液相色谱-串联质谱在农药残留测定中的应用

农药残留检测已经成为全球食品安全的重要组成部分。许多国家和国际组织都制定了严格的限量标准,规定了农产品中农药最大残留限量(MRLs),保证食品安全及进出口贸易。随着农药残留被广泛重视,分析方法不断发展,液相色谱-串联质谱因其高选择性、高灵敏度成为农药残留分析中最常用的检测技术之一。本文简述了最近两年液相色谱-串联质谱在农药残留分析中的应用,介绍了固相萃取及Qu ECh ERS净化方法、液相色谱分离以及串联质谱检测技术,包括低分辨串联质谱和高分辨串联质谱。     

重叠分辨图法用于毛细管电泳优化分离

采用重叠分辨图法对毛细管电泳的分离过程进行了研究，实验以扑草净等5种农药分离的条件为例，考察了影响分离的三个主要因素（溶液的pH、表面活性剂浓度和有机改性剂浓度）对分离度的影响，分离过程首先通过11次初步实验建立目标函数，这样可预测其它条件下的最小分离度，从最终的重叠分辨图可得到分离的最佳条件，在选定的优化条件下，5种组分可达到基线分离。     

植物源性食品中多农药残留GC-MS高通量快速检测技术研究进展

植物源性食品基质复杂、农药种类繁多、农药残留限量标准严格,因此建立植物源性食品中多农药残留高通量快速检测技术十分重要。气相色谱-质谱联用（GC-MS）技术是多农药残留高通量检测领域应用最为广泛的一种技术。然而现阶段植物源性食品中多农药残留GC-MS高通量检测仍存在问题。国内外科研工作者对其进行了大量研究,在现有设备的基础上开发前处理新技术以及复杂信号高通量解析新算法是提高该检测水平的关键。该文对近年来国内外发展的基于GC-MS的植物源性食品中多农药残留高通量快速检测技术及相关文献进行了归纳和总结,重点从适合于不同种类农药提取的新型样品前处理技术、基于“数学分离”的复杂信号高通量解析新算法等方面阐述了植物源性食品中多农药残留高通量快速检测的最新进展,并对其存在的问题提出了相关建议,旨在为食品多农药残留高通量快速检测提供参考。     

时间分辨原位同步X射线衍射技术在分子筛研究中的应用

介绍了时间分辨原位同步X射线衍射技术(in situ TR XRSD)的原理。该技术以其原位测量性和时间分辨性为特征,广泛应用于分子筛研究的各个领域。举例阐述了该技术在水热合成条件的优化、结晶动力学参数测定、成核机理探索、转晶过程和机理、晶体参数变化的监测和骨架外阳离子迁移等过程研究中的应用原理和方法。     

激发-发射荧光法同时测定大米中多菌灵和西维因残留量

样品经预处理后使用激发-发射荧光光谱仪获取荧光信号。基于交替惩罚三线性分解（APTLD）和自加权交替三线性分解（SWATLD）算法的二阶校正方法,借助显著的“二阶优势”在重叠的光谱信号中准确分辨出多菌灵和西维因的光谱,获得定性定量结果。多菌灵和西维因的回收率分别为97.4%～105.2%和103.0%～106.2%,标准偏差均小于4%,预测均方根误差（RMSEP）在接受范围内。对选择性、灵敏度、检出限、定量限等品质因子进行了计算,并使用椭圆联合置信区（EJCR）进行统计分析,表明该方法可实现大米中多种农药残留同时定量检测。     

新极谱法中重叠峰的分辨

依据新极谱信号线性迭加原理,采用标准加入法和多元线性回归,提出了新极谱法中重叠峰多元线性回归分辨方法,可以将重叠峰分辨开来,同时可求得产生重叠峰的2个组分的浓度.方法原理简明,计算速度快,具有较高的准确度和极强的分辨能力.应用于In(Ⅲ)-Cd(Ⅱ)和Pb(Ⅱ)一T1(Ⅰ)体系的阶梯扫描新极谱法测定,取得较为满意的结果。     

QuEChERS-气相色谱-串联质谱法测定农田土壤中3种嘧啶类杀菌剂的残留量

<正>我国是农药生产和使用大国,每年农药用量在70万t左右,农药的大量喷洒,给人类和环境带来了严重威胁~([1])。大部分农药都具有高毒性、难降解性、高稳定性、致癌性、易于在环境和生物体内富集、干扰生物体内分泌系统和致突变等特点。嘧啶类杀菌剂,因其具有种类丰富、生物活性好等特点,常用     

焦脱镁叶绿酸-a作为光活化农药的光活化机理研究

介绍了焦脱镁叶绿酸-a作为光活化农药的可能性, 利用激光光解时间分辨吸收技术和自旋捕获EPR技术对其光活化机制进行了研究. 研究发现, 焦脱镁叶绿酸-a的光活化反应主要沿II型即单线态氧机制进行. 另外, 还就单线态氧对选定的光敏氧化靶分子(DNA, 亚油酸和L-色氨酸)的作用情况进行了探索.     

我国环境监测实验室有机氯农药检测能力与检测方法比对分析

正近年来,持久性有机污染物(POPs)因具有高毒性、持久性、迁移性和生物蓄积性而广受全球关注。作为首批列入《关于持久性有机污染物的斯德哥尔摩公约》(POPs公约)受控名单的有机氯农药,日益成为研究的热点和重点~([1])。我国是农药生产和使用大国,在使用量上我国使用的有机氯农药主要是六六六和滴滴涕。20世纪70年代,这两种农药约占当时全部农药产量的50%~60%~([2])。我国自1983年开始禁止六六六和滴滴涕的生产及其在农业上的     

欧盟统一农药残留可能在2005年生效

欧盟委员会不久前通过了一项在欧盟范围内对植物源性和动物源性产品中的农药残留允许最高含量的统一化建议。     

Parameters affecting microwave-assisted extraction of organophosphorus pesticides from agricultural soil

This work describes an optimised method for the determination of six representative organophosphorus pesticides (OPPs) (diazinon, parathion, methyl pirimiphos, methyl parathion, ethoprophos, and fenitrothion) in agricultural soils. The method is based on microwave-assisted extraction using a water-methanol modified mixture for desorption and simultaneous partitioning on n-hexane (MAEP), together with gas chromatography-flame photometric detection (GC-FPD). To improve GC-FPD signals (peak intensity and shape) olive oil was used effectively as a "matrix mimic". The optimisation of the extraction method was achieved in two steps: an initial approach through experimental design and principal component analysis where recovery of compounds using a water-methanol mixture ranged from 54 to 77%, and the second one by studying the addition of KH2PO4 to the extracting solution where recoveries were significantly increased, molecular replacing of OPPs from adsorption sites by phosphate being the probable extraction mechanism. Under optimised conditions, recoveries of pesticides from different soils were higher than 73%, except for methyl parathion in some soils, with SD equal or lower than 11% and detection limits ranging from 0.004 to 0.012 microg g(-1). The proposed method was used to determine OPPs in soil samples from different agricultural zones of Chile.     

Evaluation of two commercial capillary columns for the enantioselective gas chromatographic separation of organophosphorus pesticides

The separation of the enantiomers of 13 organophosphorus pesticides (OPPs) has been investigated by gas chromatography (GC) with flame ionisation detection (FID) using two different commercially available chiral columns, Chirasil-Val (l-valine-tert-butylamide) and CP-Chirasil-Dex CB (heptakis (2,3,6-tri-O-metil)-β-cyclodextrin). Using the Chirasil-Val column no chiral resolution was obtained for the OPPs investigated under any tested experimental condition. The use of the CP-Chirasil-Dex CB stationary phase enabled good individual enantiomeric separation of two OPPs, ruelene and trichlorfon and partial separation of naled, chloretoxyphos, isophenphos and metamidophos. Also, the obtained chromatographic results showed that Chirasil-Dex could resolve enantiomers through the combination of different mechanism (e.g. formation of inclusion complexes and/or interactions outside the cyclodextrin cavity).

Under optimised conditions, precision, linearity range and detection limits were evaluated for the enantiomers of ruelene and trichlorfon using CP-Chirasil-Dex CB column and electron capture detection (ECD). By using the GC-ECD method the enantiomers of these OPPs could be satisfactorily detected at very low concentration levels. The detection limits observed were 1.5 ng mL⁻¹ and 11.5 ng mL⁻¹ for the enantiomers of trichlorfon and ruelene, respectively.     

Analytical methods for estimation of organophosphorus pesticide residues in fruits and vegetables: A review

Use of pesticides has turned out to be an obligatory input to agriculture and public health. Versatile use of pesticides had resulted in contamination of all basic necessities of life, i.e. air, water and food. Among various pesticides, organophosphorus pesticides (OPPs), derivative of phosphoric acid, are the most extensively used insecticides or acaricides in many crops. Due to low persistency and high killing efficiency of OPPs, many agriculturalists regularly use this group of pesticides for various vegetables and fruits crops. The continuous use of pesticides has caused the deleterious effects to ecosystem. In response to this, a number of methods have been developed by several regulatory agencies and private laboratories and are applied routinely for the quantification and monitoring of multi pesticide residues in vegetables and crops. The present review pertains to various extraction and quantification procedures used world wide to analyze OPPs residues in various vegetables and fruits.     

Application of a single-drop microextraction for the analysis of organophosphorus pesticides in juice

In this study, a new method for the determination of organophosphorus pesticides (OPPs) (ethoprophos, diazinon, parathion methyl, fenitrothion, malathion, isocarbophos and quinaphos) in orange juice was developed. Single-drop microextraction (SDME) parameters, such as organic solvent, drop volume, agitation rate, extraction time, and salt concentration were optimized through analysis of OPPs in fortified water. The orange juice was simply centrifuged and diluted with water, extracted by SDME and analyzed by gas chromatography (GC) equipped with a flame photometric detection (FPD). Fortification tests were conducted for concentrations between 10 and 500 microg/L; mean relative recoveries for each pesticide were all above 76.2% and below 108.0%. Limits of detection of the method for orange juice were below 5 microg/L for all target pesticides. The repeatability of the proposed method, expressed as relative standard deviation varied between 4.6 and 14.1% (n=5). The proposed method is acceptable in the analysis of OPPs pesticides in juice matrices.     

The potential of inductively coupled plasma-mass spectrometric detection for capillary electrophoretic analysis of pesticides

In this work, the potential of inductively coupled plasma-mass spectrometry (ICP-MS) coupled to capillary electrophoresis (CE) to determine organophosphorus pesticides (OPPs) is demonstrated. Element specific detection of (31)P with ICP-MS is performed for the detection of OPPs. Three common OPPs, including glyphosate, glufosinate, and aminomethylphosphonic acid (AMPA), were analyzed by CE-ICP-MS to demonstrate its applicability for the analysis of OPPs. The advantages of using ICP-MS with respect to other common detectors, such as flame photometric detection (FPD), for CE analysis of OPPs are shown. Additionally, different CE separation conditions were studied to achieve complete baseline separation of the pesticide compounds in short migration times. Two CE buffer systems were evaluated for the separation of OPPs using ICP-MS detection. A buffer solution containing 40 mmol.L(-1) ammonium acetate at pH 9.0 and an applied voltage of +20 kV were finally selected leading to a separation time of 10.0 min. Both migration time and area relative standard deviations (%RSD) were evaluated and their respective values were in the intervals of 1.1-3.3% and 2.7-5.3%. Detection limits obtained with the CE-ICP-MS system were in the range of 0.11-0.19 mg.L(-1) (as compound) yielding an enhancement of 130- to 230-fold with respect to FPD. The proposed methodology was finally applied for the determination of the OPPs mentioned above in natural river water samples.     

Dynamic Microwave-assisted Extraction Online Coupled with QuEChERS for the Determination of Organophosphorus Pesticides in Cereals by Gas Chromatography

A rapid analytical method was first developed to detect organophosphorus pesticides(OPPs) in cereals, which used dynamic microwave assisted extraction(DMAE) coupled online with a modified quick, easy, cheap, effective, rugged, and safe(QuEChERS) method. Cereals samples were mixed with a certain amount of quartz, C₁₈ and the primary second amine(PSA), and extracted successively with the acetonitrile-water solution(80%, V/V) under microwave irradiation. The obtained eluate was directly introduced into a collection tube containing NaCl and MgSO₄. Finally, the supernate was evaporated and reconstructed, and determined by gas chromatographic spectrometry. Some factors affecting the experimental results were studied and optimized. The extraction and purification processes were carried out coinstantaneously and 12 samples could be treated in one step in 4 min. Low limits of detection(0.43-1.31 μg/kg) for OPPs were obtained in cereals. The relative standard deviations(RSDs) were 2.1%-9.3%. The recoveries of OPPs ranged from 76.1% to 100.2%. By combining the advantages of DMAE with QuEChERS, the sample pretreatment process was simple to operate, with little amount of organic solvent. The whole extraction process was completed in a closed environment, therefore it was very appropriate for daily analysis of OPPs in cereals.     

Study on the effect of chain-length compatibility of mixed anionic–cationic surfactants on the cloud-point extraction of selected organophosphorus pesticides

The chain-length compatibility of mixed anionic-cationic surfactants was investigated for the extraction of organophosphorus pesticides (OPPs). Cationic surfactants with different chain lengths (n = 12 and 16) were mixed with sodium dodecyl sulfate (SDS; n = 12) for the mixed anionic-cationic surfactants-based extraction. Six OPPs were studied including azinphos-methyl, parathion-methyl, fenitrothion, diazinon, chlorpyrifos, and prothiophos. Reversed-phase high-performance liquid chromatography was used for the determination of the studied OPPs. The extraction was performed using mixtures of SDS and cationic surfactants including dodecyltrimethyl ammonium bromide or dodecyltrimethylammonium bromide (DTAB; n = 12) and cetyltrimethyl ammonium bromide or cetyltrimethyl ammonium bromide (CTAB; n = 16). The parameters affecting the extraction efficiencies of two extraction systems were studied and discussed. The optimum condition for SDS-DTAB was 15 mmol L(-1) SDS and 1 mmol L(-1) DTAB in the presence of 15% (w/v) sodium chloride (NaCl). Meanwhile, the condition for SDS-CTAB was 10 mmol L(-1) SDS and 1.0 mmol L(-1) CTAB with 10% (w/v) NaCl. Under the optimum conditions, the extraction efficiency of SDS-DTAB (66-85%) was slightly higher than that of SDS-CTAB (61-82%). In addition, the SDS-DTAB system also gave greater enrichment factor than SDS-CTAB for all the studied OPPs. This result may be due to the compatibility of chain length between SDS and DTAB. The extraction using SDS-DTAB was successfully applied to determine OPPs in fruit samples (i.e., pomelo, apple, and pineapple). No contamination by the studied OPPs in samples was observed. Good accuracy with recoveries ranging from 77 to 105% was obtained. Low limits of detection were in the range of 0.003-0.01 mg kg(-1) which are below the MRLs established by EU-MRLs for the OPPs residues in fruit samples.     

Determination of polar organophosphorus pesticides in water samples by hydrophilic interaction liquid chromatography with tandem mass spectrometry

A method combining hydrophilic interaction liquid chromatography (HILIC) with tandem mass spectrometry (MS/MS) was developed for the determination of polar organophosphorus pesticides (OPPs; acephate, methamidophos, monocrotophos, omethoate, oxydemeton-methyl, and vamidothion) in water samples. To extract the polar OPPs and minimize matrix effects from the water sample, an activated carbon cartridge was used for pretreatment. After pretreatment of the water sample, the eluate from the activated carbon cartridge was directly injected into the HILIC/MS/MS system. The OPPs were separated on an Atlantis HILIC silica column by isocratic elution with a mixture of acetonitrile, isopropanol, and ammonium formate buffer as a mobile phase, and they were detected by positive electrospray ionization MS/MS in the selected reaction monitoring mode. The method was validated at 0.05, 0.5, and 5 microg/L levels in water samples, and the recoveries of polar OPPs were between 76.4 and 98.6%. The limits of detection were between 0.13 and 1.0 pg on-column, and the limits of quantification were between 0.43 and 3.4 pg on-column. The method can be applied to the determination of trace amounts of OPPs in environmental water samples.     

Novel on-site sample preparation approach with a portable agitator using functional polymer-coated multi-fibers for the microextraction of organophosphorus pesticides in seawater

A novel on-site sample preparation approach for the organophosphorus pesticides (OPPs) using functional polymer-coated fibers with a portable agitation device has been developed and demonstrated. In this approach, a handheld battery-operated electric toothbrush was used to provide agitation of the sample solution at the sampling site to facilitate extraction. A functional conjugated polymer (2-(9,9-bis(6-bromo-2-ethylhexyl)9-H-fluoren-2-yl)benzene-1,4-diamine) was coated on commercial Technora fibers (each strand consisted of 1000 filaments, each of diameter ca. 9.23μm) which were then used for extraction. After extraction, the fibers were brought back to the laboratory in an icebox. The analytes were subsequently desorbed by organic solvent and the extract was analysed by gas chromatography-mass spectrometry. Six OPPs, triethylphosphorothiolate, thionazin, sulfotep, phorate, disulfoton and parathion were used as model compounds. Experimental parameters such as extraction time, desorption time, types of polymer fibers and fiber coatings as well the nature of desorption solvent were optimized in the laboratory prior to its on-site application of the procedure. Using optimum extraction conditions calibration curves were linear with correlation coefficient of 0.9748-0.9998 over the concentration range of 0.1-10μgl(-1). The method detection limits (at a signal-to-noise ratio of 3) were in the range of 0.3-30.3ngl(-1), which were lower than what could be achieved with solid-phase extraction performed at the laboratory. The proposed method was evaluated for the on-site extraction of OPPs in seawater samples.     

Physically incorporated extraction phase of solid-phase microextraction by sol-gel technology

A sol-gel method for the preparation of solid-phase microextraction (SPME) fiber was described and evaluated. The extraction phase of poly(dimethysiloxane) (PDMS) containing 3% vinyl group was physically incorporated into the sol-gel network without chemical bonding. The extraction phase itself is then partly crosslinked at 320 degrees C, forming an independent polymer network and can withstand desorption temperature of 290 degrees C. The headspace extraction of BTX by the fiber SPME was evaluated and the detection limit of o-xylene was down to 0.26 ng/l. Extraction and determination of organophosphorus pesticides (OPPs) in water, orange juice and red wine by the SPME-GC thermionic specified detector (TSD) was validated. Limits of detection of the method for OPPs were below 10 ng/l except methidathion. Relative standard deviations (RSDs) were in the range of 1-20% for pesticides being tested.