Determination of halosulfuron-methyl residues and dissipation in wheat by QuEChERS and LC-MS/MS

A sensitive and rapid analytical method based on QuEChERS (quick, easy, cheap, effective, rugged and safe) sample preparation and LC-MS/MS detection was developed for the analysis of halosulfuron-methyl residues in wheat. The recoveries of halosulfuron-methyl in both the wheat plant and grain ranged from 87% to 119% and from 75% to 97%, respectively, with relative standard deviations (RSDs) of 3–9%. The limit of quantification (LOQ) was 0.005 mg kg^?1 for wheat plant and 0.001 mg kg^?1 for wheat grain. The half-life of halosulfuron-methyl in the wheat plant was 0.9–9.5 days. The terminal residue levels of halosulfuron-methyl in wheat grain were below 0.01 mg kg^?1 at harvest.     

Multiresidue method for detection of pesticides in beef meat using liquid chromatography coupled to mass spectrometry detection (LC-MS) after QuEChERS extraction

Beef meat is an important food that can be contaminated by pesticides. This study aimed to optimize a multiresidue method for identification and quantification of pesticides in beef meat by liquid chromatography coupled to mass spectrometry detection (LC-MS). The extraction and clean-up procedures were adapted from the QuECHERS method. From the 188 analytes tested, the method was validated as qualitative method for 19 compounds and as quantitative method for 152 compounds. The results were satisfactory, yielding coefficients of variation of less than 20% and recoveries ranging from 70% to 120% and expanded uncertainty of less than 50%. The quantification limit was typically 10 µg kg^?1 (but 25 µg kg^?1 for 12 of the compounds) and the detection limit was 5.0 µg kg^?1. Thirty-two real samples of commercialized beef meat were analyzed without any residual pesticide being found. Thus, the results showed that the multiresidue method for detecting 171 pesticides, using adapted QuECHERS for extraction and LC-MS for detection, is suitable for analyzing beef meat.     

Development and validation of LC-MS/MS method with QuEChERS clean-up for detecting cannabinoids in foods and dietary supplements

ABSTRACT

a rapid and simple liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed and validated for the determination of cannabidiol (CBD) and Δ⁹-tetrahydrocannabinol (THC) using a QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) clean-up for a variety of foods and dietary supplements (DS). QuEChERS is widely used in extraction or clean-up procedures to eliminate interference of matrices such as sugars, organic acids, lipids, and fatty acids. The samples were categorised into three types, and various pretreatment methods were compared for each type. In all types, the QuEChERS was superior and selected as the final pretreatment method. The optimised method was validated for specificity, limit of detection (LOD), limit of quantification (LOQ), linearity, recovery, precision and accuracy. All of the validation results met the requirements of the international guidelines for all types of samples. The validated method was applied to 30 commercial food samples, CBD was detected in 17 samples, with 2 of them detected below the LOQ level and the rest detected in a range of 70 μg/kg to 31305 mg/kg (3.1%, w/w). Meanwhile, THC was detected in 14 samples; 2 of them were detected below the LOQ level and the rest detected in a 0.08–98.62 μg/g range. These results indicated that the validated method can be successfully applied for the determination of cannabinoids in a variety of samples. Furthermore, it will be useful for controlling the illegal distribution of cannabinoids.     

改良QuEChERS技术结合液相色谱-串联质谱联用法同时快速检测辣椒制品中14种非法添加工业染料

采用改良Qu ECh ERS技术作为前处理方法,建立了辣椒制品中14种非法添加工业染料的液相色谱-串联质谱联用快速检测方法。样品采用乙腈-丙酮(7∶3,V/V)提取,经EMR-Lipid净化,以Agilent Poroshell 120 EC C18(50 mm×2.1 mm,2.7μm)色谱柱分离,采用多反应监测模式检测,外标法定量分析。14种成分在11 min内完成分离,检出限为0.4~7.1μg/kg,不同加标水平的平均回收率为70.5%~102.1%,相对标准偏差为0.3%~9.3%。本方法准确、快速、重复性好,可为辣椒制品中非法添加工业染料的检测提供一种更加快速、简便的技术支持。     

LC-MS/MS技术在食品中农药多残留分析的应用进展

液相色谱-串联质谱(LC-MS/MS)技术在食品中多类农药的高通量、高效率筛查和确证分析方面发挥了重要作用。本文对基于四级杆滤质器的LC-MS/MS技术近年来在食品中农药多残留分析方面的应用进展进行了综述,重点讨论了液相色谱-低分辨串联质谱(三重四级杆串联质谱和四级杆线性离子阱串联质谱)以及液相色谱-高分辨串联质谱(四级杆飞行时间串联质谱和四级杆静电场轨道阱串联质谱)在多类农药多残留分析中的应用。     

Development and validation of multi-residue method for determination of 412 pesticide residues in cotton fiber using GC-MS/MS and LC-MS/MS

The new global concept is to care about textiles and clothes safety to improve the protection of the human health and the environment from the harmful pesticide residues. Very few articles have been published for determination of several pesticide classes in cotton fibers in one multi-residue method. A simple, efficient, sensitive, accurate, and reliable multi-residue method was developed for the determination of 412 residual pesticides in cotton fibers using modified QuEChERS method with Liquid and Gas Chromatography coupled to Triple Quadrupole Mass Spectrometer (LC-MS/MS &; GC-MS/MS) for qualitative and quantitative analysis according to the international standards concepts. The developed method covered several pesticide classes, including 43 carbamates, 16 pyrethroids, 27 organochlorines (OCs), 54 organophosphorus (Ops), 31 urea derivatives, 7 Polychlorinated biphenyl (PCBs), 6 Neonicotinoid, and 228 other pesticides. Most of the target pesticides were listed in Oeko-Tex Standards, the EU Ecolabel for textile products, and the Egyptian recommendations of the Agricultural Pesticide Committee (APC-Egypt). The method optimization and validation were carried out according to the EU guidelines. The results were shown to be reliable where the corresponding average recoveries within the acceptable range of 70–120%; the relative standard deviations were less than 20%. The limit of quantitation (LOQ) of this method is 0.01 mg kg^?1 all pesticides except for 3 GC-compounds and 19 LC-compounds which have LOQ of 0.05 mg kg^?1.     

Analysis of multiresidue pesticides in dried hops by LC–MS/MS using QuEChERS extraction together with dSPE clean‐up

A simple and selective method is reported for the simultaneous determination of 48 fungicide, insecticide and herbicide residues in hops by LC–MS/MS. The extraction of pesticide residues from the hop matrix was conducted by a method based on the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) sample preparation approach in combination with dispersive solid‐phase extraction using various sorbent blends consisting of primary–secondary amine, C₁₈ and zirconia based sorbents. The matrix effect of all applied sorbent blends was evaluated. The results showed that the QuEChERS method required further optimization of the dispersive solid‐phase extraction cleaning step owing to co‐extraction of matrix components such as chlorophyll and hop resins. These contaminants resulted in signal suppression, elevated background, and other negative matrix effects. The accuracy, precision, specificity, linearity, limit of detection and limit of quantification were evaluated. The recovery ranged from 70 to 120% for most of the pesticides and RSD was <20% for all pesticides. The limit of quantification was estimated at 0.02 mg/kg or, in the worst cases, 0.05 mg/kg. The results meet the European Commission standard legislation, implying that this method is both accurate and reproducible. Copyright © 2018 The Institute of Brewing & Distilling     

高效液相色谱串联质谱法分析烟草中15种农药残留

为检测烟草中的“吡蚜酮”等农药残留,建立了乙腈提取、分散固相萃取净化和高效液相色谱-质谱联用(LC-MS/MS)快速分析烟草中15种农药残留的方法.结果表明:15种农药在0.10,0.25和0.50 μg/g 3个加标水平的回收率为70.43% ～ 117.81%,相对标准偏差(RSD)为1.16%-13.89%,检出限为0.004～0.030 μg/g.该方法适合于批量烟草样品中多种农药残留的快速分析.     

Multiresidue method for the determination of 77 pesticides in wine using QuEChERS sample preparation and gas chromatography with mass spectrometry

A method based on a QuEChERS (quick, easy, cheap, effective, rugged, safe) sample preparation method and gas chromatography with mass spectrometric detection by selected ion monitoring (GC/MS-SIM) was developed for simultaneous determination of 77 pesticide residues in wine. An extraction of 10 ml of sample with acetonitrile followed by liquid–liquid partition formed by the addition of 4 g MgSO₄ and 3 g NaCl was applied in the sample preparation. The clean-up was carried out by applying dispersive solid-phase with 150 mg MgSO₄ as well as 50 mg primary secondary amine (PSA). One quantitation ion and at least two identification ions were selected in the analytical method for each pesticide compound by GC/MS. The recovery data were obtained by spiking blank samples at two concentration levels (0.05 and 0.2 mg l^?1). The recoveries of all pesticides were in the range 70–110%, with intra-day precision of less than 15%, and the inter-day precision of less than 22% and 15% for 0.05 and 0.2 mg l^?1 fortification levels, respectively. Linearity was between 0.02 and 2 mg l^?1 with determination coefficients (R ²) greater than 0.98 for all compounds. The limits of quantification (LOQs) for the 77 pesticides ranged from 0.003 to 0.05 mg l^?1. This method was applied for routine analysis in market products.     

液相色谱—串联质谱法检测纺织品中芦荟成分

建立高效液相色谱—串联质谱法测定纺织品中芦荟苷、芦荟大黄素和大黄酚含量的方法。样品经甲醇60℃超声波浴提取30 min后,在Agilent Eclipse XDB-C18(2.1 mm×150 mm,3.5 m)色谱柱上分离,以10 mmol/L乙酸铵溶液(pH=5.75)和乙腈为流动相进行梯度洗脱。三重四级杆质谱采用电喷雾离子源负离子模式在多反应监测(MRM)模式下检测被分析物,外标法定量。纺织样品在3个加标水平时,平均回收率为85.5%～99.9%,相对标准偏差(RSDs)为1.76%～5.92%。该方法具有快速、灵敏、准确、可重复的特点,可应用于纺织品中芦荟成分的痕量分析。     

Corticosteroids in liver and urine in Sicilian cattle by a LC-MS/MS method

The presence of corticosteroid residues was assessed in urine and liver samples from livestock of Sicily. A total of 630 bovine samples were collected from farms and slaughterhouses. The samples were analysed using solid-phase extraction (SPE) coupled with ultra-performance liquid chromatography tandem mass spectrometry (UHPLC–MS/MS). All the corticosteroids found were under the maximum residue limit imposed by Commission Regulation (EC) 37/2010. About 4% of liver samples showed dexamethasone levels above the limit of detection (LOD), with a mean of 1.5 ± 0.2 µg kg^?1. Betamethasone was found only in seven liver samples, with a mean of 1.6 ± 0.1 µg kg^?1. Furthermore, prednisolone and prednisone were found only in urine and liver samples from slaughterhouse, probably related to the high rate of stress for bovines. These results suggest good control practices adopted by Sicilian farms, able to ensure the quality of food products.     

A multiresidue method for the determination of 107 pesticides in cabbage and radish using QuEChERS sample preparation method and gas chromatography mass spectrometry

A rapid, specific and sensitive multiresidue method based on the modified Quick Easy Cheap Effective Rugged and Safe (QuEChERS) sample preparation method and gas chromatography with the electron impact mass spectrometric detection in the selected ion monitoring mode (GC–MS-SIM) using one target and two qualifier ions for the routine analysis of 107 pesticides in cabbage and radish has been developed. The recoveries for all the pesticides studied were from 80% to 115% with relative standard deviation lower than 15% in the concentration range of 0.030–0.360 mg/kg. The limit of quantitation (LOQ) for most compounds met MRLs for pesticides in cabbage and radish in Korea. This method was successfully applied to analysis commercial cabbage and radish samples.     

QuEChERS-UPLC-Q/Orbitrap MS法快速测定草鱼中14种糖皮质激素类药物残留

运用QuEChERS前处理技术,结合超高效液相色谱—四级杆/静电场轨道阱高分辨质谱(UPLC-Q/Orbitrap MS)建立草鱼中14种糖皮质激素类药物残留的快速检测方法。结果表明:14种糖皮质激素在2.0~100.0ng/mL时具有良好的线性关系(R~2≥0.999),方法检出限为1.3~6.0μg/kg,定量限为4.5~20.0μg/kg,加标回收率为76.9%~103.3%,RSD (n=6)为1.6%~6.3%。该方法简单高效、准确度高,适用于大批量草鱼中糖皮质激素的快速检测。     

LC-MS/MS法测定人血浆中曲司氯铵的浓度

目的建立测定人血浆中曲司氯铵浓度的LC—MS／MS方法。方法血浆样品经液-液提取后,以甲醇（含0．1％乙酸）：水（含0．1％乙酸＋2．5mmol／L酸铵）（80：20）为流动相,使用Agilent1100VL型离子阱质谱仪,电喷雾离子源正离子模式,采用多反应离子监测方式测定曲司氯铵（MRM,m／z392→164＋182）。结果血浆中曲司氯铵线性范围为0．1～10．0ng／mL,定量下限为0．1ng／mL,准确度85％～115％,日内、日间精密度（RSD）&#177;15％。结论该方法准确,专属性强,可用于曲司氯铵药动学研究。     

Development of an LC-MS/MS method for the determination of pesticides and patulin in apples

A method for the simultaneous determination of 33 pesticides or degradation products together with patulin in apples by liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed. The method involved homogenization of the apples, extraction with ammonium acetate–acetic acid solution in methanol–water by ultrasonication, filtration, and determination by LC-MS/MS. The repeatability and within-laboratory reproducibility for the three spiking levels 0.02, 0.04 and 0.2 mg kg^?1 were between 4% and 35%. In general, the repeatability and reproducibility were about 10–20%. The limits of quantification (LOQs) were between 0.01 and 0.14 mg kg^?1. The method was used on incurred samples from parts of the ISAFRUIT project financed by the European Commission under the 6th Framework Programme. Samples were analysed at four different stages: after harvest, after storage (controlled), after a water bath, and after 28 days at room temperature. Pesticide residues were found at all stages, but no significant differences in the concentration were seen between the stages analysed. The concentration decreased significantly only for tolylfluanid after storage at room temperature for 28 days when only 0–6% of the original amount of tolylfluanid remained in the apples. No patulin was found in the apples stored for 28 days at room temperature and no growth of Penicillium expansum was observed on these apples. However, when the apples were inoculated with a spore suspension of P. expansum, high concentrations of patulin were found.     

LC-MS/MS定量分析卷烟中的烟草特有亚硝胺(TSNAs)

烟草特有亚硝胺(TSNAs)是所有烟草特有的成分。传统上采用气相色谱-热能分析仪(GC-TEA)测定卷烟烟丝和烟气中的TSNAs,该法的缺点是纯化步骤多,分析时间长。本法-即LC-MS/MS法采用0.1%AA(乙酸胺)水溶液直接对卷烟烟丝或收集主流烟气的剑桥滤片进行简单的超声萃取,萃取液与乙腈(含氘化的内标物)等体积混合,高速离心,上层清液用带有正离子电子喷雾装置的LC-MS/MS仪进行分析。本法性能稳定,分析的样品数量大,数据可靠,萃取效率及回收率高;仪器检测限比传统分析方法低得多;分析时间短(每个样仅3min左右)。本文给出了烟草中4种特有亚硝胺的LC-MS/MS法的液相操作条件、质谱分析测定参数,TSNAs的仪器最低检测限值、回收率、精密度、定量分析曲线等,还对国内外市场上销售的44种卷烟进行了定量分析测定。      

卷烟主流烟气中挥发性醛酮的LC-MS/MS分析

采用2,4-二硝基苯肼衍生-LC-MS/MS法测定了32种卷烟样品主流烟气中的甲醛、乙醛、丙烯醛、丙酮、丙醛、巴豆醛、甲基丙烯醛、2-丁酮、丁醛、苯甲醛、戊醛、己醛.结果表明:①方法的检测限为0.1～0.5 ng/mL,回收率在91.6%～100.3%之间,相对标准偏差为3.28%～7.86%;②卷烟样品主流烟气的挥发性醛酮成分中主要为乙醛和丙酮,苯甲醛、已醛含量较小;③与进口烟相比,国产烤烟型卷烟主流烟气中的挥发性醛酮含量相对较高,混合型卷烟的相对较低;④不管是烤烟型还是混合型,焦油量高的卷烟主流烟气中的挥发性醛酮含量均相对较高.     

LC-MS/MS法分析清爽型黄酒中的嘌呤含量

嘌呤是引起痛风的关键因素,检测黄酒中的嘌呤含量具有重要意义。本研究建立了一种采用液相色谱串联质谱法(LC-MS/MS)测定黄酒中嘌呤含量的方法。结果表明,清爽型黄酒中鸟嘌呤为0.67 mg/L,次黄嘌呤为0.62 mg/L,腺嘌呤为0.82 mg/L,总含量为2.12 mg/L。LC-MS/MS法样品加标回收率在98.2%-100.6%之间,相关系数大于0.995,相对标准偏差为3.8%-5.2%。     

Analysing organochlorine pesticides in strawberry jams using GC-ECD,GC-MS/MS and QuEChERS sample preparation

This paper describes a comparison of adaptations of the QuEChERS (quick, easy, cheap, effective, rugged and safe) approach for the determination of 14 organochlorine pesticide (OCP) residues in strawberry jam by concurrent use of gas chromatography (GC) coupled to electron capture detector (ECD) and GC tandem mass spectrometry (GC-MS/MS). Three versions were tested based on the original QuEChERS method. The results were good (overall average of 89% recoveries with 15% RSD) using the ultrasonic bath at five spiked levels. Performance characteristics, such as accuracy, precision, linear range, limits of detection (LOD) and quantification (LOQ), were determined for each pesticide. LOD ranged from 0.8 to 8.9?µg?kg^?1; LOQ was in the range of 2.5–29.8?µg?kg^?1; and calibration curves were linear (r ^2?>?0.9970) in the whole range of the explored concentrations (5–100?µg?kg^?1). The LODs of these pesticides were much lower than the maximum residue levels (MRLs) allowed in Europe for strawberries. The method was successfully applied to the quantification of OCP in commercially available jams. The OCPs were detected lower than the LOD.     

QuEChERS结合液相色谱-串联质谱法测定食用菌中13种农药残留

目的:建立并应用QuEChERS结合液相色谱-串联质谱法测定食用菌中13种农药残留。方法:样品5.0 g用乙腈-水(4:1)15 mL超声提取,经N-丙基乙二胺(PSA)30.0 mg和无水硫酸镁15.0 mg分散固相萃取吸附剂净化。使用HSS T3色谱柱,0.1%甲酸和乙腈为流动相梯度洗脱。质谱采用电喷雾正离子源和多反应监测模式。结果:13种农药的质量浓度在0.5~200 μg/L范围内与峰面积呈良好的线性关系,检出限(S/N=3)0.03~0.3 μg/kg。加标回收率84.3%~102%,相对标准偏差(n=6)2.8%~6.3%。结论:该方法可用于食用菌中13种农药残留的检测。