固相萃取-超高效液相色谱-串联质谱法检测环境水体中18种农药残留

建立了固相萃取-超高效液相色谱-串联质谱（SPE-UPLC-MS/MS）同时检测环境水体中不同极性范围的18种农药残留的分析方法。样品经大体积固相萃取装置，以2 mL/min的速率通过Cleanrt^®-PEP固相萃取柱进行净化和富集，浓缩50倍后结合UPLC-MS/MS检测，外标法定量。研究表明，目标化合物在0.5~50 μg/L范围内线性关系良好，线性相关系数（R²）≥0.995；在10、100和1000 ng/L 3个添加水下，18种农药在3种不同环境水体中的平均回收率为71.3%~105.9%，相对标准偏差（RSD，n=5）为1.3%~9.9%；定量限（LOQ）均为10 ng/L。该方法应用于泰安市区周围水环境的检测，各采集位点均未检出农药残留。该方法具有净化效果好、通用性强、灵敏度高、准确度高和操作简单等优点，适用于环境水体中18种农药的残留检测。     

高效液相色谱-串联质谱法同时测定贝类中22种农药残留

建立了高效液相色谱-三重四极杆质谱（HPLC-MS/MS）同时测定贝类中22种农药残留的分析方法。样品经含0.1%（v/v）甲酸的乙腈提取，N-丙基乙二胺（PSA）和石墨化碳黑（GCB）净化，然后采用ACE UltraCore 2.5 SuperC18柱（100 mm×2.1 mm，2.5 μm）分离，以甲醇-0.1%（v/v）甲酸水溶液为流动相梯度洗脱，流速为0.4 mL/min，柱温为35 ℃，然后以电喷雾电离（ESI）源，在多反应监测（MRM）、正离子模式下，采用三重四极杆质谱检测。22种农药在各自的线性范围内线性关系良好，相关系数均大于0.997，检出限为0.1~0.3 μg/kg，定量限为0.3~1.0 μg/kg。在3个添加水平下，22种农药的平均回收率为65.2%~109.4%，相对标准偏差为1.3%~15.2%（n=6）。该方法操作简单，快速，准确度高，灵敏度高，可用于贝类中22种农药残留的同时检测。     

快速滤过型净化结合气相色谱-串联质谱法同时检测茶叶中10种拟除虫菊酯农药残留

建立了快速滤过型净化（m-PFC）结合气相色谱-串联质谱（GC-MS/MS）测定茶叶中10种拟除虫菊酯类农药残留的方法。比较了采用不同提取溶剂（乙腈、丙酮和乙酸乙酯）和不同提取方式（不加水浸泡和加水浸泡）时10种农药的提取效率；比较了2种QuEChERS净化管和m-PFC柱对茶叶提取液的净化效果和农药残留的回收率。结果表明，茶叶样品不加水浸泡，用乙腈提取效果最好；m-PFC柱对茶叶提取液净化效果良好，而且能保证较高的农药回收率。10种拟除虫菊酯农药在相应的范围内有良好的线性关系，相关系数（R²）大于0.9980；10种农药在4个水平添加下的回收率为87.5%~111.3%，RSD为2.1%~8.9%。方法的检出限为0.001~0.015 mg/kg，定量限为0.003~0.05 mg/kg。利用该方法检测市售50例茶叶样品中10种拟除虫菊酯农药的残留，检出率为48%，但农药残留量均在国家标准限量值以下。与传统QuEChERS法和固相萃取法相比，该方法具有操作简单、准确度和精密度良好等优点，为多种拟除虫菊酯类农药在茶叶中的残留测定提供了快速检测的新方法。     

QuEChERS-气相色谱-质谱联用法快速测定人参中农药多残留

建立了QuEChERS-气相色谱-质谱联用（GC-MS）法同时测定人参中20种农药残留量的检测技术。样品前处理采用改进的QuEChERS方法,人参粉加水浸润后,用乙腈均质提取,用N-丙基乙二胺（PSA）和MgSO₄净化,结合GC-MS检测系统,在电子轰击源（EI）选择离子监测（SIM）模式下进行检测,使用HP-5毛细管柱进行分离。在优化条件下,20种农药在一定范围内线性关系良好,相关系数大于0.990,方法检出限（信噪比S/N=3）为0.001~0.007 mg/kg,定量限（S/N=10）为0.002~0.024 mg/kg,平均回收率为70.41%~114.06%,相对标准偏差（RSD）为0.76%~15.47%。该方法操作简单快捷、灵敏度高。     

自制双层固相萃取柱在新会陈皮及其制品中11种有机磷农药测定中的应用

以自制改性多壁碳纳米管（MWNTs）和N-丙基乙二胺（PSA）填料分层填装的双层固相萃取柱为净化柱,建立了测定陈皮及其制品中11种有机磷农药残留的分析方法。样品经乙酸乙酯提取、离心后,固相萃取柱净化,净化液经Agilent RTS-1701毛细管柱分离,火焰光度检测器检测,外标法定量。考察了填料类型、填料用量、洗脱方式等因素对提取效率的影响。在优化条件下,11种有机磷农药检测的线性范围为0.020~1.0 mg/L,相关系数为0.9990~0.9998,检出限为3.5~9.6 μ g/kg。样品在10、25、100 μg/kg 3种水平下的加标回收率为50.8%~109%,相对标准偏差为2.7%~8.5%。该法准确度和灵敏度高、操作简单、快速,检出限能满足对有机磷农药残留的限量要求。自制固相萃取柱可降低成本,值得推广应用。     

改进的QuEChERS方法结合液相色谱-四极杆-飞行时间质谱快速筛查与确证调味茶中52种农药残留

建立了调味茶中52种农药残留的QuEChERS方法结合液相色谱-四极杆-飞行时间质谱（LC-Q-TOF-MS）快速筛查方法。采用乙腈提取样品，经N-丙基乙二胺（PSA）、石墨化炭黑（GCB）、C₁₈净化，LC-Q-TOF-MS测定。结果表明：52种农药在调味茶中4个添加水平（10、20、50和100 μg/kg）下的回收率均在70%~120%之间，相对标准偏差（RSD，n=3）均小于20%，52种农药线性良好，线性相关系数（r）均大于0.99。52种添加农药的筛查限为0.001~0.01 mg/kg，定量限为0.002~0.02 mg/kg，均低于添加农药的欧盟最大残留限量（MRL）标准。该方法样品前处理简单、分析时间短、灵敏、可靠，适用于茶叶中多种农药残留的检测。     

凝胶渗透色谱-气相色谱同时测定糙米中拟除虫菊酯、有机氯农药和多氯联苯的残留量

基于凝胶渗透色谱（GPC）对脂类和色素的优良分离能力,系统研究了其对有机氯农药、拟除虫菊酯农药、多氯联苯和糙米基体的分离行为。介绍了一种可同时测定糙米中35种拟除虫菊酯、有机氯农药和多氯联苯的方法。样品用乙酸乙酯提取,凝胶渗透色谱净化,气相色谱-电子捕获检测法(GC-ECD)检测,外标法定量。在低、中、高浓度3个添加水平上的回收率分别为70.1%~107.4%,70.3%~109.9%和70.8%~109.5%,相对标准偏差（RSD）为2.3%~13.3%;有机氯农药和多氯联苯的检出限为0.07 μg/k     

超高效液相色谱-四极杆-飞行时间质谱法快速筛查辣椒粉中27种农药残留

建立了超高效液相色谱-四极杆-飞行时间质谱（UPLC-Q-TOF/MS）快速筛查辣椒粉中27种农药残留的检测方法。样品采用乙腈提取,经Carb/NH₂固相萃取小柱净化,用乙腈-乙酸乙酯（3：1,v/v）洗脱,电喷雾正离子模式检测。在一级质谱模式下,以目标物的保留时间、精确质量数、同位素分布和同位素丰度比定性,以准分子离子峰的峰面积定量。在Targeted MS/MS模式下,通过相应碰撞能量下的离子碎片信息进一步确证。27种化合物在各自的线性范围内线性关系良好,相关系数均大于0.997。27种化合物的定量限为2.5~5.0 μg/kg,在3个添加水平下的回收率为72.3%~118.9%,相对标准偏差（RSD）为0.21%~12.7%（n=6）。该方法快速、灵敏、准确,适用于辣椒粉中多种农药残留的同时检测。     

果实类中药材中20种有机磷农药残留量的同时测定

建立了果实类中药材中多种有机磷农药残留同时测定的方法,并对影响提取、净化、检测效率的因素进行优化。样品用乙酸乙酯提取,凝胶渗透色谱收集9~15 min流分,ENVI-Carb固相萃取柱净化,DB-1701毛细管色谱柱分离,火焰光度检测器检测,外标法定量。在优化条件下,20种有机磷农药在0.01~2.0mg/L范围内具有良好的线性关系,相关系数为0.996 6~0.999 5,检出限(S/N=3)为0.66~5.78μg/kg。3个加标水平下的平均回收率为80.2%~109.9%,相对标准偏差为2.3%~13%。该方法操作简便、准确、净化效果好,可满足果实类中药材中多种有机磷农药残留的同时测定要求。     

液相色谱-串联质谱法同时测定8种花草茶中77种农药残留

以QuEChERS作为样品前处理手段,采用高效液相色谱-串联质谱（HPLC-MS/MS）检测技术,建立了适用于8种花草茶中77种农药残留同时检测的方法。8种花草茶样品均采用1%（v/v）乙酸乙腈溶液和1 g乙酸铵提取,经4 g无水硫酸镁、0.50 g C18、0.50 g N-丙基乙二胺（PSA）和0.05 g石墨化炭黑（GCB）分散萃取净化,然后采用Venusil MP C18色谱柱分离,以0.1%（v/v）甲酸水溶液和乙腈为流动相梯度洗脱,在电喷雾电离（ESI）源、正负离子交替扫描模式下进行检测,基质匹配标准溶液定量。结果表明,77种农药在0.5~100.0 μ g/L范围内线性关系良好,相关系数大于0.995;77种农药的加标回收率为70.3%~110.0%,相对标准偏差为2.6%~9.8%,检出限为1.0~10.0 μ g/kg。该法灵敏度、准确度和精密度均符合相关农药残留测定的技术要求。     

气相色谱-串联质谱双内标法测定茶叶中53种农药残留

建立了气相色谱-串联质谱（GC-MS/MS）动态多反应离子监测（dMRM）模式,结合串联双色谱柱检测茶叶中53种农药残留量的分析方法。样品中加入QuEChERS缓冲盐,用乙腈提取,采用石墨化炭黑/氨基柱（ENVI-Carb/NH₂）净化。为减少农药在GC-MS/MS分析中基质效应的影响,在标准溶液中加入古洛糖酸内酯和山梨醇作为保护剂,用蒽醌-D8和磷酸三苯酯作双内标定量。结果表明,除了氯氰菊酯的线性范围是40~1000 μg/L外,其他52种农药的线性范围均为20~500 μg/L,线性关系良好,相关系数均大于0.99;有28种农药的定量限（LOQ）小于10 μg/kg,其余25种农药的定量限为10~20 μg/kg;加标回收率为72.5%~130.9%;相对标准偏差（RSD）为0.4%~19.4%。该方法能有效地减少茶叶在GC-MS/MS上的基质效应,操作简单快速,灵敏度和选择性高,适用于农药残留的日常检测。     

气相色谱-四极杆-飞行时间质谱和气相色谱-串联质谱对水果、蔬菜中208种农药残留筛查确证能力的对比

对比研究了气相色谱-串联质谱(GC-MS/MS)与气相色谱-四极杆-飞行时间质谱(GC-QTOF/MS)在水果、蔬菜中208种农药多残留检测中基质效应及方法学效能的差异,提出两种仪器在农药残留检测方面的特点和适用范围,为残留检测分析提供参考。在苹果、柑橘、番茄、黄瓜4种基质,3个添加浓度(5.0、10.0和20.0 μg/kg)下,两种仪器中均有93.0%以上的农药回收率在70%~120%范围内且相对标准偏差(RSD)≤20%(n=5)。检测灵敏度方面,绝大部分农药在两种仪器的检出限均低于5.0 μg/kg,满足各国农药残留限量的要求,且GC-MS/MS灵敏度更高,线性范围更宽,定量能力更加准确。筛查确证方面,GC-QTOF/MS在快速、高通量筛查、准确定性及非目标化合物鉴定等方面表现出了优势。     

气相色谱-串联质谱法快速筛查测定中药材中144种农药残留

利用气相色谱-串联质谱(GC-MS/MS)检测技术,采用QuEChERS法作为样品前处理方法,建立了能应用于11种中药材中144种农药残留的检测方法。探究了样品前处理过程中提取溶剂、缓冲盐体系、净化剂组成和用量对样品提取、净化等方面的影响,最终确定了用乙腈提取,甲苯复溶,以混合净化剂净化,过有机膜后经GC-MS/MS测定,外标法定量。144种农药在10~2000 μg/kg之间线性关系良好,相关系数(r²)>0.983;除乙酰甲胺磷、灭虫威、西玛津、克菌丹、异狄氏剂、异菌脲外,其余农药的定量限(LOQ)均低于20 μg/kg;在20、50、200 μg/kg的添加水平下,除乙酰甲胺磷、艾氏剂和双甲脒回收率偏低外,其余141种农药的平均回收率在74.3%~111.8%之间,相对标准偏差(RSD)为0.5%~14.6%。与已有的标准方法对比,此方法不仅检测结果一致,而且高效、快速,准确性好,灵敏度高,适用于中药材中144种农药残留的快速筛查与定量分析。     

Simplified pesticide multiresidue analysis in virgin olive oil by gas chromatography with thermoionic specific, electron-capture and mass spectrometric detection

In the present work, an analytical multiresidue method has been developed for the analysis of 32 organochlorine, organophosphorus and organonitrogen pesticides at microg kg(-1) levels in virgin olive oil. The method consists of the extraction of the pesticides with acetonitrile saturated in n-hexane followed by a clean-up process based on gel permeation chromatography (GPC) with ethyl acetate-ciclohexane (1:1) as mobile phase to separate the low-molecular mass pesticides from the high-molecular mass fat constituents of the oil. The target compounds were determined in the final extract by gas chromatography (GC) using thermoionic specific (TSD) and electron-capture (ECD) detection. In the case of positive samples, the amounts found were confirmed by GC-MS/MS, being the results in good agreement. Recoveries and RSDs (n = 10) values were 91-124% and 1-8% (GC-ECD), 82-100% and 9-20% (GC-TSD), and 89-105% and 4-14% (GC-MS/MS), respectively. The three proposed methods were applied to samples collected directly in two olive mills located in the Jaén province (Spain). Specifically, 24 samples of virgin olive oil were collected. The most frequently pesticide residues found were the herbicides terbuthylazine and diuron and endosulfan sulfate, a degradation product of the insecticide endosulfan. The herbicide concentration was higher in those oil samples obtained from olives which were collected from the ground after they had fallen down than in those oil samples from olives harvested directly from the tree. The GC-MS/MS developed method was also applied to the analysis of an olive oil sample from a proficiency test spiked with organochlorine pesticides and all the values obtained were within the specified "satisfactory" range.     

Evaluation of the QuEChERS sample preparation approach for the analysis of pesticide residues in olives

This paper describes the use of a quick, easy, cheap, effective, rugged, and safe (QuEChERS) method for extraction and cleanup of 16 pesticide residues of interest in olives and olive oil. These products contain a high lipid content, which can adversely affect pesticide recoveries and harm traditional chromatographic systems. For extraction, the main factors (oil and water content) were studied and optimized in experiments to maximize pesticide recoveries. Dispersive SPE with different sorbents was also investigated to minimize matrix coextractives and interferences. For analysis, a new automated DSI device was tested in GC-MS to avoid nonvolatile coextractives from contaminating the instrument. LC-MS/MS with positive ESI was used for those pesticides that were difficult to detect by GC-MS. The final method was validated for olives in terms of recoveries, repeatabilities, and reproducibilities using both detection techniques. The results demonstrated that the method achieved acceptable quantitative recoveries of 70-109% with RSDs < 20% for DSI-GC-MS and 88-130% with RSDs < 10% for LC-MS/MS, and LOQ at or below the regulatory maximum residue limits for the pesticides were achieved.     

基于壳聚糖的QuEChERS-气相色谱-串联质谱法测定人参中30种农药残留

建立了一种以壳聚糖为净化材料的QuEChERS-气相色谱-串联质谱检测人参中30种农药残留的检测方法。探究了吸附剂及其用量对样品提取和净化效果的影响,确定壳聚糖为吸附剂净化。采用选择离子监测(SRM)模式,基质匹配标准曲线外标法定量。30种农药在各自的浓度范围内,线性关系良好(r> 0.996);检出限范围为1.5~3.0μg/kg,定量限范围为5.0~10.0μg/kg。3个添加水平(10,20,100μg/kg)的回收率在84.1%~113.7%之间,相对标准偏差均小于15%。该方法适用于检测人参中农药残留。     

气相色谱-三重四极杆质谱动态多反应监测模式测定枸杞干果中118种农药残留

枸杞中丰富的营养物质深受广大消费者喜爱,但也极易受到病虫侵害,农药残留问题引起了人们的广泛关注。基质干扰是微量分析的一个难点,高灵敏度和高选择性的色谱-串联质谱技术是复杂基质中微量分析强有力的工具,动态扫描监测模式的优越性逐渐取代传统的多反应监测扫描模式,简便、快速、省时的QuEChERS前处理方法已被广泛应用于食品的农药残留检测中。采用改良QuEChERS法结合动态多反应监测模式(dMRM),建立了同时检测枸杞干果中118种农药残留的气相色谱-三重四极杆质谱分析方法。实验比较了不同加水量、提取溶剂、提取过程中温度提取条件,以及无水硫酸镁吸水剂、乙二胺-N-丙基硅烷化硅胶PSA、十八烷基硅烷键合硅胶C₁₈净化填料添加量时农药的回收率,确定出最优前处理方法。结果表明,5 g样品经10 mL超纯水复水,用10 mL乙腈浸提,于-18 ℃冷冻10 min后,用缓冲体系盐包提取后,经800 mg无水硫酸镁、150 mg PSA、150 mg C₁₈混合填料净化,基质匹配外标法定量。118种农药在一定范围内线性关系良好,相关系数R²≥0.9923,检出限和定量限分别为0.006~28.344 μg/kg和0.021~94.480 μg/kg, 4个添加水平的回收率为64.97%~126.21%, RSDs均小于19%(n=6)。基质效应考察结果表明,82%的农药呈现为基质增强效应,其他为基质抑制效应;9%的农药表现为强基质效应,其他为中等或弱基质效应;采用基质匹配标准曲线校正,可有效降低基质效应的影响。应用建立的方法测定10批枸杞样品,全部样品有农药检出,共检出农药22种。该方法操作简便快速,准确可靠,适用于枸杞干果中农药多残留的日常检测和快速筛查。     

气相色谱-串联质谱技术分析烟草中49种农药残留

采用改进的QuEChERS(quick, easy, cheap, effective, rugged and safe)前处理法,结合气相色谱-串联质谱(GC-MS/MS)技术建立了检测烟草中49种农药残留的分析方法。样品用含0.1%乙酸的乙腈溶液提取,提取液被氮吹至干后,残渣用乙腈-乙酸乙酯(1:1, v/v)溶液溶解,溶解液经N-丙基乙二胺(PSA)吸附剂、无水MgSO4、C18吸附剂净化后,直接进行GC-MS/MS测定,内标法定量。实验结果表明,49种农药在低质量浓度(0.05 μg/L)的加标水平下的平均加标回收率为60.4%～104.8%,高质量浓度(5 μg/L)的平均加标回收率为70%～115%,相对标准偏差均小于15%;其中16种农药的方法检出限(LOD)分别为0.01～0.03 μg/kg,其余33种农药的LOD均小于0.01 μg/kg;相关系数都大于或等于0.991。该方法样品前处理简单、分析时间短、灵敏度和精密度均符合农药多残留痕量检测技术的要求,适用于烟草中多种农药残留的检测。     

Development of a multi-residue screening method for the determination of pesticides in cereals and dry animal feed using gas chromatography-triple quadrupole tandem mass spectrometry

A multi-residue screening method for simultaneous analysis of 122 gas chromatography amenable pesticides in dry matrices such as cereal grain and certain feedingstuffs was developed. The method entails a simple extraction of re-hydrated sample with acetonitrile followed by a dispersive solid phase extraction (dispersive-SPE) clean-up step prior to the final determination by gas chromatography/triple quadrupole tandem mass spectrometry (GC-MS/MS). Due to complexity of analyzed matrices, two MS/MS transitions were set for each pesticide to eliminate the need for re-analysis of potentially positive samples, and provide unequivocal identification of detected pesticides in accordance with recent guidelines, in a single analytical run. Thus, in the developed GC-MS/MS acquisition method, a total of 216 different multiple reactions monitoring (MRM) transitions were monitored in one set of experimental conditions. To evaluate performance of the method, validation experiments were carried out on wheat grain at three spiking levels (0.01, 0.02 and 0.05 mg kg(-1)). Additional recovery tests at 0.05 mg kg(-1) were carried out on several other matrices. The recoveries ranged between 73 and 129% with associated relative standard deviations between 1 and 29% for the majority of pesticides. Limits of detection were less or equal to 0.01 mg kg(-1) for approximately 68% of pesticides. The applicability of the proposed method to detect and quantify pesticide residues has been demonstrated in the analysis of 136 real samples. Additionally, the method was favorably compared with an acetone extraction method (accepted as a reference method by some of European and U.S. authorities) in the analysis of real samples known to contain pesticide residues.     

气相色谱-三重四极杆串联质谱法快速测定蔬菜水果中129种农药的残留量

采用QuEChERS方法结合气相色谱-串联质谱法(GC-MS/MS)建立了蔬菜、水果中129种农药残留同时检测的分析方法。试样用1%乙酸乙腈均质提取,采用混合型固相分散萃取剂净化后,用GC-MS/MS在多反应离子监测(MRM)模式下进行检测,外标法定量。结果表明,129种药物在一定的含量范围内线性关系良好,相关系数(r2)均大于0.98;不同基质在10 μg/kg添加水平下大部分农药的平均回收率为66.2%～124.7%,相对标准偏差(RSD)为0.9%～24.4%;方法的定量限(LOQ)为0.03～16.7 μg/kg。结果表明,该方法简便快速、灵敏可靠、经济有效,适用于蔬菜、水果中农药多残留的同时快速筛查测定。