CN101782558A - Method for detecting organophosphorus multi-pesticide residue in tea based on matrix effect compensation - Google Patents
Method for detecting organophosphorus multi-pesticide residue in tea based on matrix effect compensation Download PDFInfo
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Abstract
基于基质效应补偿的茶叶中有机磷类多农残测定方法,属于食品安全检测技术领域。本发明包括以下步骤:1)农药标准溶液配制,2)样品溶液制备,3)由气相色谱测定待测样和混合标准溶液,该方法快速、简单、经济、灵敏度高,有效地减小或消除了来自茶叶的复杂基质给有机磷农药残留测定的干扰,为进一步完善茶叶质量安全的评价体系提供了科学依据。
The invention discloses a method for determining organophosphorus polypesticide residues in tea based on matrix effect compensation, belonging to the technical field of food safety detection. The invention comprises the following steps: 1) preparation of pesticide standard solution, 2) preparation of sample solution, 3) determination of sample to be tested and mixed standard solution by gas chromatography, the method is fast, simple, economical, highly sensitive, effectively reduces or eliminates The interference of the complex matrix from tea to the determination of organophosphorus pesticide residues was eliminated, and a scientific basis was provided for further improving the evaluation system of tea quality and safety.
Description
技术领域technical field
本发明属于食品安全检测技术领域,具体涉及一种基于基质效应补偿的茶叶中有机磷类多农残测定方法。The invention belongs to the technical field of food safety detection, and in particular relates to a method for measuring organophosphorus polypesticide residues in tea based on matrix effect compensation.
背景技术Background technique
农药残留色谱检测是复杂混合物中痕量组分的分析,基质效应问题的影响异常显著。农药残留分析过程中的基质效应,即样品中除分析物以外的其它基质成分导致待测物测定值偏离真值,影响待测物的定量准确度和精密度,且影响因素多变,很难被完全消除,严重影响检测结果的准确性。在气相色谱分析中大多数农药,表现出不同程度的基质增强效应,尤其是有机磷类农药的基质效应非常明显,如高脂肪含量样品中有机磷农药的检测,多数含P=0基团的农药回收率会超过130%,这种现象称为基质引起的响应值增强效应。Pesticide residue chromatographic detection is the analysis of trace components in complex mixtures, and the influence of matrix effect issues is extremely significant. The matrix effect in the process of pesticide residue analysis, that is, the matrix components other than the analyte in the sample cause the measured value of the analyte to deviate from the true value, affecting the quantitative accuracy and precision of the analyte, and the influencing factors are changeable, it is difficult to be completely eliminated, seriously affecting the accuracy of the test results. In gas chromatography analysis, most pesticides show different degrees of matrix enhancement effect, especially the matrix effect of organophosphorus pesticides is very obvious. Pesticide recoveries can exceed 130%, a phenomenon known as matrix-induced response enhancement.
茶叶因其作为多年生木本植物及后续加工过程的繁复,样品基质背景异常丰富,样品基质的影响本就比一般水果蔬菜要复杂得多,基质效应的影响更是相当复杂。基质效应增大随机误差及系统误差,影响分析的准确度和灵敏度,严重影响农残测定准确定量和正确定性。Because tea is a perennial woody plant and the subsequent processing is complicated, the background of the sample matrix is extremely rich. The influence of the sample matrix is much more complicated than that of ordinary fruits and vegetables, and the influence of the matrix effect is even more complicated. The matrix effect increases the random error and systematic error, affects the accuracy and sensitivity of the analysis, and seriously affects the accurate quantification and correctness of the determination of pesticide residues.
现在,国外用来弥补基质效应的较常见有基质匹配标准校正法。如1993年Erney D R等对有机磷农药的气相色谱基质增强效应研究;1998年Kocourek V等对农药在植物提取基质中的稳定性研究;2004年Martinez.Vidal J L等对在6种食品中气质联用测定农残品评价的研究。目前国外许多农残方法开发都使用基质匹配标准来进行校准,以使标样中的基质环境与样品中的相同,但是要取得与每一种样品严格匹配的基质,这对于常规实验室的大量的日常工作来说是不现实的。弥补基质效应另外还有标准添加法、多重净化法、校正因子校准法等多种方法。如2001年Podhomiak L V等气谱pfpd测定典型果蔬基质中有机磷农残的研究;2001年Schenck F J等深度净化减少气谱对食品中农残测定的基质效应的研究;2002年Gonz-lez等气谱ecd测定典型蔬菜中农药多残留的基质效应研究、2003年Martinez-Galera M等用标准曲线相对校正蔬菜中pyrethro ids的定量测定的系统误差;2003年Ferndndez Gonzdl ez C等气质联用测定白葡萄中的杀真菌剂的研究;2004年Albero B等spe、气质联用测定蜂蜜中农残测定研究;2005年Consuelo S等用基质保护剂抵消基质效应法对农残气质联用的测定研究。At present, the matrix matching standard correction method is commonly used to compensate for the matrix effect in foreign countries. For example, in 1993, Erney DR et al. studied the gas chromatography matrix enhancement effect of organophosphorus pesticides; in 1998, Kocourek V et al. studied the stability of pesticides in plant extraction matrices; in 2004, Martinez.Vidal J L et al. Research on the evaluation of pesticide residues determined by GC-MS. At present, many methods for pesticide residues in foreign countries use matrix matching standards for calibration, so that the matrix environment in the standard sample is the same as that in the sample, but it is necessary to obtain a matrix that strictly matches each sample, which is very difficult for a large number of conventional laboratories. It is unrealistic for daily work. To make up for the matrix effect, there are other methods such as standard addition method, multiple purification method, and correction factor calibration method. For example, in 2001, Podhomiak L V et al. studied the determination of organophosphorus pesticide residues in typical fruit and vegetable matrices by gas spectrometer pfpd; in 2001, Schenck F J et al. studied the matrix effect of gas spectrometry on the determination of pesticide residues in food by deep purification; in 2002, Gonz-lez et al. Research on the matrix effect of gas spectrum ecd determination of pesticide residues in typical vegetables, in 2003 Martinez-Galera M et al used the standard curve to relatively correct the systematic error of the quantitative determination of pyrethroids in vegetables; in 2003 Ferndndez Gonzdlez C et al Research on fungicides in grapes; in 2004, Albero B et al. spe, GC-MS determination of pesticide residues in honey; in 2005, Consuelo S et al. used matrix protective agent to offset the matrix effect method on the determination of pesticide residues by GC-MS.
目前国内对此问题的研究较少,目前国内许多的农药残留分析方法的开发大多还没有对基质效应所产生的影响给予足够重视,也没有采取相应的补偿措施。仅有2006年赵海峰用气质联用测定蔬菜中的农残研究,以基质匹配标准进行校正基质增强效应;2006年黄宝勇用气质联用测定果蔬中农药多残留研究,进行了农药单浓度的基质效应研究和基质保护剂探索等几篇研究报道。At present, there are few researches on this issue in China, and the development of many pesticide residue analysis methods in China has not paid enough attention to the influence of matrix effect, and has not taken corresponding compensation measures. Only in 2006, Zhao Haifeng used GC-MS to measure pesticide residues in vegetables, and used the matrix matching standard to correct the matrix enhancement effect; in 2006, Huang Baoyong used GC-MS to measure pesticide residues in fruits and vegetables, and carried out the matrix effect of single concentration of pesticides. Research and exploration of matrix protective agents and several other research reports.
由于基质效应的产生对于化合物的准确定性与定量具有较大影响,所以对基质效应进行考察评估并采取有效措施进行消除或补偿是进行农药残留分析方法开发或方法验证过程中不可缺少的一个重要环节,是要获得更为精确和准确的结果必须考虑到的一个基本的前提。Since the generation of matrix effects has a great influence on the accurate identification and quantification of compounds, it is an indispensable and important link in the process of pesticide residue analysis method development or method validation to investigate and evaluate matrix effects and take effective measures to eliminate or compensate them. , is a basic premise that must be taken into account in order to obtain more precise and accurate results.
发明内容Contents of the invention
针对现有技术存在的问题,本发明的目的在于设计提供一种快速、简单、经济、灵敏度高,且能够有效地减小或消除了来自茶叶的复杂基质给有机磷农药残留测定的干扰的基于基质效应补偿的茶叶中有机磷类多农残测定方法。Aiming at the problems existing in the prior art, the purpose of the present invention is to design and provide a fast, simple, economical, high-sensitivity, and can effectively reduce or eliminate the interference from the complex matrix of tea leaves to the determination of organophosphorus pesticide residues. Determination method of organophosphorus polypesticides in tea with matrix effect compensation.
所述的基于基质效应补偿的茶叶中有机磷类多农残测定方法,其特征在于包括以下步骤:The method for the determination of organophosphorus and many pesticide residues in tea based on matrix effect compensation is characterized in that it comprises the following steps:
1)农药标准溶液配制1) Preparation of pesticide standard solution
a.农药混合标准储备溶液配制:称取各种有机磷类农药标准品,用丙酮稀释,逐一配制成1000mg/L的单一农药标准储备液,根据各农药的仪器响应,用丙酮配制成混合标准储备溶液;a. Preparation of pesticide mixed standard stock solution: Weigh various organophosphorus pesticide standard products, dilute them with acetone, and prepare them one by one into 1000mg/L single pesticide standard stock solution, and prepare mixed standard with acetone according to the instrument response of each pesticide stock solution;
b.基质保护剂溶液配制:将果糖在水中溶解后,用丙酮定容,配制成浓度为35-45mg/mL的基质保护剂A,将L-古洛糖酸-γ-内酯在水中溶解后,用丙酮定容,配制成浓度为15-25mg/mL的基质保护剂B;b. Preparation of matrix protective agent solution: dissolve fructose in water, dilute to volume with acetone, prepare matrix protective agent A with a concentration of 35-45 mg/mL, and dissolve L-gulonic acid-γ-lactone in water Finally, dilute to volume with acetone, and prepare matrix protective agent B with a concentration of 15-25 mg/mL;
c.农药混合标准工作液配制:取1.0mL农药混合标准储备溶液,加入基质保护剂A 0.05-0.15mL和B 0.05-0.15mL配制成农药混合标准工作液,备用;c. Preparation of pesticide mixed standard working solution: take 1.0mL of pesticide mixed standard stock solution, add 0.05-0.15mL of substrate protection agent A and B 0.05-0.15mL to prepare pesticide mixed standard working solution, and set aside;
2)样品溶液制备2) Sample solution preparation
a.试料制备:取茶叶样品,经粉碎机粉碎后,制成待测样,备用;a. Sample preparation: take the tea sample, pulverize it with a pulverizer, and make it into a sample to be tested, and set it aside;
b.待测样品提取:取待测样4g,加入10-15ml丙酮,在振荡器中快速振荡5-15分钟,然后在离心机转速3500-5000rpm条件下离心10-15min,取上清液;b. Extraction of the sample to be tested: take 4g of the sample to be tested, add 10-15ml of acetone, oscillate rapidly in the shaker for 5-15 minutes, then centrifuge for 10-15min at a centrifuge speed of 3500-5000rpm, and take the supernatant;
c.净化:取5ml上清液,旋转真空浓缩直至上清液近干后,用丙酮溶解定容至2.0ml,再转移至离心管中,并在离心管中加入(C18)80-120mg,在旋涡混合器上混匀2-4min,然后在离心机转速3500-5000rpm条件下离心5-10min,离心后取上清液1ml,最后加入基质保护剂A 0.05-0.15mL和B 0.05-0.15mL,供色谱测定;c. Purification: Take 5ml of supernatant, concentrate in vacuum until the supernatant is almost dry, dissolve it with acetone to 2.0ml, then transfer to a centrifuge tube, and add (C18) 80-120mg to the centrifuge tube, Mix on a vortex mixer for 2-4min, then centrifuge at a speed of 3500-5000rpm for 5-10min, take 1ml of the supernatant after centrifugation, and finally add matrix protective agent A 0.05-0.15mL and B 0.05-0.15mL , for chromatographic determination;
3)由气相色谱测定待测样和混合标准溶液3) Determine the sample to be tested and the mixed standard solution by gas chromatography
a.测定:由自动进样器吸取1.0μL农药混合标准工作液和经净化后的待测样注入色谱仪中,以双柱保留时间定性,以分析柱A获得的样品溶液峰面积与标准溶液峰面积定量;a. Determination: Draw 1.0 μL of pesticide mixed standard working solution and the purified sample to be tested into the chromatograph by the automatic sampler, and use the dual-column retention time for qualitative analysis, and analyze the peak area of the sample solution obtained by column A and the standard solution. Peak area quantification;
b.结果分析:双柱测得的样品中未知组分的保留时间分别与标样在同一色谱柱上的保留时间相比较,如果样品中某组分的两组保留时间与标准中某一农药的两组保留时间相差都在±0.05min内的可认定为该农药;b. Result analysis: the retention time of the unknown component in the sample measured by the double column is compared with the retention time of the standard sample on the same chromatographic column. If the difference between the retention times of the two groups is within ±0.05min, it can be identified as the pesticide;
样品中被测农药残留量以质量分数ω计,计算公式如下:The measured pesticide residue in the sample is calculated as the mass fraction ω, and the calculation formula is as follows:
式中:In the formula:
Ψ-标准溶液中农药的含量,单位为毫克/升(mg/L);Ψ-the content of pesticides in the standard solution, in milligrams per liter (mg/L);
A-样品中被测农药的峰面积;The peak area of the tested pesticide in the A-sample;
As-农药标准溶液中被测农药的峰面积;A s - the peak area of the tested pesticide in the pesticide standard solution;
V1-提取溶剂总体积;V 1 - total volume of extraction solvent;
V2-吸取出用于检测的提取溶液的体积;V 2 - the volume of the extraction solution drawn out for detection;
V3-样品定容体积;V 3 -sample constant volume;
m-样品的质量。m - the mass of the sample.
所述的基于基质效应补偿的茶叶中有机磷类多农残测定方法,其特征在于所述的步骤1)中称取敌百虫、敌敌畏、甲胺磷、速灭磷、乙酰甲胺磷、丙线磷、甲拌磷、氧乐果、百治磷、乙拌磷、胺丙畏、异稻瘟净、除线磷、久效磷、乐果、磷胺、皮蝇磷、甲基嘧啶硫磷、毒死蜱、甲基对硫磷、嘧啶磷、马拉硫磷、杀螟硫磷、对硫磷、乙基溴硫磷、水胺硫磷、稻丰散、杀虫畏、灭菌磷、甲基硫环磷、乙硫磷、三唑磷、伐灭磷、苯硫磷、亚胺硫磷、伏杀硫磷、谷硫磷、吡菌磷、益棉磷、蝇毒磷、二溴磷、治螟磷、二嗪农、地虫硫磷、地毒磷、倍硫磷、溴硫磷、对氧磷、异柳磷、丙溴磷和硫环磷农药标准品,逐一用丙酮稀释,配制成51种农药1000mg/L的单一农药标准储备液,并用丙酮配制成混合标准储备溶液;待色谱测定时,取1.0mL农药混合标准储备溶液,加入基质保护剂A 0.1mL和B 0.1mL配制成农药混合标准工作液。The described method for measuring organophosphorus polypesticide residues in tea leaves based on matrix effect compensation is characterized in that trichlorfon, dichlorvos, methamidophos, memethaphos, acephate, Propyrophos, phorate, omethoate, dicrotophos, diphorate, amphetamine, isofradine, phenophos, monocrotophos, dimethoate, phosphamide, phosphophos, methylpyrimidine Thion, chlorpyrifos, methyl parathion, pyrimiphos, malathion, fenitrothion, parathion, ethyl bromthion, isocarbophos, Daofengsan, insecticide fear, fenphos , methylthiocyclophos, ethion, triazophos, fenfofos, fenthion, imidophos, azinphos, azinphos, pyritropin, yibafos, amaphos, di Pesticide standard products of bromphos, fenfofos, diazinon, fenthion, fenthion, fenthion, brothion, paraoxon, isofenphos, profenofos and thionon, one by one with acetone Dilute and prepare a single pesticide standard stock solution of 1000mg/L for 51 pesticides, and prepare a mixed standard stock solution with acetone; when the chromatographic determination is performed, take 1.0mL of the pesticide mixed standard stock solution, add matrix protective agent A 0.1mL and B 0.1 mL to prepare the pesticide mixed standard working solution.
所述的基于基质效应补偿的茶叶中有机磷类多农残测定方法,其特征在于所述的步骤1)中步骤b在果糖1.75-2.25g中加水8.5mL溶解,再用丙酮定容至50mL,制得浓度为35-45mg/mL的基质保护剂A;在L-古洛糖酸-γ-内酯0.75-1.25g中加水10mL溶解,再用丙酮定容至50mL,制得浓度为15-25mg/mL的基质保护剂B。The method for the determination of organophosphorus pesticide residues in tea based on matrix effect compensation is characterized in that in step b of step 1), 8.5 mL of water is added to 1.75-2.25 g of fructose to dissolve, and then the volume is adjusted to 50 mL with acetone , to prepare matrix protective agent A with a concentration of 35-45 mg/mL; add 10 mL of water to 0.75-1.25 g of L-gulonic acid-γ-lactone to dissolve, then dilute to 50 mL with acetone to obtain a concentration of 15 - 25 mg/mL of stroma protectant B.
所述的基于基质效应补偿的茶叶中有机磷类多农残测定方法,其特征在于所述的步骤2)中步骤b离心采用4000rpm条件下离心10min。The method for the determination of organophosphorus polypesticide residues in tea based on matrix effect compensation is characterized in that the step b in step 2) is centrifuged at 4000 rpm for 10 min.
所述的基于基质效应补偿的茶叶中有机磷类多农残测定方法,其特征在于所述的步骤2)中步骤c离心采用4000rpm条件下离心5min。The method for the determination of organophosphorus polypesticide residues in tea based on matrix effect compensation is characterized in that the centrifugation in step 2) is performed at 4000 rpm for 5 minutes.
所述的基于基质效应补偿的茶叶中有机磷类多农残测定方法,其特征在于所述的步骤2)中步骤c离心后取上清液1ml,最后加入基质保护剂A 0.1mL和B 0.1mL,供色谱测定;净化后的待测样过于混浊,用0.2μm滤膜过滤后再进行色谱测定。The method for determining the amount of organophosphorus pesticide residues in tea leaves based on matrix effect compensation is characterized in that 1ml of the supernatant is obtained after centrifugation in step c in the step 2), and finally 0.1mL of matrix protecting agents and 0.1mL of B are added. mL, for chromatographic determination; the purified sample to be tested is too turbid, filtered through a 0.2 μm filter membrane before chromatographic determination.
所述的基于基质效应补偿的茶叶中有机磷类多农残测定方法,其特征在于所述的步骤3)中气相色谱条件为:The method for determining the amount of organophosphorus pesticide residues in tea based on matrix effect compensation is characterized in that the gas chromatographic conditions in the described step 3) are:
色谱柱:预柱,1.0m,0.32mm内径,脱活石英毛细管柱,采用两根色谱柱,分别为:A柱:50%聚苯基甲基硅氧烷柱,30m×0.32mm×0.25μm,Chromatographic column: pre-column, 1.0m, 0.32mm inner diameter, deactivated quartz capillary column, using two chromatographic columns, respectively: A column: 50% polyphenylmethylsiloxane column, 30m×0.32mm×0.25μm ,
B柱:100%聚甲基硅氧烷柱,30m×0.32mm×0.25μm;温度:进样口温度为220℃,检测器温度为250℃;升温程序:初始为80℃,保持1min后,以15℃/min升温速度升到220℃,保持1min;然后以20℃/min升温速度升到250℃,保持7min;B column: 100% polymethylsiloxane column, 30m×0.32mm×0.25μm; temperature: inlet temperature is 220°C, detector temperature is 250°C; heating program: initially 80°C, hold for 1min, then Raise to 220°C at a heating rate of 15°C/min and keep for 1min; then raise to 250°C at a heating rate of 20°C/min and keep for 7min;
气体及流量:Gas and Flow:
载气:氮气,纯度≥99.999%,流速为10mL/min,Carrier gas: nitrogen, purity ≥99.999%, flow rate 10mL/min,
燃气:氢气,纯度≥99.999%,流速为75mL/min,Gas: hydrogen, purity ≥ 99.999%, flow rate 75mL/min,
助燃气:空气,流速为100mL/min;Supporting gas: air, the flow rate is 100mL/min;
进样方式:不分流进样。Injection method: splitless injection.
所述的基于基质效应补偿的茶叶中有机磷类多农残测定方法,其特征在于所述的各种农药的纯度大于等于96%。The method for the determination of organophosphorus polypesticide residues in tea based on matrix effect compensation is characterized in that the purity of the various pesticides is greater than or equal to 96%.
本发明的原理:样品中有机磷类农药经丙酮提取,提取溶液经基质分散萃取净化、浓缩后,加入基质保护剂,用双塔自动进样器同时注入气相色谱的两个进样口,样品中组分经不同极性的两根毛细管柱分离,火焰光度检测器(FPD)检测。外标法定性、定量。The principle of the present invention: the organophosphorus pesticide in the sample is extracted by acetone, and after the extraction solution is purified and concentrated by matrix dispersion extraction, the matrix protective agent is added, and the two-tower autosampler is simultaneously injected into the two injection ports of the gas chromatograph, and the sample The middle component is separated by two capillary columns with different polarities and detected by a flame photometric detector (FPD). Qualitative and quantitative by external standard method.
本发明用丙酮试剂提取茶叶中有机磷农药残留后,用C18进行分散固相萃取净化;在前提取净化溶液中加入基质保护剂-果糖和古洛糖酸内酯的混和物以补偿基质效应;用气相色谱-火焰光度检测器进行测定,提高了51种有机磷农残检测正确度,最低检出限降低至0.005mg/L-0.02mg/L;并且在一定程度上延长了仪器维护周期,减少仪器维护成本。该方法快速、简单、经济、灵敏度高,有效地减小或消除了来自茶叶的复杂基质给有机磷农药残留测定的干扰,为进一步完善茶叶质量安全的评价体系提供了科学依据。The present invention uses acetone reagent to extract organophosphorus pesticide residues in tea leaves, and then uses C18 to carry out dispersive solid-phase extraction and purification; add a matrix protective agent-a mixture of fructose and gulonolactone to the pre-extraction purification solution to compensate for the matrix effect; Determination by gas chromatography-flame photometric detector has improved the detection accuracy of 51 kinds of organophosphorus pesticide residues, and the minimum detection limit has been reduced to 0.005mg/L-0.02mg/L; and the maintenance cycle of the instrument has been extended to a certain extent. Reduce instrument maintenance costs. The method is fast, simple, economical, and highly sensitive, and effectively reduces or eliminates the interference of complex matrix from tea leaves on the determination of organophosphorus pesticide residues, and provides a scientific basis for further improving the evaluation system of tea quality and safety.
本发明与现有技术相比存在的优点为:Compared with the prior art, the present invention has the following advantages:
(1)本发明提出了可代替基质匹配标准校正的基质保护剂1种(果糖和古洛糖酸内酯),以替代繁琐的基质匹配标准校正的补偿基质效应的方法,操作简便快速经济,容易掌握,方法加标回收率80-110%,RSD 0.98~6.6%,足以满足日常农药残留检测要求。(1) The present invention proposes one kind of matrix protective agent (fructose and gulonolactone) that can replace the matrix matching standard correction, to replace the cumbersome matrix matching standard correction method for compensating the matrix effect, the operation is simple, fast and economical, Easy to master, the recovery rate of the method is 80-110%, and the RSD is 0.98-6.6%, which is enough to meet the requirements of daily pesticide residue detection.
(2)本发明加入基质保护剂提高了茶园中常用和茶叶出口常检的有机磷农药-甲胺磷、乙酰甲胺磷、毒死蜱、乐果、水胺硫磷、马拉硫磷、异稻瘟净等51种有机磷农残检测正确度,如(同浓度样品/标样)甲胺磷8.31倍增强,乙酰甲胺磷4.90倍增强等有机磷农药都校正至1左右,有效地减小或消除了来自茶叶的复杂基质给有机磷农药残留测定的干扰。(2) The present invention adds matrix protection agent and has improved the organophosphorus pesticide-methamidophos, acephate, chlorpyrifos, dimethoate, isacarbophos, malathion, isomyces commonly used in the tea garden and the organophosphorus pesticide that tea export often checks The detection accuracy of 51 kinds of organophosphorus pesticide residues such as Wenjing, such as (same concentration sample/standard sample) methamidophos 8.31 times enhancement, acephate 4.90 times enhancement and other organophosphorus pesticides are corrected to about 1, effectively reducing Or eliminate the interference from the complex matrix of tea leaves to the determination of organophosphorus pesticide residues.
(3)本发明加入基质保护剂还能改善目标有机磷农药的峰形,使其信噪比得到显著改善,降低51种有机磷农残的检测限至0.005-0.02mg/kg,提高了茶叶中有机磷农药残留检测的灵敏度。(3) The addition of matrix protective agent in the present invention can also improve the peak shape of the target organophosphorus pesticide, significantly improve its signal-to-noise ratio, reduce the detection limit of 51 kinds of organophosphorus pesticide residues to 0.005-0.02mg/kg, and improve the tea leaves. Sensitivity for the detection of organophosphorus pesticide residues.
(4)本发明一定程度上延长了仪器维护周期,使气相色谱仪日常每100个样品必须进行1次日常保养维护增加至每150-200个样品进行1次日常保养维护,减少仪器维护成本,提高了检测效率。(4) The present invention prolongs the maintenance cycle of the instrument to a certain extent, so that the daily maintenance of the gas chromatograph must be carried out once every 100 samples to every 150-200 samples, which reduces the maintenance cost of the instrument. The detection efficiency is improved.
附图说明Description of drawings
图1为应用本发明的方法对添加了13种有机磷农药的空白茶叶样品进行有机磷农药残留检测得到的色谱图。Fig. 1 is the chromatogram obtained by applying the method of the present invention to the blank tea sample added with 13 kinds of organophosphorus pesticides to detect the residues of organophosphorus pesticides.
图中:1-甲胺磷,2-乙酰甲胺磷,3-甲拌磷,4-氧乐果,5-乐果,6-甲基对硫磷,7-杀螟硫磷,8-对硫磷,9-水胺硫磷,10-杀扑磷,11-乙硫磷,12-三硫磷,13-三唑磷。In the picture: 1-Methamidophos, 2-Acephate, 3-Phorate, 4-Omethoate, 5-Dimethoate, 6-Methylparathion, 7-Fenitrothion, 8- Parathion, 9-Isocarbophos, 10-Methion, 11-Ethion, 12-Trithion, 13-Triazophos.
具体实施方式Detailed ways
以下通过具体实施例来进一步说明本发明。The present invention is further illustrated below through specific examples.
实施例:Example:
1.农药标准溶液配制1. Preparation of pesticide standard solution
单一农药标准储备液:准确称取一定量某农药标准品,用丙酮稀释,逐一配制成51种农药1000mg/L的单一农药标准储备液,贮存在-18℃以下冰箱中。Single pesticide standard stock solution: Accurately weigh a certain amount of a certain pesticide standard product, dilute it with acetone, and prepare 51 kinds of pesticide 1000mg/L single pesticide standard stock solution one by one, and store it in a refrigerator below -18°C.
农药混合标准储备溶液及农药混合标准工作液:将51种农药分为2组,按照表1中组别,根据分离效率把51种有机磷农药分成2组,根据各农药的仪器响应,逐一吸取一定体积的同组别的单个农药储备液分别注入同一容量瓶中,用丙酮稀释至刻度,采用同样方法配制成2组农药混合标准储备溶液。待色谱测定时,取1.0mL农药混合标准储备溶液,加入基质保护剂A 0.1mL和B 0.1mL配置成农药混合标准工作液,或加入基质保护剂A 0.05mL和B 0.1mL,或基质保护剂A 0.1mL和B 0.15mL,或基质保护剂A 0.15mL和B 0.15mL。Pesticide mixed standard stock solution and pesticide mixed standard working solution: divide 51 kinds of pesticides into 2 groups, according to the groups in Table 1, divide 51 kinds of organophosphorus pesticides into 2 groups according to the separation efficiency, and absorb them one by one according to the instrument response of each pesticide A certain volume of individual pesticide stock solutions of the same group were poured into the same volumetric flask, diluted to the mark with acetone, and two groups of pesticide mixed standard stock solutions were prepared in the same way. When the chromatographic determination is to be made, take 1.0mL pesticide mixed standard stock solution, add matrix protective agent A 0.1mL and B 0.1mL to configure pesticide mixed standard working solution, or add matrix protective agent A 0.05mL and B 0.1mL, or matrix protective agent A 0.1mL and B 0.15mL, or matrix protective agent A 0.15mL and B 0.15mL.
表1 51种有机磷农药列表及分组Table 1 List and grouping of 51 organophosphorus pesticides
2.基质保护剂溶液配制2. Matrix protectant solution preparation
称取果糖2g加水8.5mL溶解,用丙酮定容至50mL,记为基质保护剂A;称取L-古洛糖酸-γ-内酯1g加水10mL溶解,用丙酮定容至50mL,记为基质保护剂B。贮存在4℃左右冰箱中待用。也可配制成35、40或45mg/mL的基质保护剂A和15、20或25mg/mL的基质保护剂BWeigh 2 g of fructose and add 8.5 mL of water to dissolve, dilute to 50 mL with acetone, and record it as matrix protective agent A; weigh 1 g of L-gulonic acid-γ-lactone, add 10 mL of water to dissolve, dilute to 50 mL with acetone, and record as Matrix protectant B. Store in a refrigerator at around 4°C until use. Also formulated as 35, 40 or 45 mg/mL of matrix protectant A and 15, 20 or 25 mg/mL of matrix protectant B
3.分析步骤3. Analysis steps
3.1试料制备3.1 Sample preparation
取不少于100g茶叶样品,放入粉碎机中粉碎,制成待测样,放入分装容器中备用。Take not less than 100g of tea samples, put them into a pulverizer and pulverize them to make samples to be tested, and put them into sub-packaging containers for later use.
3.2提取3.2 Extraction
准确称取4.0g试料放人15mL离心管中,加入10mL或12ml丙酮,在振荡器中上快速振荡10或15min,后用离心机4000或5000rpm离心10或15min,取上清液待净化。Accurately weigh 4.0g of the sample and put it into a 15mL centrifuge tube, add 10mL or 12ml of acetone, shake rapidly on the shaker for 10 or 15min, and then centrifuge with a centrifuge at 4000 or 5000rpm for 10 or 15min, and take the supernatant to be purified.
3.3净化3.3 Purification
取5.0mL上清液旋转真空浓缩近干,用丙酮溶解准确定容至2.0mL,并转移至5mL离心管中,加入C1880、100或120mg,旋涡混合器上混匀2min后,在离心机上4000或5000rpm离心5或10min,取上清液1.0mL,加入基质保护剂A 0.1mL和B 0.1mL,或加入基质保护剂A 0.05mL和B 0.1mL,或基质保护剂A 0.1mL和B 0.15mL,或基质保护剂A 0.15mL和B 0.15mL。Take 5.0mL of supernatant and concentrate it in a vacuum to dryness, dissolve it in acetone and adjust the volume to 2.0mL, transfer it to a 5mL centrifuge tube, add C1880, 100 or 120mg, mix on a vortex mixer for 2min, and then put it in a centrifuge at 4000 Or centrifuge at 5000rpm for 5 or 10min, take supernatant 1.0mL, add matrix protective agent A 0.1mL and B 0.1mL, or add matrix protective agent A 0.05mL and B 0.1mL, or matrix protective agent A 0.1mL and B 0.15mL , or matrix protectant A 0.15mL and B 0.15mL.
供色谱测定。如样品过于混浊,应用0.2μm滤膜过滤后再进行测定。For chromatographic determination. If the sample is too turbid, it should be filtered with a 0.2 μm filter membrane before measurement.
3.4测定3.4 Determination
3.4.1色谱参考条件3.4.1 Chromatographic reference conditions
3.4.1.1色谱柱3.4.1.1 Columns
预柱,1.0m,0.32mm内径,脱活石英毛细管柱。Pre-column, 1.0m, 0.32mm inner diameter, deactivated quartz capillary column.
采用两根色谱柱,分别为:Two chromatographic columns are used, namely:
A柱:50%聚苯基甲基硅氧烷(DB-1701)柱,30m×0.32mm×0.25μm;A column: 50% polyphenylmethylsiloxane (DB-1701) column, 30m×0.32mm×0.25μm;
B柱:100%聚甲基硅氧烷(DB-1)柱,30m×0.32mm×0.25μm。B column: 100% polymethylsiloxane (DB-1) column, 30m×0.32mm×0.25μm.
3.4.1.2温度3.4.1.2 Temperature
进样口温度,220℃。Injection port temperature, 220°C.
检测器温度,250℃;Detector temperature, 250°C;
升温程序:初始为80℃(保持1min)以15℃/min升温速度升到220℃(保持1min);然后以20℃/min升温速度升到250℃(保持7min)。Heating program: Initially 80°C (hold for 1min) to 220°C at a rate of 15°C/min (hold for 1min); then increase to 250°C at a rate of 20°C/min (hold for 7min).
3.4.1.3气体及流量3.4.1.3 Gas and flow rate
载气:氮气,纯度≥99.999%,流速为10mL/min。Carrier gas: nitrogen, purity ≥ 99.999%, flow rate 10mL/min.
燃气:氢气,纯度≥99.999%,流速为75mL/min。Gas: hydrogen, purity ≥ 99.999%, flow rate 75mL/min.
助燃气:空气,流速为100mL/min。Supporting gas: air, the flow rate is 100mL/min.
3.4.1.4进样方式3.4.1.4 Sample injection method
不分流进样。样品一式两份,由双塔自动进样器同时进样。Splitless injection. Samples were performed in duplicate and injected simultaneously by a dual-tower autosampler.
3.4.2色谱分析3.4.2 Chromatographic analysis
由自动进样器吸取1.0μL标准混合溶液(或净化后的样品)注入色谱仪中,以双柱保留时间定性,以分析柱A获得的样品溶液峰面积与标准溶液峰面积比较定量。Draw 1.0 μL standard mixed solution (or purified sample) from the autosampler and inject it into the chromatograph, use the dual-column retention time for qualitative analysis, and compare the peak area of the sample solution obtained by analytical column A with the peak area of the standard solution for quantitative analysis.
4.结果表述4. Result presentation
4.1定性4.1 Qualitative
双柱测得的样品中未知组分的保留时间(RT)分别与标样在同一色谱柱上的保留时间(RT)相比较,如果样品中某组分的两组保留时间与标准中某一农药的两组保留时间相差都在±0.05min内的可认定为该农药。The retention time (RT) of the unknown component in the sample measured by the double column is compared with the retention time (RT) of the standard sample on the same chromatographic column. The difference between the retention times of the two groups of pesticides is within ±0.05min, which can be identified as the pesticide.
4.2计算4.2 Calculation
样品中被测农药残留量以质量分数ω计,数值以毫克每千克(mg/kg)表示,按公式(1)计算。The measured pesticide residue in the sample is expressed as mass fraction ω, and the value is expressed in milligrams per kilogram (mg/kg), calculated according to formula (1).
式中:In the formula:
Ψ-标准溶液中农药的含量,单位为毫克/升(mg/L);Ψ-the content of pesticides in the standard solution, in milligrams per liter (mg/L);
A-样品中被测农药的峰面积;The peak area of the tested pesticide in the A-sample;
As-农药标准溶液中被测农药的峰面积;A s - the peak area of the tested pesticide in the pesticide standard solution;
V1-提取溶剂总体积;V 1 - total volume of extraction solvent;
V2-吸取出用于检测的提取溶液的体积;V 2 - the volume of the extraction solution drawn out for detection;
V3-样品定容体积;V 3 -sample constant volume;
m-样品的质量。m - the mass of the sample.
计算结果保留三位有效数。The calculation result retains three significant digits.
(1)应用上述的方法对添加了13种有机磷农药的空白茶叶样品进行有机磷农药残留检测,色谱图见图1,检测结果见表2。(1) Apply the method above to detect the residues of organophosphorus pesticides on the blank tea samples added with 13 organophosphorus pesticides. The chromatogram is shown in Figure 1 and the test results are shown in Table 2.
表2添加样品检测结果Table 2 Added sample detection results
(2)应用上述的方法对市场上的53个不同的茶叶样品(范围覆盖绿茶、红茶、乌龙、普洱等)进行了有机磷农药残留检测,结果在15个样品中检测到11种有机磷农药残留,具体结果见表3。(2) Using the method above, 53 different tea samples on the market (covering green tea, black tea, oolong, Pu'er, etc.) were tested for organophosphorus pesticide residues. As a result, 11 kinds of organophosphorus were detected in 15 samples Pesticide residues, the specific results are shown in Table 3.
表3实际样品中有机磷农药残留检测结果Table 3 Detection results of organophosphorus pesticide residues in actual samples
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