from cork stoppers and cork barks using synthetic wine. The method performance was evaluated through the estimation of its linearity (R² > 0.99), repeatability (RSD value = 5.72%) and sensitivity (recovery > 86%, LOD = 0.177–0.368 ng/L) in different types of samples. Due to the complexity of the samples used, the study has been especially focused on the matrix effects that were identified causing significant bias to the quantitative analysis of 2,4,6-TCA in cork soaks, where there is a lack of previous studies.     

发酵食品中氨基甲酸乙酯污染状况调查与分析

采用液液萃取和基质固相分散的样品前处理技术,应用气相色谱-串联质谱的检测方法对发酵食品中氨基甲酸乙酯(ethyl carbamate,EC)的污染状况进行调查和分析,共检测发酵食品437批次,其中EC阳性样品343批次,阳性率为78.49%,阳性率最高的是果酒100%,其次是酱油98.17%、醋86.67%和黄酒78.38%,最低的是啤酒,为未检出。饮料酒中EC平均值最高的是黄酒90.4μg/L,其次为保健酒62.9μg/L,最低为葡萄酒,为7.6μg/L,调味品中酱油和醋EC平均值分别为84.1μg/kg和76.2μg/kg,焙烤食品中面包EC平均值24.3μg/kg。研究结果表明,黄酒、酱油和醋中EC的阳性率、平均值相对较高,在今后的研究和监测中需要重点关注。     

葡萄酒中赭曲霉素A测定方法的研究

采用固相萃取小柱对葡萄酒中的赭曲霉素A(OTA)进行浓缩处理,选择高效液相荧光法和超高效液相质谱联用法,分别测定葡萄酒中的OTA含量。采用HPLC-FLD法测定葡萄酒中OTA时,线性良好,R2=0.9997;经固相萃取小柱浓缩后,测定方法检出限可达到0.002μg/L;回收率为85.7%～102.6%;RSD(n=5)为4.5%。通过HPLC-FLD和UPLC-MS/MS测定OTA方法对比发现HPLC-FLD方法具有更好的灵敏度和检出限。     

Analysis of six fungicides and one acaricide in still and fortified wines using solid-phase microextraction-gas chromatography/tandem mass spectrometry

A multiresidue gas chromatographic method for the determination of six fungicides (captan, chlorthalonil, folpet, iprodione, procymidone and vinclozolin) and one acaricide (dicofol) in still and fortified wines was developed. Solid-phase microextraction (SPME) was chosen for the extraction of the compounds from the studied matrices and tandem mass spectrometry (MS/MS) detection was used. The extraction consists in a solvent free and automated procedure and the detection is highly sensitive and selective. Good linearity was obtained with correlation coefficients of regression (R²) > 0.99 for all the compounds. Satisfactory results of repeatability and intermediate precision were obtained for most of the analytes (RSD ? 20%). Recoveries from spiked wine ranged from 80.1% to 112.0%. Limits of quantification (LOQs) were considerably below the proposed maximum residue limits (MRLs) for these compounds in grapes and below the suggested limits for wine (MRLs/10), with the exception of captan.     

SPE-GC/MS外标法测定酒中氨基甲酸乙酯

建立固相萃取(SPE)结合气相色谱质谱联用仪(GC/MS)测定酒中氨基甲酸乙酯。试样经硅藻土固相萃取柱净化,乙酸乙酯/乙醚洗脱后,气相色谱-质谱联用仪测定,利用选择离子监测模式及外标法对其进行定性、定量。氨基甲酸乙酯在10—120μg/L浓度范围内线性关系良好,r2=0.9993,检测限为1.6μg/kg,定量限为3.0μg/kg,加标回收率在81.0%—97.4%之间,RSD为2.6%—5.5%(n=6)。应用此方法,对市场销售的各种酒进行了检测,氨基甲酸乙酯的含量在5.8—93.6μg/kg之间。此方法可靠、便捷,净化效果好,灵敏度、准确度均满足检测要求,可作为酒中氨基甲酸乙酯含量的检测方法。     

Determination of Chloroanisoles and Chlorophenols in Cork and Wine by using HS‐SPME and GC‐ECD Detection

Cork taint is an off‐flavor problem in wine, the main reason being the presence of 2,4,6‐trichloroanisole (TCA) in the cork stopper. In addition to the TCA, the presence of other chloroanisole and chlorophenol family compounds (the perception limits of which are very low) can also result in, or contribute to, cork taint problem. In this study, the levels of 2,4‐dichloroanisole (DCA), 2,4,6‐trichloroanisole (TCA), 2,3,4,6‐tetrachloroanisole (TeCA), pentachloroanisole (PCA), 2,4,6‐trichlorophenol (TCP), 2,3,4,6‐tetrachlorophenol (TeCP) and penthaclorophenol (PCP) were assayed in cork stoppers (natural, agglomerated and colmate) and in red wine samples from different wineries in Turkey using HS‐SPME and GC‐ECD detection. The performance parameters for all chloroanisole and chlorophenol compounds were as follows: recovery 92.48–102.53%, R 0.992‐0.996. The LOQ values were DCA (8.4 ng/L), TCA (0.8 ng/L), TeCa (0.6 ng/L), PCP (0.8 ng/L), TCP (0.8 ng/L), TeCP (1.2 ng/L), and PCP (1.1 ng/L) respectively. In cork stoppers, the amounts of 2,4,6 TCA ranged between 5.4–130.6 ng/g. The 2,3,4,6 TeCA ranged between 1.12‐8.2 ng/g and the PCA ranged between nd (not detected)‐11.01 ng/g. In the wine samples, 2,4,6 TCA ranged between 1.42–70.2 ng/L. The 2,3,4,6 TeCA ranged between nd‐15.1 ng/L and the PCA ranged from nd‐5.16 ng/L. The results indicated that there was a significant correlation between the TCA in wines and the TCA in cork stoppers.