间苯氧基苯甲酸分子印迹膜的电化学聚合制备及其应用

研究间苯氧基苯甲酸快速准确的检测方法可为环境中间苯氧基苯甲酸监测以及拟除虫菊酯农药代谢物的生态风险评价提供技术支持。本实验以邻氨基酚为功能单体,以间苯氧基苯甲酸为模板分子,采用循环伏安法在玻碳电极表面聚合形成可用于检测间苯氧基苯甲酸的分子印迹膜,结合电化学技术用于水中间苯氧基苯甲酸的检测研究,30 s可对间苯氧基苯甲酸完成响应,在2.00～11.00 mg/L质量浓度范围内,分子印迹膜的响应电流变化值与间苯氧基苯甲酸质量浓度呈线性关系,线性方程为y=0.29x＋2.16,相关系数为0.99,方法的检出限为1.47 mg/L;对加标水样进行检测,回收率在92.00%～101.00%之间。     

平菇及其培养料中5种拟除虫菊酯类农药的残留消解动态

在确证平菇培养料中联苯菊酯、甲氰菊酯、高效氟氯氰菊酯、高效氯氰菊酯和溴氰菊酯5种拟除虫菊酯类农药多残留分析方法的基础上,研究供试拟除虫菊酯类农药在平菇和培养料中的消解动态规律。结果表明:5种供试拟除虫菊酯类农药在平菇和培养料中的消解半衰期分别为3.01～5.06、25.48～54.59d。平菇培养料的灭菌会显著减少其中拟除虫菊酯类农药的残留量,降解率达18.80%～61.16%。平菇在含有联苯菊酯等5种拟除虫菊酯类农药的培养料中栽培42、62、83、103d后,培养料中供试农药残留量仍较高,分别为1.29～7.40、1.55～6.81、0.32～1.78、0.14～1.76mg/kg,同步采集的平菇子实体中均未检测到供试农药的残留量。因此,平菇培养料中供试拟除虫菊酯类农药残留不会向平菇子实体转移,对食用菌产品质量安全的影响较小。     

固相萃取-气相色谱法检测金银花中9 种拟除虫菊酯农药残留

采用固相萃取净化,气相色谱电子捕获检测器检测,建立了金银花中9 种拟除虫菊酯农药残留量的检测方法。金银花样品经正己烷涡旋振荡提取、TPH固相萃取柱净化后,用气相色谱检测。9 种拟除虫菊酯农药的线性范围在0.01～0.8 mg/L,平均回收率为82.8%～104.6%,相对标准偏差为3.5%～5.7%,检出限为0.002～0.005 mg/L。该方法灵敏、准确,适用于金银花中9 种拟除虫菊酯类农药残留量分析。     

枸杞中拟除虫菊酯类农药残留水平及累积暴露评估

目的检测枸杞中的农药残留水平,并对拟除虫菊酯类农药的累积暴露风险进行评估,为是否需要制定枸杞中最大残留限量提供依据。方法收集40份不同来源不同产地的枸杞样品,对332种农药残留进行测定,其中包括15种拟除虫菊酯类农药。采用危害指数(HI)法对通过枸杞摄入拟除虫菊酯类农药产生的急性和慢性累积风险进行评估。结果通过方法学验证得出此方法适用于枸杞中拟除虫菊酯类农药的测定。结果显示4种拟除虫菊酯农药检出率均高于25%,分别为氯氰菊酯、氰戊菊酯、甲氰菊酯和氯氟氰菊酯。采用HI法进行累积暴露评估,得出拟除虫菊酯类农药的急性和慢性危害指数分别为0.497和0.016。结论枸杞在拟除虫菊酯类农药的累积摄入风险虽然较小,但由于其检出率较高,应持续保持对样品的监控,并考虑制定相应的最大残留限量值。     

不同处理方式对蔬菜中拟除虫菊酯类农药残留的影响

目的探究不同处理方式对蔬菜中拟除虫菊酯类农药残留的影响。方法分别于2016年10月、2017年1月、2月在济南市农贸市场随机抽样采集根茎类,叶菜类,果菜类,薯芋类蔬菜样品共34份,将样品粉碎后提取拟除虫菊酯,采用酶联免疫吸附法(enzyme linked immunosorbent assay,简称ELISA)检测蔬菜中拟除虫菊酯残留量。随后,分别通过碱水溶液浸泡、洗涤剂清洗的方法处理样品,检测处理后蔬菜中拟除虫菊酯残留量,评价不同处理方法对蔬菜中拟除虫菊酯类残留的影响。结果 34份蔬菜中拟除虫菊酯检出率为100%;蔬菜中拟除虫菊酯类农药的残留量随着采样时间的不同而发生变化,秋季残留量较高,冬季残留量较低;碱处理和洗涤剂洗涤对蔬菜中拟除虫菊酯无明显去除效果。结论拟除虫菊酯类农药普遍存在与蔬菜中,且经碱处理和洗涤剂处理均无法有效去除蔬菜中此类农药残留。     

拟除虫菊酯类农药多残留的IC-ELISA检测方法研究

为检测样品中拟除虫菊酯类农药多残留,以间苯氧基苯甲酸(PBA)为半抗原,用活性酯法将PBA与牛白蛋白(BSA)偶联,制备多克隆抗体,并建立间接竞争酶联免疫吸附测定法。用方阵滴定确定包被抗原的最适工作浓度为5.0μg/mL,抗体最佳浓度为10.0μg/mL,该方法的最低检测限为0.301μg/mL,在0.1～200μg/mL工作浓度范围内,标准曲线表现良好的线性关系。     

拟除虫菊酯类农药残留检测技术的研究进展

近年来,随着拟除虫菊酯类农药的广泛使用,其残留问题也日益突出。拟除虫菊酯类农药的大量使用给我国的出口贸易以及人类健康带来重大隐患。加强拟除虫菊酯类农药残留检测技术的研究是解决其残留超标问题的重要步骤。文中主要对用于拟除虫菊酯农药残留检测的气相色谱法、液相色谱法、质谱技术、分光光度法、生物传感器等技术进行了综述,并对其发展趋势进行了展望。     

气相色谱法测定茶叶中菊酯类农药残留量

为了建立一种气相色谱法测定茶叶中拟除虫菊酯类农药残留的分析方法。采用气相色谱法-电子捕获检测器对6种拟除虫菊酯类农药残留量进行检测。发现6种拟除虫菊酯类农药分离效果较好,峰高与浓度呈良好的线性关系(R≥0.9948),该法检出限为0.005~0.02mg/kg,样品加标回收率为79.6%~118.5%。证明其方法简单,净化效果好,精密度好、回收率高,能够满足茶叶中拟除虫菊酯类农药测定的要求。     

QuEChERS气相色谱联用法检测马铃薯中4种拟除虫菊酯类农药残留及基质效应的影响

目的采用QuEChERS前处理结合气相色谱联用技术建立测定马铃薯中4种拟除虫菊酯类(pyrethroid)农药残留的快速高效检测方法。方法样品粉碎后采用1%乙酸乙腈提取,无水硫酸镁和氯化钠盐析,经十八烷基键合硅胶柱(C_(18))净化,气相色谱法对样品进行检测,外标法定量,提取后样品进行加标实验,对马铃薯中拟除虫菊酯类农药检测的基质效应评估。结果马铃薯基质对4种拟除虫菊酯类农药均存在基质增强效应,增强比为121.12%～143.43%,4种拟除虫菊酯在马铃薯基质加标水平(20、50、100μg/kg)的回收率为76.8%～82.5%;检出限(S/N=3)与定量限分别为2.8～3.7μg/kg和8.0～10.0μg/kg,相对标准偏差小于8.9%。结论该方法简单、灵敏度高、净化效果好,适用于果蔬中拟除虫菊酯的快速检测。     

含氰基类拟除虫菊酯农药残留免疫检测方法研究进展

概述近年来含氰基拟除虫菊酯类农药残留免疫检测方法,总结各种含氰基拟除虫菊酯半抗原的设计,以及所达到的检测限,讨论有待于进一步研究的内容;简述正在进行的有关含氰基拟除虫菊酯类农药多残留免疫检测方法的研究内容。     

Residues of insecticides, and fungicides in fruit produced in Ontario, Canada, 1986-1988

Between 1986 and 1988, 306 composite samples of fruit representing eight commodities were collected from farm deliveries to the marketplace in Ontario, Canada. All samples were analysed for insecticides and fungicides. The analysis procedure included tests for organochlorine, organophosphorus, synthetic pyrethroid and methylcarbamate insecticides and dithiocarbamate, dicarboximide and organochlorine fungicides. The commodities tested included apples, blueberries, cherries, grapes, peaches, pears, raspberries and strawberries. In 14% of all fruit samples, pesticide residues were below the detection limits, which ranged between 0.005 and 0.02 mg/kg. A further 14% had total combined pesticide residues below 0.1 mg/kg. Total combined fungicide and insecticide residues ranged from 0.1 to 11 mg/kg in 72% of samples. Six different pesticides were in violation of maximum residue limits (MRL) on 11 (3.6%) of fruit samples. Captan exceeded the 5 mg/kg MRL in five samples and EBDC exceeded the 7 mg/kg MRL in two. Other violations included single fruit samples with dicofol, endosulphan, phosalone and iprodione above the MRL. Raw grapes harvested for wine contained residues of 10 pesticides and the number changed little following the crushing of the grapes; however, fermentation into wine significantly reduced residues. Six insecticides and four fungicides were present on the raw grapes and 4/105 were above the MRL. Following crushing, four insecticides and five fungicides were identified and 4/40 were above the MRL. In wine only three insecticides were identified and all were well below the MRL. Carbaryl appeared to be the most persistent, declining very little between raw grapes and wine.     

Residues of insecticides and fungicides on Ontario-grown vegetables, 1986-1988

Between 1986 and 1988, 433 composite vegetable samples representing 16 commodities were collected from farm deliveries to the marketplace in Ontario, Canada. All samples were analysed for insecticides and fungicides. The analyses included organochlorine, organophosphorus, synthetic pyrethroid, and N-methylcarbamate insecticides and dithiocarbamate, dicarboximide, and organochlorine fungicides. The commodities tested included asparagus, beans, carrots, celery, cole crops, cucumbers, lettuce, onions, peppers, potatoes, radishes, rutabagas and tomatoes. In 64% of samples, no pesticide residues were identified to the limits of detection which ranged from 0.005 to 0.05 mg/kg. A further 22% had combined insecticide and fungicide residues below 0.1 mg/kg. Most of the positive findings were a fraction of the Maximum Residue Limit permitted for each commodity under the Canadian Food and Drugs Act and Regulation. Three samples (0.7%) had residues that exceeded the MRL. These involved diazinon and parathion on celery and chlorothalonil on peppers. While some commodities had no detectable residues others had measurable residues of up to three separate pesticides. The most were found on celery, lettuce and field tomatoes.     

固相萃取-气相色谱法检测蔬菜中8种菊酯类 农药残留

目的建立一种固相萃取-毛细管柱气相色谱方法,可以同时检测蔬菜中8种菊酯类农药残留。方法蔬菜样品匀浆后,经正己烷/丙酮(V:V=50:50)提取,Florisil固相萃取柱净化,HP-5毛细管气相色谱柱进行分离,GC-ECD进行定性及定量分析。结果 8种菊酯类农药残留的色谱图分离效果良好,线性相关系数均大于0.995,方法检出限在0.0025~0.02 mg/kg之间。8种菊酯类农药的添加水平为0.025~2 mg/kg,回收试验表明该方法平均回收率在73.6%~97.0%之间,相对标准偏差小于5%。结论该方法样品处理简单、仪器配置要求较低、净化效果好、易于推广使用,适合蔬菜中多种菊酯类农药残留的检测和安全监控。     

气相色谱法快速测定食品中有机氯、拟除虫菊酯、有机磷农药残留量

本文通过气相色谱法检测食品中有机氯、拟除虫菊酯、有机磷农药残留量。本文采用乙腈作为提取溶剂,超声波提取目标农残,溶液用气相色谱(ECD检测器)检测有机氯和拟除虫菊酯,同样的溶液用气相色谱(FPD检测器)检测有机磷农残。该方法在国标基础上简化了前处理方法,实现了有机氯、拟除虫菊酯、有机磷农药残留量检测前处理的统一,大大缩短了前处理时间,减少了溶剂的消耗。16种有机氯、拟除虫菊酯以及11种有机磷的分离度好,相关系数0.9986～0.99998,定量限0.001～0.06mg/kg,相对标准偏差RSD小于5.0,加标回收率90.8%～108.3%。     

气相色谱-质谱联用法测定水溶肥料中10种拟除虫菊酯类农药含量

目的建立气相色谱-质谱联用法测定肥料中10种拟除虫菊酯农药的分析方法。方法样品经丙酮超声提取,DB-5MS毛细管气相色谱柱分离,用气相色谱-质谱法测定。结果 10种化合物浓度在各自线性范围内与相应峰面积呈线性关系,相关系数r 0.990,加标回收率为78.12%～120.63%,精密度(relative standard deviation,RSD)为1.24%～11.91%。称样量为0.5 g时,联苯菊酯检出限为0.06 mg/kg;醚菊酯检出限为0.1mg/kg;甲氰菊酯、氯菊酯、氟胺氰菊酯检出限为0.2 mg/kg;氯氟氰菊酯、氟氯氰菊酯、氯氰菊酯、氰戊菊酯、溴氰菊酯检出限为0.4 mg/kg。结论该方法样品前处理简单、快捷,重复性及回收率均能达到检测分析要求,可以应用于水溶肥料中拟除虫菊酯农药的检测。     

Analysis of polychlorinated biphenyls, pyrethroid insecticides and fragrances in human milk using a laminar cup liner in the GC injector

 Since 1970 the State Laboratory of Basle City has been periodically analyzing human milk from the region (the latest in 1998/99) as a bioindicator for the environmental load of organochlorine pesticides [1, 2]. The analysis of human milk is very complex including several clean-up steps and is therefore time consuming. The focus is mainly on organochlorine pesticides, polychlorinated biphenyls (PCB), and nitro-musk compounds; analytes which are easily detectable with gas chromatography and electron capture detection (ECD). Our aim was to minimize the clean-up steps for the analysis of ECD sensitive substances. Furthermore, analytes insensitive to EC detection that require MS detection, such as polycyclic musk substitutes, were of interest. With the help of a specially designed GC liner in the vaporizing injector of the gas chromatograph, the laminar cup liner, we have considerably reduced the time and effort in the sample preparation. With the described clean-up procedure we analyzed 53 human milk samples from the region of Basle for PCB, pyrethrins, and pyrethroid insecticides and fragrances (nitro-musk compounds and polycyclic musk substitutes). While PCB showed a general downward trend in mean concentrations since 1980, residues of the polycyclic musk substitutes galaxolide and tonalide were detectable in almost every sample (e.g., 73 μg/kg fat of HHCB, 74 μg/kg fat of AHTN). Pyrethrins and pyrethroid insecticides were detected only at low concentrations between 0.03 and 0.46 mg/kg fat. Received: 28 September 1999 / Revised version: 2 May 2000     

蔬菜水果中菊酯类农药残留快速检测的方法研究

为研究一种蔬菜水果中菊酯类农药残留快速检测方法,通过选购市场上常见的胶体金免疫层析产品及菊酯类农药,对蔬菜水果中菊酯农残的快速检测进行前处理步骤的优化,并考察每种胶体金免疫层析产品在果蔬基质样品检测中的灵敏度、特异性、假阳性率、假阴性率和准确度,以实现胶体金免疫层析产品的整体性评价。结果表明,直接稀释法检测大白菜、韭菜和柑橘时,检测限较高,无法满足检测要求;直接提取法适用于大白菜、韭菜和柑橘的快速检测,检测限为2 mg/kg。方法学验证结果表明：以大白菜、韭菜和柑橘作为空白基质的检测限为2 mg/kg,灵敏度均为100%,特异性为100%,假阳性率为0,假阴性率为0。该方法快速准确、灵敏度高,可适用于蔬菜水果中菊酯类农药残留的快速检测。     

固相萃取-气相色谱质谱法测定茶叶中11种农药残留量

目的建立固相萃取-气相色谱质谱联用法测定茶叶中11种农药残留量的分析方法。方法茶叶样品中的农药残留经丙酮提取,无水硫酸镁除水,采用Carbon/NH_2固相萃取柱在线净化与富集,DB-17MS毛细管柱分离检测,多离子反应模式,外标法定量。结果在20～200 mg/L的浓度范围, 11种农药残留均与其对应的峰面积呈线性关系,方法的检出限(S/N=3)在0.001～0.018 mg/kg之间。以空白样品为基体进行加标回收实验,所得回收率在72.0%～93.2%之间,测定值的相对标准偏差(n=6)在2.35%～6.34%之间。结论该方法准确度较高、稳定性较好、检出限低,适用于茶叶样品中有机磷、氨基甲酸酯、拟除虫菊酯和杀菌剂等多组分农药残留量的同时测定。     

Determination of Pyrethroid Insecticides in Crude and Canned Vegetable Samples by Supercritical Fluid Chromatography

A supercritical fluid chromatography method for the determination of seven pyrethroid insecticides (allethrin, resmethrin, phenothrin, permethrin, tetramethrin, cypermethrin, deltamethrin) and one of their common metabolites, phenoxybenzyl alcohol, in whole and peeled potatoes and mixed vegetables was developed. The efficiencies of the two extraction techniques, supercritical fluid extraction and microwave-assisted extraction, for the extraction of pyrethroids from vegetable samples were also compared. The retention times of various pyrethroids ranged from 8.4 to 22.9 min, while all of the peaks were well-resolved and distinctly identified. The limits of detection of pyrethroid insecticides ranged between 0.31 and 0.54 ppm, whereas the limits of detection of phenoxybenzyl alcohol was 0.62 ppm. The recoveries of pyrethroid insecticides from whole potatoes, peeled potatoes, and mixed vegetables ranged as 93.83–99.8%, 92.3–105.8%, and 93.67–102.7%, respectively, with the use of supercritical fluid extraction. The corresponding recovery ranges while using microwave-assisted extraction were 94.2–102%, 96.6–101.2%, and 96–103.2%. These findings suggested that supercritical fluid chromatography was a sensitive and rapid technique for the analysis of pyrethroids in complex matrices, such as vegetables, fruits, and other agricultural products.     

气相色谱法测定蜂蜜中10种拟除虫菊酯类农药残留

目的为了结合《蜂蜜卫生标准》的修订要求中补充农药残留等相关指标和检验方法的需要,建立气相色谱法同时测定蜂蜜中10种拟除虫菊酯类农药残留的方法。方法通过对毛细管柱的类型、溶剂的种类、固相萃取小柱种类的选择实验,确定应用二氯甲烷为提取溶剂,经弗罗里硅土固相萃取柱净化,DB-17(0.25 mm×0.25μm×20 m)的毛细管柱作为分离柱,以GC-ECD测定,峰面积定量。结果 10种农药加标回收率为77.3%～103.0%,相对标准偏差2.5%～7.5%,检出限为0.000 5～0.005 mg/kg(当称样量为5.00 g时)。结论该方法适合蜂蜜中多种拟除虫菊酯类农药残留的同时检测。