气相色谱质谱法同时测定大米中有机氯、拟除虫菊酯类杀虫剂及酰胺类除草剂的研究
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摘要
农药残留问题越来越受人们的关注,农药在水稻上的使用,一方面能有效提高粮食的产量;另一方面也影响着大米的米质,同时对环境造成一定的污染。传统的针对某一种单一组分农药残留的检测方法已经不能满足现代实验室的需要,快速、简单、便宜,对环境污染少及能有效除去杂质的多残留检测是分析检测工作者追求的目标。本研究采用改进了的分散固相萃取(QuEChERS)前处理技术,用气相色谱-质谱法(GC/MS)对大米中的有机氯、拟除虫菊酯类杀虫剂及酰胺类除草剂农药残留进行快速检测,可对未来快速发展农药残留的检测方法提供参考依据。所得结果如下:
①在样品前处理上,分别对样品称样量、提取方法、提取溶剂及净化方式进行了优化研究,结果表明:称取5g样品加入15mL水代替传统方法中的样品称样量,能减少试剂的消耗量并有效降低样品浓缩后的基质效应;涡旋提取2min,在没有降低提取率的前提下,大大缩减了样品前处理时间,明显提高检测效率;提取溶剂采用乙酸乙酯代替乙腈,减少样品前处理的环境污染,保护分析工作者的身体健康;用PSA作为分散剂,采用分散固相萃取方法,简化步骤,节省试剂,能有效去除基质中的干扰物质。
②各农药组分的分离检测,首先用全扫描方式(Scan)确定每种农药组分的保留时间,并得到总离子流图和质谱图,由此,根据保留时间分组确定每种化合物1个定量离子,2～3个定性离子,进行选择离子方式(SIM)检测,减少背景离子干扰,有效提高检测灵敏度。
③采用基质加标的方法考察了不同农药的基质效应,并有效补偿由基质效应造成的定量误差,在大米样品基质中,乙草胺、敌稗、丙草胺、氯菊酯、氯氰菊酯、氰戊菊酯和溴氰菊酯存在着明显的基质效应,而且溴氰菊酯在大米样品基质中会使一个异构体向另一异构体转变。
④采用上述的优化条件,用毛细管色谱柱进行分离,一次进样在30min内将不同种类和性质的农药进行有效的色谱分离,各农药的检出限为0.0125～0.075mg/kg,平均回收率在80.0%～107.8%之间,相对标准偏差为1.37%～11.94%。
⑤对两种不同的定量方式分别进行不确定度评定,分析试验过程中可能引入的不确定度分量,计算合成标准不确定度和扩展不确定度,选择适合本方法的定量方式。由于质谱仪本身的特点,检测背景大,各农药组分在低浓度时受背景影响明显,仪器在积分时与实际浓度存在一定偏差。因此本方法适合选择单点定量方式进行定量。
综上所述,本研究建立的方法能满足现代实验室大批量样品检测的需求,实现了快速、简单、便宜、减少污染且能有效去除杂质的目的。对整个分析试验过程进行不确定度分析,反应了仪器设备条件的符合性,而对不确定度分量的分析,为提高分析准确度提供依据。
Pesticides residues had attracted more and more attention in recent years. Pesticides used in rice effectively improved the producing yield,but also influenced the quality of the rice and brought pollution to the environment.Traditional determination method only for single residue could not meet the need of the nowadays laboratory.A fast,simple,inexpensive,non-pollution to environment and effective matrix component remove method for determination for multi-residues is essential for laboratory.A rapid determination of organochlorine,pyrethriod insecticide and amide herbicides in rice by GC/MS with improved dispersive-SPE(QuEChERS)method was set up in the study to provide the reference for the rapid determination for multi-residues.The results were as follows:
①The extraction condition including sample weight,extraction method, extraction solvent and cleanup method were studied.The results showed that:5g sample with 15mL water instead of sample weight in the traditional method reduced the solvent consumption and reduced the matrix-induced effects;sample homogenized by Vortex mixer for 2min obviously reduced the sample preparation time without decreased the extraction rate;Pesticides in rice extracted with EtAc was better for the health of the analyst than with MeCN and also protected the environment; Dispersive-SPE with dispersive sorbent of PSA used in upclean effectively removed many polar matrix components.
②Pesticide residues were determined by GC/MS,retention time and total current chromatograms were obtained by Scan program.One target ion and tow or three quality ions were obtained by SIM program to minimize the background to improve the sensitivity of the determination.
③Matrix-induced effects were reviewed between standard and matrix matched standard.A method for compensation for matrix-induced effects to reduce the error for quantitative analysis was carried out.Acetochlor,propanil,prelolachlor, permethrin,cypermethrin,fenvalerate and deltamethrin had obvious matrix-induced effects.In rice matrix,one isomer of deltamethrin could transfer to anther.
④All pesticides with different character tics were separated perfectly with selection-ion monitoring mode in one injection with 30min.Limits of detection(LOD) were between 0.0125～0.075mg/kg,average recoveries ranged from 80.0%～107.8% and RSD%were between 1.37%～11.94%.
⑤Uncertainty measurement with two quantitative methods was evaluated and uncertainty factors which may be introduced in the testing process were analyzed. Combined uncertainty and expanded uncertainty were calculated to choose the suitable quantitative method for the testing.Single point quantitative method was suitable for GC/MS method.
To concluded,the method of fast,simple,inexpensive,non-pollution to environment and effective matrix component remove for determination for multi-residues set up in the study can meet the need of laboratory with large amount of sample.The result of evaluation of the uncertainty of the testing process showed the conformance of the testing condition.The uncertainty factors analyzed to improve the analysis accuracy.
①在样品前处理上,分别对样品称样量、提取方法、提取溶剂及净化方式进行了优化研究,结果表明:称取5g样品加入15mL水代替传统方法中的样品称样量,能减少试剂的消耗量并有效降低样品浓缩后的基质效应;涡旋提取2min,在没有降低提取率的前提下,大大缩减了样品前处理时间,明显提高检测效率;提取溶剂采用乙酸乙酯代替乙腈,减少样品前处理的环境污染,保护分析工作者的身体健康;用PSA作为分散剂,采用分散固相萃取方法,简化步骤,节省试剂,能有效去除基质中的干扰物质。
②各农药组分的分离检测,首先用全扫描方式(Scan)确定每种农药组分的保留时间,并得到总离子流图和质谱图,由此,根据保留时间分组确定每种化合物1个定量离子,2～3个定性离子,进行选择离子方式(SIM)检测,减少背景离子干扰,有效提高检测灵敏度。
③采用基质加标的方法考察了不同农药的基质效应,并有效补偿由基质效应造成的定量误差,在大米样品基质中,乙草胺、敌稗、丙草胺、氯菊酯、氯氰菊酯、氰戊菊酯和溴氰菊酯存在着明显的基质效应,而且溴氰菊酯在大米样品基质中会使一个异构体向另一异构体转变。
④采用上述的优化条件,用毛细管色谱柱进行分离,一次进样在30min内将不同种类和性质的农药进行有效的色谱分离,各农药的检出限为0.0125～0.075mg/kg,平均回收率在80.0%～107.8%之间,相对标准偏差为1.37%～11.94%。
⑤对两种不同的定量方式分别进行不确定度评定,分析试验过程中可能引入的不确定度分量,计算合成标准不确定度和扩展不确定度,选择适合本方法的定量方式。由于质谱仪本身的特点,检测背景大,各农药组分在低浓度时受背景影响明显,仪器在积分时与实际浓度存在一定偏差。因此本方法适合选择单点定量方式进行定量。
综上所述,本研究建立的方法能满足现代实验室大批量样品检测的需求,实现了快速、简单、便宜、减少污染且能有效去除杂质的目的。对整个分析试验过程进行不确定度分析,反应了仪器设备条件的符合性,而对不确定度分量的分析,为提高分析准确度提供依据。
Pesticides residues had attracted more and more attention in recent years. Pesticides used in rice effectively improved the producing yield,but also influenced the quality of the rice and brought pollution to the environment.Traditional determination method only for single residue could not meet the need of the nowadays laboratory.A fast,simple,inexpensive,non-pollution to environment and effective matrix component remove method for determination for multi-residues is essential for laboratory.A rapid determination of organochlorine,pyrethriod insecticide and amide herbicides in rice by GC/MS with improved dispersive-SPE(QuEChERS)method was set up in the study to provide the reference for the rapid determination for multi-residues.The results were as follows:
①The extraction condition including sample weight,extraction method, extraction solvent and cleanup method were studied.The results showed that:5g sample with 15mL water instead of sample weight in the traditional method reduced the solvent consumption and reduced the matrix-induced effects;sample homogenized by Vortex mixer for 2min obviously reduced the sample preparation time without decreased the extraction rate;Pesticides in rice extracted with EtAc was better for the health of the analyst than with MeCN and also protected the environment; Dispersive-SPE with dispersive sorbent of PSA used in upclean effectively removed many polar matrix components.
②Pesticide residues were determined by GC/MS,retention time and total current chromatograms were obtained by Scan program.One target ion and tow or three quality ions were obtained by SIM program to minimize the background to improve the sensitivity of the determination.
③Matrix-induced effects were reviewed between standard and matrix matched standard.A method for compensation for matrix-induced effects to reduce the error for quantitative analysis was carried out.Acetochlor,propanil,prelolachlor, permethrin,cypermethrin,fenvalerate and deltamethrin had obvious matrix-induced effects.In rice matrix,one isomer of deltamethrin could transfer to anther.
④All pesticides with different character tics were separated perfectly with selection-ion monitoring mode in one injection with 30min.Limits of detection(LOD) were between 0.0125～0.075mg/kg,average recoveries ranged from 80.0%～107.8% and RSD%were between 1.37%～11.94%.
⑤Uncertainty measurement with two quantitative methods was evaluated and uncertainty factors which may be introduced in the testing process were analyzed. Combined uncertainty and expanded uncertainty were calculated to choose the suitable quantitative method for the testing.Single point quantitative method was suitable for GC/MS method.
To concluded,the method of fast,simple,inexpensive,non-pollution to environment and effective matrix component remove for determination for multi-residues set up in the study can meet the need of laboratory with large amount of sample.The result of evaluation of the uncertainty of the testing process showed the conformance of the testing condition.The uncertainty factors analyzed to improve the analysis accuracy.
引文
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56.Souverain S,Rudaz S,Veuthey J L.Matrix effect in LC-ESI-MS and LC-APCI-MA with off-line and on-line extraction procedures.J ChromatogrA,2004,1058:61-66
57.Schenck F J,Lehotay S J.Does further clean-up reduce the matrix enhancement effects:a critical point in the gas chromatographic analysis of pesticide residues.J chromatogr A,1998,800(2):283-295
58.Fernandez Gonzalez C,Rial Otero R,Cancho Grande B,et al.Determination of fungicide residues in white grapes for winemaking by gas chromatography with mass spectrometric detection and assessment of matrix effects.J AOAC Int.,2003,86:1008-1014
59.Mart nez-Vidal J L,Arrebola F J,Garrido F A.Validation of a Gas Chromatographic-Tandem Mass Spectrometric Method for Analysis of Pesticide Residues in Six Food Commodities.Selection of a Reference Matrix for Calibration.Chromatographia.2004,59:321-327
60.Anastassiades M,Mastovska K,Lebotay S J.Evaluation of analyte protectants to improve gas chromatographic analysis of pesticides.Journal of Chromatography A.2003,1015:163-184
61.方彩云,翟建军,刘锋等.基质中加入少量盐类改善MALDI-TOFMS的谱图信噪比.高等学校化学学报,2005,36(4):660-662
62.Gonzalez E,Hernandez M E,et al.Matrix-effects of vegetable commodities in electron-capture detection applied to pesticide multiresidue analysis.Journal of Chromatography A,2002,966:155-165
63.Cuadros-Rodriguez L,Garc a-Campafia A M,Almansa-Lopez E,et al.Correction function on biasied results due to matrix effects Application to the routine analysis of pesticide residues.Analytica Chimica Acta,478(2003)281-301
64.Martinez-Galeta M,Lopez-lopez T,Gil-Garcia M.D,et al.A compatative study of the correction of systematic errors in the quantitation of pyrethroids in vegetables using calibration curves prepared using standards in pure solvent.Anal Bioanal Chem,2003,375:653-660
65.Menkissoglu-Spiroudi U;Fotopoulou A;Albanis T A.Matrix effect in gas chromatographic determination of insecticides and fungicides in vegetables.Int.J Environ.Anal.Chem.2004,84:15-27
66.Alder Lutz,L deritz Sonja,Lindtner Karen,Start Hans-Juren.The ECHO technique- the more effective way of datsa evaluation in liquid chromatography-tandem mass spectrometry analysis.J Chromatogr A,2004,1058:67-79
67.Benijts T,Dams R,Lambert W.Countering matrix effects in environmental liquid chromatography-electrospray ionization tandem mass spectrometry water analysis for endocrine disruptiong chemicals.J Chromatogr A,2004,1029:153-159
68.GB/T5009.19-2003食品中六六六、滴滴涕残留量的测定方法.
69.GB/T5009.110-2003植物性食品中氯氰菊酯、氰戊菊酯和溴氰菊酯残留量的测定.
70.GB/T 5009.146-2003植物性食品中有机氯和拟除虫菊酯类农药多种残留的测定.
71.GB/T 19649-2005粮谷中405种农药多残留测定方法 气相色谱-质谱和液相色谱-串联质谱法.
72.GB/T5009.164-2003大米中丁草胺残留量的测定.
73.NY/T 761.2-2004蔬菜和水果中有机氯类、拟除虫菊酯类农药多残留检测方法.
74.GB/T5009.177-2003大米中敌稗残留量的测定.
75.Ana Aguera,Mariano Contreras,Juan Crespo,Amadeo R Fernandez-Alba.Multiresidue method for the analysis of multiclass pesticides in agricultural products by gas chromatography-tandem mass spectrometry.Analyst.2002 Mar;127(3):347-354
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54.Patel,K,Fussell R J,Goodall D M,Keely B J.Evaluation of large volume-difficult matrix introduction-gas chromatography-time of flight-mass spectrometry(LV-DMI-GC-TOF-MS)for the determination of pesticides in fruit-based baby foods.Food Additives & Contaminants,2004,21(7):658-669
55.Pate K,Fussel R J,Goodal D M,Keeky B J.Analysis of pesticide residues in lettuce by large volume-difficult matrix introduction-gas chromatography-time of flight-mass spectrometry.Analyst,2003,128(10):1228-1231
56.Souverain S,Rudaz S,Veuthey J L.Matrix effect in LC-ESI-MS and LC-APCI-MA with off-line and on-line extraction procedures.J ChromatogrA,2004,1058:61-66
57.Schenck F J,Lehotay S J.Does further clean-up reduce the matrix enhancement effects:a critical point in the gas chromatographic analysis of pesticide residues.J chromatogr A,1998,800(2):283-295
58.Fernandez Gonzalez C,Rial Otero R,Cancho Grande B,et al.Determination of fungicide residues in white grapes for winemaking by gas chromatography with mass spectrometric detection and assessment of matrix effects.J AOAC Int.,2003,86:1008-1014
59.Mart nez-Vidal J L,Arrebola F J,Garrido F A.Validation of a Gas Chromatographic-Tandem Mass Spectrometric Method for Analysis of Pesticide Residues in Six Food Commodities.Selection of a Reference Matrix for Calibration.Chromatographia.2004,59:321-327
60.Anastassiades M,Mastovska K,Lebotay S J.Evaluation of analyte protectants to improve gas chromatographic analysis of pesticides.Journal of Chromatography A.2003,1015:163-184
61.方彩云,翟建军,刘锋等.基质中加入少量盐类改善MALDI-TOFMS的谱图信噪比.高等学校化学学报,2005,36(4):660-662
62.Gonzalez E,Hernandez M E,et al.Matrix-effects of vegetable commodities in electron-capture detection applied to pesticide multiresidue analysis.Journal of Chromatography A,2002,966:155-165
63.Cuadros-Rodriguez L,Garc a-Campafia A M,Almansa-Lopez E,et al.Correction function on biasied results due to matrix effects Application to the routine analysis of pesticide residues.Analytica Chimica Acta,478(2003)281-301
64.Martinez-Galeta M,Lopez-lopez T,Gil-Garcia M.D,et al.A compatative study of the correction of systematic errors in the quantitation of pyrethroids in vegetables using calibration curves prepared using standards in pure solvent.Anal Bioanal Chem,2003,375:653-660
65.Menkissoglu-Spiroudi U;Fotopoulou A;Albanis T A.Matrix effect in gas chromatographic determination of insecticides and fungicides in vegetables.Int.J Environ.Anal.Chem.2004,84:15-27
66.Alder Lutz,L deritz Sonja,Lindtner Karen,Start Hans-Juren.The ECHO technique- the more effective way of datsa evaluation in liquid chromatography-tandem mass spectrometry analysis.J Chromatogr A,2004,1058:67-79
67.Benijts T,Dams R,Lambert W.Countering matrix effects in environmental liquid chromatography-electrospray ionization tandem mass spectrometry water analysis for endocrine disruptiong chemicals.J Chromatogr A,2004,1029:153-159
68.GB/T5009.19-2003食品中六六六、滴滴涕残留量的测定方法.
69.GB/T5009.110-2003植物性食品中氯氰菊酯、氰戊菊酯和溴氰菊酯残留量的测定.
70.GB/T 5009.146-2003植物性食品中有机氯和拟除虫菊酯类农药多种残留的测定.
71.GB/T 19649-2005粮谷中405种农药多残留测定方法 气相色谱-质谱和液相色谱-串联质谱法.
72.GB/T5009.164-2003大米中丁草胺残留量的测定.
73.NY/T 761.2-2004蔬菜和水果中有机氯类、拟除虫菊酯类农药多残留检测方法.
74.GB/T5009.177-2003大米中敌稗残留量的测定.
75.Ana Aguera,Mariano Contreras,Juan Crespo,Amadeo R Fernandez-Alba.Multiresidue method for the analysis of multiclass pesticides in agricultural products by gas chromatography-tandem mass spectrometry.Analyst.2002 Mar;127(3):347-354