基于QuEChERS的UHPLC-MS/MS同时检测鸡蛋中19种农药残留量

目的：构建一种同时、快速、高效的检测鸡蛋中多种农残方法。方法：将QuEChERS与UHPLC-MS/MS结合用于鸡蛋中19种农药残留量的检测。结果：所建方法的检出限（LOD）和定量限（LOQ）分别为（0.39±0.66）,（1.28±2.17） μg/kg;加标回收率为79.25%～102.14%,相对标准偏差均值（RSD）为9.34%～16.72%;除恶唑菌酮外,鸡蛋中其余18种农药的线性相关系数接近0.999。所测鸡蛋中鸡蛋中19种农残检出总频率为2.82%,农残问题主要涉及辛硫磷和毒死蜱,其检出频率分别为22%,15%,浓度范围分别为2.08～729.74,0.81～46.89 μg/kg。结论：所建方法准确可靠,符合相关检测要求;湖北省境内鸡蛋中农残检出频次低、安全隐患较小。     

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.     

Simultaneous multiresidue analysis of 41 pesticide residues in cooked foodstuff using QuEChERS: Comparison with classical method

The principal objective of this study was to develop a simple multiresidue method involving a quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction method for the identification and quantification of 41 pesticide residues in cooked foodstuffs including cooked potatoes, radishes, and rice using GC-μECD. The analytes were subsequently confirmed via GC–MS. The results were then compared using the classical method established by the KFDA. The quantitation of individual pesticides was based on matrix-matched calibration curves with a correlation coefficient in excess of 0.993 for the 41 pesticides selected herein. Using QuEChERS, the mean recoveries ranged between 68.6 and 130.0% for the majority of the tested pesticides; however, the classical method exhibited low recoveries for dichlofluanid, tetraconazole, oxadixyl, fenbuconazloe, and paclobutrazol. After QuEChERS, the LODs and LOQs ranged between 0.004 and 0.3 μg/kg and 0.0125 and 1.0 μg/kg, respectively. The proposed method was applied successfully to determine the residue levels in cooked foodstuffs, and none of the samples contained detectable amounts of pesticide residues.     

QuEChERS-TOF-MS/MS 检测食品农产品中残留的未知农药

目的 利用 LC-Triple TOF 仪器建立筛查食品/农产品中未知农药的分析方法。 方法 采用 QuEChERS 法对多种食品/农产品中残留的农药进行提取, PeakView 软件全智能分析, 对照每个化合物的 TOF-MS 质量精度及同位素分布情况, 以及对照化合物 TOF-MS/MS 与标准品谱库, 给出匹配度, 对照化合物与标准品的保留时间, 对化合物作出定性判断。同时利用 MultiQuant 软件对检出的化合物含量结果进行定量分析。结果 该方法通过自动校正系统, 能自动进行批校正, 长时间内系统的准确质量数稳定, 且该系统的质量准确度小于1 mg/kg。结论 该方法满足对食品/农产品中农药残留的筛查检测要求, 适用于检测部门的日常筛查工作。     

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.     

QuEChERS 方法在茶叶农药残留检测中的应用研究进展

茶叶的农药残留检测关系到茶叶的质量安全。茶叶样品基质复杂,干扰物质多,其样品前处理是农药残留检测过程中耗时最长、工作量最大的部分,前处理技术的好坏也决定着分析的准确性和精密度。QuEChERS(quick, easy, cheap, effective, rugged, safe)方法作为一种农药多残留分析的前处理方法,由于具有快速、简单、廉价、有效、可靠、安全的特点而成为近年来的研究热点。本文就QuEChERS方法及其在茶叶农药残留检测中的应用研究进展进行评述。     

QuEChERS-LC-MS/MS联用技术对浆果中多种农药残留的测定

为建立检测浆果中多种农残的方法,运用QuEChERS前处理技术,结合高效液相色谱与串联质谱联用（HPLC-MS/MS）技术同时测定浆果中10种农药残留。结果显示,最优分散剂组合为10 g样品中加入PSA 50 mg,GCB 2.5 mg和C18 50 mg进行基质的净化,此条件下平均回收率达到75.38%。10种农药对照品在1～100 μg/L范围内,呈现良好的线性关系,测定蓝莓中10种农药残留的加标回收率为95.31%～111.26%,相对标准偏差为0.90%～4.16%,测定葡萄中10种农药残留的加标回收率为90.37%～116.20%,相对标准偏差为0.80%～5.09%。该方法简便、快速、准确,适用于常见浆果中农药残留的分析。     

Evaluation of QuEChERS method for the determination of organochlorine pesticide residues in selected groups of fruits

This paper reports a method for organochlorine pesticide determination in selected fruit species where pesticide residues were extracted and cleaned using a buffered QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method, followed by GC–MS analysis. The method results showed the matrix-matched calibration curve linearity was >0.99 for all target analytes. With pesticide recovery rates (spiked at 0.008 mg kg⁻¹) ranging from 70% to 120%, and RSD values <17% for most compounds, the limit of quantification ranged from 0.001–0.013 mg kg⁻¹. Finally, the method ruggedness was further demonstrated by analysis of actual commercial fruits and baby food samples.     

QuEChERS净化-UPLC-MS/MS法测定番茄中19种农药残留

采用QuEChERS净化-超高效液相色谱-串联三重四极杆质谱法（UPLC-MS/MS）测定番茄中19种农药残留。经改进的QuEChERS方法进行前处理,采用Aglient-C18色谱柱分离,以4 mmol/L甲酸水溶液和甲醇为流动相进行梯度洗脱。质谱采用电喷雾（ESI）正离子源和多反应监测（MRM）模式,外标法定量。结果表明,19种农药的质量浓度为2.0～200.0 μg/L时,线性关系良好,相关系数（R2）＞0.998,定量限为0.15～1.50 μg/kg,回收率为79.8%～103.9%,相对标准偏差（RSD）为3.2%～11.8%。说明该方法灵敏度高,适合番茄中19种农药残留检测的要求。     

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。     

Determination of pesticide residues in food matrices using the QuEChERS methodology

The determination of pesticide residues in food matrices is a formidable challenge mainly because of the small quantities of analytes and large amounts of interfering substances which can be co-extracted with analytes and, in most cases, adversely affect the results of an analysis. However, safety concerns require that pesticides of the wide range of chemical properties (including acidic, basic and neutral) should be monitored. Because of the wide variety of food matrices, the sample must initially be cleaned up before final analysis. That is why the analytical chemist is faced with the need to devise new methodologies for determining such residues to be determined in a single analytical run. To accomplish the goal, QuEChERS methodology has been developed. It is a streamlined and effective extraction and cleanup approach for the analysis of diverse analyte residues in food matrices. So far, there have been achieved promising results by liquid or gas chromatography analysis, including pesticides, but also acrylamide, pharmaceuticals and veterinary drugs.     

QuEChERS-液相色谱-串联质谱法测定葵花籽中30种农药残留

目的 建立QuECHERS-液相色谱-串联质谱法测定葵花籽中30种农药残留的分析方法.方法 葵花籽用1％乙酸-乙腈溶液提取,QuEChERS试剂净化,液相色谱-串联质谱法(liquid chromatography-tandem mass spectrometry,LC-MS/MS)测定,多反应监测模式(multipl...     

QuEChERS-超高效液相色谱-串联质谱法测定葡萄中388种农药残留

目的:建立了同时测定葡萄中388种农药残留量的方法。方法:样品经1%冰醋酸乙腈振荡提取后,加入无水醋酸钠、无水硫酸镁,提取液经300 mg硅胶、300 mg C₁₈、600 mg N-丙基乙二胺(PSA)和900 mg无水硫酸镁分散固相萃取吸附剂净化,上清液经氮吹浓缩,以乙腈-0.1 mol/L乙酸铵溶液(1:1)溶解进样,采用超高效液相色谱-串联质谱仪(UPLC-MS/MS)测定,分析物均采用电喷雾离子源,正离子扫描,多反应监测(MRM)模式,基质匹配内标法定量。结果:388种农药在0.005~0.4 mg/L浓度范围内线性关系良好,相关系数(r)在0.99以上,方法检出限均为0.005 mg/kg,3个加标水平的回收率为60%~120%,相对标准偏差均小于20%(n=7)。结论:该方法可同时测定388种农药残留,耗时较短,灵敏度高,分析物出峰均匀稳定,适用于葡萄中多农药残留的日常检测。     

QuEChERS/气相色谱三重四级杆质谱法测定枸杞籽油中多环芳烃类物质

建立了同时检测保健食品枸杞籽油中16种多环芳烃(PAHs)的QuEChERS/气相色谱三重四级杆质谱(GC-MS/MS)方法。样品(0. 5 g)经3 mL乙腈提取2次,采用含200 mg PSA和100 mg C18吸附填料粉进行净化,净化后采用GC-MS/MS进行分析测定。结果表明:在优化条件下,16种PAHs分离度良好,在1. 0～200 ng/mL范围内线性关系良好;回收率为60. 04%～119. 00%,RSD在2. 92%～13. 03%之间;检出限在0. 2～3. 5μg/kg之间,定量限在0. 7～11. 5μg/kg之间。该方法数据可靠、简便快速、灵敏度高,适合保健食品枸杞籽油中多环芳烃的测定。     

QuEChERS方法及其在食品农药多残留分析中的应用

农药残留分析是分析化学中最复杂的领域,其原因主要是需分离和测定的残留农药量往往是在ng、pg甚至在fg级.一次成功的分析需要有许多操作条件的正确结合和选择,尤其是萃取和净化方法的成功应用,传统样品前处理技术存在许多不足,如单个样品提取、净化时间较长,有毒溶剂消耗量大,给操作者及环境带来危害,现代样品制备技术正向着经济、节约、减少环境污染、微型化和自动化的方向发展.2003年,由美国农业部农业研究服务中心的Anastassiades M,Lehotay SJ[1]等开发了一种快速、简便、价格低廉的预处理方法来实现高质量的农药多残留物分析方法-QuEChERS法.QuEChERS是一种快速 (Quick)、简便 (Easy)、廉价 (Cheap)、有效 (Effective)、耐用 (Rugged)、安全 (Safe),用于检测食品中农药残留的前处理方法,该法采用含1%醋酸的乙腈提取,加入硫酸镁和氯化钠混合物促使其分层,上清液加入PSA和无水硫酸镁净化分离,最后加入分析保护剂进行GC/MS分析.QuEChERS法的平均样品添加回收率高于85%,干扰目标物检测的杂质少,溶剂用量小,操作简便、快速等特点,将是世界各国小型实验室常规检测农药多残留物的首选预处理方法.     

Estimation of the uncertainty in a multiresidue method for the determination of pesticide residues in fruit and vegetables

The estimation of uncertainty of an analytical result has become important in analytical chemistry. It is especially difficult to determine uncertainties for multiresidue methods, e.g. for pesticides in fruit and vegetables, as the varieties of pesticide/commodity combinations are many. In the present study, recommendations from the International Organisation for Standardisation's (ISO) Guide to the Expression of Uncertainty and the EURACHEM/CITAC guide Quantifying Uncertainty in Analytical Measurements were followed to estimate the expanded uncertainties for 153 pesticides in fruit and vegetables. Data from in-house validation were used in the estimation of the uncertainty. No significant difference in the relative standard deviation for reproducibility (RSD_R) were found between the different concentration levels at concentration levels exceeding 2.5 times the detection limit. Therefore, it was possible to pool the RSD_R within a single matrix. However, a difference in RSD_R between matrices was seen, thus the poorest RSD_R of the investigated matrices was chosen for the uncertainty estimation. The expanded uncertainties ranged from 7 to 78% with an average of 32% and median of 32%. Furthermore, only RSD_R contributed to the uncertainty estimation.     

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法在农药多残留检测中的应用

QuEChERS法是一种用于检测蔬菜水果中农药多残留的前处理方法,因其简单高效而得到广泛的应用。随着面对的基质越来越复杂,QuEChERS法也在不断地进行优化改良。因此研究人员会根据基质的不同性质,在提取溶剂、缓冲盐、盐析、净化材料等方面不断的进行优化,得到更好的实验效果。本研究在阐述传统QuEChERS法的基础上,从方法的关键步骤,提取和净化2方面进行分析,系统阐述了近几年QuEChERS法的改良过程及其在农药多残留检测方面的应用,为QuEChERS法在不同类型基质的检测应用提供参考。     

QuEChERS-GC-MS/MS法同时测定刺梨中15种有机氯农药残留

建立刺梨中15种有机氯农药残留的气相色谱-三重四级杆串联质谱（GC-MS/MS）检测法。刺梨样品采用QuEChERS前处理,正己烷溶液进行提取,经乙二胺-N-丙基硅烷（PSA）和C18各50 mg固相分散净化,浓缩定容后用GC-MS/MS法在多反应监测（MRM）模式下进行测定,通过保留时间、特征离子及其相对丰度定性,外标法定量。15种有机氯农药在0.05～1.00 μg/mL质量浓度范围内呈良好的线性关系,相关系数R2均＞0.997。分别向刺梨样品中分别加入标准品25 μg/kg、50 μg/kg、100 μg/kg时,加标平均回收率在81.98%～105.55%之间,相对标准偏差（n=6）均＜10%,检出限（S/N=3）在0.001 2～0.021 2 mg/kg。该方法具有经济、快速、灵敏度高、重现性好等优势,适用于食品中多种农药残留的同时快速测定。     

QuEChERS结合超高效液相色谱-串联质谱法同时测定梅花鹿鹿茸中18种磺胺

该文采用分散固相萃取的前处理技术,建立超高效液相色谱-串联质谱(ultra performance liquid chromatography-tandem mass spectrometry,UPLC-MS/MS)法同时测定梅花鹿鹿茸中18种磺胺的检测方法。以乙腈为提取剂,70 mg PSA (乙二胺基-N-丙基)、100 mg C_(18)(十八烷基硅烷)与50 mg的中性氧化铝为净化剂,液相色谱条件:Acquity UPLC BEH柱(2.1 mm×100 mm,1.7μm),流动相为25 mmol/L甲酸乙腈-水,柱温35℃,流速0.3 mL/min;质谱条件:正离子模式(ESI+),多反应监测(multiple reaction monitoring,MRM)模式。鹿茸中磺胺含量采用外标法定量,结果18种磺胺在0.025～50 ng/mL内线性关系良好,相关系数R~2均大于0.999 1,7种磺胺的LOD(limits of detection)为0.025μg/kg,LOQ(limits of quantitation)为0.075μg/kg,11种磺胺的LOD为0.075μg/kg,LOQ为0.25μg/kg。18种磺胺的平均加样回收率为80.4%～107.2%,相对标准偏差(relative standard deviation, RSD)均小于5%。该方法具有操作简便,净化效果显著,灵敏度高、准确性好、检出限低等优点,可用于梅花鹿鹿茸中18种磺胺的检测。