灵芝中17种农药的QuEChERS-气相色谱-质谱联用快速检测技术
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摘要
建立改进的QuEChERS提取和净化方法,结合气相色谱-质谱联用法测定灵芝中17种农药残留的检测方法。干燥的灵芝粉加水浸润后,经乙腈均质提取,正丙基乙二胺、MgSO4净化去杂,结合气相色谱-质谱检测系统,电子电离源,HP-5毛细管柱分离,程序升温,离子扫描模式检测。在优化条件下17种杀菌剂在一定质量浓度范围内线性关系良好,相关系数大于0.98,方法检出限(RSN=3)在0.002～0.022 mg/kg之间,定量限(RSN=10)在0.007～0.072 mg/kg之间,方法的平均回收率为71.10%～119.55%,相对标准偏差为0.47%～20.05%。本方法具有操作简单快捷、灵敏度高等优点。
In this study, a modified quick, easy, cheap, effective, rugged, and safe(QuEChERS) sample pretreatment method coupled with gas chromatography-mass spectrometry(GC-MS) was established to determine 17 pesticide residues in Ganoderma tsugae. A total of 1.0 g of dry G. tsugae powder was mixed with 10 mL of water, and then extracted by homogenization with aceonitrile. The extract was cleaned up with n-propyl ethylenediamine(PSA) and MgSO4 to remove the interferences from co-extractives. The separation was accomplished on an HP-5 capillary column and programmed heating was carried out. The target compounds were detected by electron impact ionization in the single ion monitoring(SIM) mode. Under the optimum conditions, the method showed a good linear relationship for all these pesticides in certain concentration ranges, with correlation coefficients greater than 0.98. Moreover, the limits of detection(LODs)(RSN = 3) were0.002–0.022 mg/kg, the limits of quantitation(LOQs)(RSN =10) were 0.007–0.072 mg/kg. The average recoveries of this method were in the range of 71.10%–119.55% with relative standard deviations(RSDs) between 0.47% and 20.05%. In comparison with previous methods, the new procedure has the characteristics of simple sample preparation and higher sensitivity.
In this study, a modified quick, easy, cheap, effective, rugged, and safe(QuEChERS) sample pretreatment method coupled with gas chromatography-mass spectrometry(GC-MS) was established to determine 17 pesticide residues in Ganoderma tsugae. A total of 1.0 g of dry G. tsugae powder was mixed with 10 mL of water, and then extracted by homogenization with aceonitrile. The extract was cleaned up with n-propyl ethylenediamine(PSA) and MgSO4 to remove the interferences from co-extractives. The separation was accomplished on an HP-5 capillary column and programmed heating was carried out. The target compounds were detected by electron impact ionization in the single ion monitoring(SIM) mode. Under the optimum conditions, the method showed a good linear relationship for all these pesticides in certain concentration ranges, with correlation coefficients greater than 0.98. Moreover, the limits of detection(LODs)(RSN = 3) were0.002–0.022 mg/kg, the limits of quantitation(LOQs)(RSN =10) were 0.007–0.072 mg/kg. The average recoveries of this method were in the range of 71.10%–119.55% with relative standard deviations(RSDs) between 0.47% and 20.05%. In comparison with previous methods, the new procedure has the characteristics of simple sample preparation and higher sensitivity.
引文
[1]吴兴亮,戴玉成,林龙河.中国灵芝科资源及其地理分布I[J].贵州科学,2004(2):27-33;4.
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[8]汪义平.灵芝病虫害种类调查[J].安徽农学通报,2009,15(1):136-137.DOI:10.16377/j.cnki.issn1007-7731.2009.01.035.
[9]李现合,杜适普,王亚光,等.袋栽灵芝常见的生理性病害及防治方法[J].食用菌,2011(5):58.
[10]解宜林.安徽灵芝病害调查与防治[J].中国食用菌,2013(6):45-47.DOI:10.13629/j.cnki.53-1054.2013.06.004.
[11]曹美桃.灵芝的无公害病虫害防治技术探讨[J].农家科技旬刊,2016(10):161.
[12]于延申.灵芝竞争性杂菌发生与综合防治措施[J].吉林蔬菜,2017(9):26.DOI:10.16627/j.cnki.cn22-1215/s.2017.09.015.
[13]罗佳.食用菌农药残留问题与解决办法[J].中国农学通报,2007(23):284-289.
[14]黎志银.食用菌重金属、农药的吸收规律与残留研究[D].福州:福建农林大学,2010:61.
[15]康文斌.食用菌栽培料农药残留情况调查及对子实体安全生产的影响研究[D].福州:福建农林大学,2011:25-53.
[16]杨慧,赵志辉,王瑞霞,等.食用菌中农药残留安全及风险预测[J].食用菌学报,2011,18(3):105-110.DOI:10.16488/j.cnki.1005-9873.2011.03.007.
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[20]邹永生,董娇,李洁实,等.新农药残留限量标准对食用菌标准的影响分析[J].中国食用菌,2013,32(2):53-54.DOI:10.13629/j.cnki.53-1054.2013.02.004.
[21]曲明清.三种食用菌中农药残留及富集研究[D].长春:吉林农业大学,2006:20.
[22]张晓柠.灵芝对四种重金属富集作用的研究[D].北京:中国协和医科大学,2007:69.
[23]康文斌,陈剑,林原,等.食用菌菌丝对农药富集能力的研究[J].食药用菌,2011(3):27-30.
[24]刘军虎,洪之国,胡承成.食用菌农药残留检测方法研究现状探讨[J].农产品质量与安全,2017(4):80-84.
[25]陆继伟,夏晶,苗水,等.GC测定灵芝中24种有机磷农药残留量[J].中国药学杂志,2007(3):227-231.
[26]王怀豫,郭晓蕾,朱龙平,等.不同产地灵芝中重金属和有机氯类农药残留含量比较[J].中药材,2011,34(11):1672-1674.DOI:10.13863/j.issn1001-4454.2011.11.006.
[27]刘志风,徐靖,李建淼,等.GC-MS与GC-MS/MS在灵芝农药残留分析中的应用[J].现代中药研究与实践,2015,29(5):20-23.DOI:10.13728/j.1673-6427.2015.05.007.
[28]The Standards Policy and Strategy Committee.Food of plant origindetermination of pesticide residues using GC-MS and/or LC-MS/MS following acetonitrile extraction/partitioning and clean-up by dispersive SPE-QuEChERS-method.British standard:EN 15662-2008[S].British:The Standards Policy and Strategy Committee,2008.
[29]Association of Official Analytical Chemists.Pesticide residues in foods by acetonitrile extraction and partitioning with magnesium sulfate:AOAC official method 2007.01[S].2007.
[30]张雪莲,张耀海,焦必宁.气相色谱-串联质谱法结合Qu ECh ERS方法快速检测柑橘中52种农药多残留[J].食品科学,2013,34(6):152-155.
[31]钟志铭,黄子敬,符靖雯.QuEChERS结合PTV-GC-MS/MS测定食用菌中多种农药残留[J].分析试验室,2016(6):648-653.DOI:10.13595/j.cnki.issn1000-0720.2016.0151.
[32]谢景丽,李凌云,刘新艳,等.改进的QuEChERS-液相色谱串联质谱法快速测定中草药中147种农药残留[J].农产品质量与安全,2016(2):65-69.
[33]ANASTASSIADES M,LEHOTAY S J,STAJNBAHER D,et al.Fast easy multiresidue method employing acetonitrile extraction/partitioning,“dispersive solid-phase extraction”for the determination of pesticide residues in produce[J].Journal of AOAC International,2003,86(2):412-431.
[34]付文雯,罗彤,朱影,等.QuEChERS-气相色谱-串联质谱测定牛奶中有机氯农药及多氯联苯的分析[J].食品科学,2018,39(8):309-313.DOI:10.7506/spkx1002-6630-201808048.
[35]刘远晓,关二旗,卞科,等.QuEChERS法在食品有机污染物检测中的研究进展[J].食品科学,2017,38(19):294-300.DOI:10.16488/j.cnki.1005-9873.2011.03.011.
[36]周帅,张劲松,刘艳芳,等.不同粉碎程度对灵芝多糖与三萜提取得率的影响[J].食用菌学报,2011,18(3):67-70.
[37]黄晓会,薛健.人参、黄芪、白菊中农药残留提取方法比较研究[J].中华中医药杂志,2013,28(7):2126-2128.
[38]侯彩霞,全灿,樊丽华,等.毛细管气相色谱法测定人参须中有机氯农药残留[J].化学试剂,2010,32(11):997-999.DOI:10.13822/j.cnki.hxsj.2010.11.009.
[2]国家药典委员会.中华人民共和国药典[M].北京:中国医药科技出版社,2015:174-175.
[3]周州,余梦瑶,江南,等.我国灵芝栽培研究近况及其未来发展趋势探讨[J].中国食用菌,2017,36(4):5-7.
[4]万鲁长,曹德强,解思泌,等.灵芝常见病虫害及其防治研究[J].食用菌,1994(增刊1):37-38.
[5]蒋时察,周仲刚,殷志龙.灵芝病虫害调查及其主要病虫害防治[J].食药用菌,1996(1):34-35.
[6]孙平.灵芝病虫害的发生与防治技术[J].植物医生,2001,14(5):21.
[7]陈文杰,张瑞青,张晓芳.灵芝的无公害病虫害防治技术探讨[J].食用菌,2007,29(6):59-61.
[8]汪义平.灵芝病虫害种类调查[J].安徽农学通报,2009,15(1):136-137.DOI:10.16377/j.cnki.issn1007-7731.2009.01.035.
[9]李现合,杜适普,王亚光,等.袋栽灵芝常见的生理性病害及防治方法[J].食用菌,2011(5):58.
[10]解宜林.安徽灵芝病害调查与防治[J].中国食用菌,2013(6):45-47.DOI:10.13629/j.cnki.53-1054.2013.06.004.
[11]曹美桃.灵芝的无公害病虫害防治技术探讨[J].农家科技旬刊,2016(10):161.
[12]于延申.灵芝竞争性杂菌发生与综合防治措施[J].吉林蔬菜,2017(9):26.DOI:10.16627/j.cnki.cn22-1215/s.2017.09.015.
[13]罗佳.食用菌农药残留问题与解决办法[J].中国农学通报,2007(23):284-289.
[14]黎志银.食用菌重金属、农药的吸收规律与残留研究[D].福州:福建农林大学,2010:61.
[15]康文斌.食用菌栽培料农药残留情况调查及对子实体安全生产的影响研究[D].福州:福建农林大学,2011:25-53.
[16]杨慧,赵志辉,王瑞霞,等.食用菌中农药残留安全及风险预测[J].食用菌学报,2011,18(3):105-110.DOI:10.16488/j.cnki.1005-9873.2011.03.007.
[17]管道平,胡清秀.食用菌药残留限量与产品质量安全[J].中国食用菌,2008,27(2):3-6.
[18]国家食品药品监督管理总局.食品中农药最大残留限量:GB 2763-2016[S].北京:中国标准出版社,2016:10-225.
[19]董娇,邰丽梅.国内外食用菌农药残留限量标准比较分析[J].中国食用菌,2017,36(5):1-5.DOI:10.13629/j.cnki.53-1054.2017.05.001.
[20]邹永生,董娇,李洁实,等.新农药残留限量标准对食用菌标准的影响分析[J].中国食用菌,2013,32(2):53-54.DOI:10.13629/j.cnki.53-1054.2013.02.004.
[21]曲明清.三种食用菌中农药残留及富集研究[D].长春:吉林农业大学,2006:20.
[22]张晓柠.灵芝对四种重金属富集作用的研究[D].北京:中国协和医科大学,2007:69.
[23]康文斌,陈剑,林原,等.食用菌菌丝对农药富集能力的研究[J].食药用菌,2011(3):27-30.
[24]刘军虎,洪之国,胡承成.食用菌农药残留检测方法研究现状探讨[J].农产品质量与安全,2017(4):80-84.
[25]陆继伟,夏晶,苗水,等.GC测定灵芝中24种有机磷农药残留量[J].中国药学杂志,2007(3):227-231.
[26]王怀豫,郭晓蕾,朱龙平,等.不同产地灵芝中重金属和有机氯类农药残留含量比较[J].中药材,2011,34(11):1672-1674.DOI:10.13863/j.issn1001-4454.2011.11.006.
[27]刘志风,徐靖,李建淼,等.GC-MS与GC-MS/MS在灵芝农药残留分析中的应用[J].现代中药研究与实践,2015,29(5):20-23.DOI:10.13728/j.1673-6427.2015.05.007.
[28]The Standards Policy and Strategy Committee.Food of plant origindetermination of pesticide residues using GC-MS and/or LC-MS/MS following acetonitrile extraction/partitioning and clean-up by dispersive SPE-QuEChERS-method.British standard:EN 15662-2008[S].British:The Standards Policy and Strategy Committee,2008.
[29]Association of Official Analytical Chemists.Pesticide residues in foods by acetonitrile extraction and partitioning with magnesium sulfate:AOAC official method 2007.01[S].2007.
[30]张雪莲,张耀海,焦必宁.气相色谱-串联质谱法结合Qu ECh ERS方法快速检测柑橘中52种农药多残留[J].食品科学,2013,34(6):152-155.
[31]钟志铭,黄子敬,符靖雯.QuEChERS结合PTV-GC-MS/MS测定食用菌中多种农药残留[J].分析试验室,2016(6):648-653.DOI:10.13595/j.cnki.issn1000-0720.2016.0151.
[32]谢景丽,李凌云,刘新艳,等.改进的QuEChERS-液相色谱串联质谱法快速测定中草药中147种农药残留[J].农产品质量与安全,2016(2):65-69.
[33]ANASTASSIADES M,LEHOTAY S J,STAJNBAHER D,et al.Fast easy multiresidue method employing acetonitrile extraction/partitioning,“dispersive solid-phase extraction”for the determination of pesticide residues in produce[J].Journal of AOAC International,2003,86(2):412-431.
[34]付文雯,罗彤,朱影,等.QuEChERS-气相色谱-串联质谱测定牛奶中有机氯农药及多氯联苯的分析[J].食品科学,2018,39(8):309-313.DOI:10.7506/spkx1002-6630-201808048.
[35]刘远晓,关二旗,卞科,等.QuEChERS法在食品有机污染物检测中的研究进展[J].食品科学,2017,38(19):294-300.DOI:10.16488/j.cnki.1005-9873.2011.03.011.
[36]周帅,张劲松,刘艳芳,等.不同粉碎程度对灵芝多糖与三萜提取得率的影响[J].食用菌学报,2011,18(3):67-70.
[37]黄晓会,薛健.人参、黄芪、白菊中农药残留提取方法比较研究[J].中华中医药杂志,2013,28(7):2126-2128.
[38]侯彩霞,全灿,樊丽华,等.毛细管气相色谱法测定人参须中有机氯农药残留[J].化学试剂,2010,32(11):997-999.DOI:10.13822/j.cnki.hxsj.2010.11.009.