吉林省食用菌中二硫代氨基甲酸酯类农药残留监测及结果分析
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摘要
目的建立气相色谱-质谱法测定菌类中二硫代氨基甲酸酯类农药的含量,了解吉林省内几种菌类食品中二硫代氨基甲酸酯的残留情况。方法样品在加热密闭的顶空瓶中进行前处理,进入气相色谱-质谱仪进行检测,以CS_2为检测目标物,程序升温,选择性离子监测,外标法定量。结果食用菌类中二硫代氨基甲酸酯类农药检出限为0.005 mg/kg,定量限为0.015 mg/kg,在0.02～0.5 mg/L范围内线性关系良好(r>0.9990)。部分菌类食品中存在二硫代氨基甲酸酯的残留检出率为25.2%,检出浓度为0.011～0.098mg/kg,其中香菇的检出率最高为57.89%。结论吉林省内菌类食品中含有一定量的二硫代氨基甲酸酯的残留,均低于GB2763-2016中规定的最大残留量1mg/kg,但是检出率较高,需要加强日常监管。
Objective To establish a method for determination of dithiocarbamate pesticides in fungi by gas chromatography-mass spectrometry, and investigate the residue of dithiocarbamate in several fungus foods in Jilin province. Methods The sample was pretreated in a heated closed headspace bottle and passed into a gas chromatography-mass spectrometer for detection. CS_2 was used as the detection target, programmed heating, selective ion monitoring, and quantitative determination by external standard method were used. Results The limit of detection of dithiocarbamate pesticides in edible fungi was 0.005 mg/kg, the limit of quantitation was 0.015 mg/kg, and linear relationship was good in the range of 0.02-0.5 mg/L(r>0.9990). The residual detection rate of dithiocarbamate in some fungus foods was 25.2%, and the detected concentrations were 0.011-0.098 mg/kg. The highest detection rate of shiitake mushrooms was 57.89%. Conclusion There is a certain amount of residual dithiocarbamate in the fungus food in Jilin province, which is lower than the maxi mum residual amount of 1 mg/kg stipulated in GB 2763-2016, but the detection rate is relatively high, and it is necessary to strengthen daily supervision.
Objective To establish a method for determination of dithiocarbamate pesticides in fungi by gas chromatography-mass spectrometry, and investigate the residue of dithiocarbamate in several fungus foods in Jilin province. Methods The sample was pretreated in a heated closed headspace bottle and passed into a gas chromatography-mass spectrometer for detection. CS_2 was used as the detection target, programmed heating, selective ion monitoring, and quantitative determination by external standard method were used. Results The limit of detection of dithiocarbamate pesticides in edible fungi was 0.005 mg/kg, the limit of quantitation was 0.015 mg/kg, and linear relationship was good in the range of 0.02-0.5 mg/L(r>0.9990). The residual detection rate of dithiocarbamate in some fungus foods was 25.2%, and the detected concentrations were 0.011-0.098 mg/kg. The highest detection rate of shiitake mushrooms was 57.89%. Conclusion There is a certain amount of residual dithiocarbamate in the fungus food in Jilin province, which is lower than the maxi mum residual amount of 1 mg/kg stipulated in GB 2763-2016, but the detection rate is relatively high, and it is necessary to strengthen daily supervision.
引文
[1]秦曙,乔雄梧,王霞,等.气相色谱法检测22种基质中的4种二硫代氨基甲酸盐类农药残留[J].色谱,2010,28(12):1162-1167.Qin W,Qiao X,Wang X,et al.Determination of four dithiocarbamate pesticide residues in 22 substrates by gas chromatography[J].Chin JChromatogr,2010,28(12):1162-1167.
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[3]张秋萍,王春民,马晓艳.气相色谱法测定水果中二硫代氨基甲酸盐(酯)类农药残留[J].中国卫生检验杂志,2016,(24):3524-3526.Zhang QP,Wang CM,Ma XY.Determination of dithiocarbamate(pesticide)residues in fruits by gas chromatography[J].Chin J Health Lab Technol,2016,26(24):3524-3526.
[4]李伟华,胡小宁,吕雪霞,等.比色法快速测定小麦中福美双的残留量[J].农药,2011,50(3):213-214.Li WH,Hu XN,Lu XX,et al.Rapid determination of thiram residues in wheat by colorimetry[J].Pesticide,2011,50(3):213-214.
[5]鲁晋南,王丽,张国平,等.溶剂萃取-气相色谱法测定水果中二硫代氨基甲酸盐类农药残留方法研究[J].中国卫生检验杂志,2016,(19):2770-2772.Lu JN,Wang L,Zhang GP,et al.Determination of dithiocarbamate pesticide residues in fruits by solvent extraction-gas chromatography[J].Chin J Health Lab Technol,2016,(19):2770-2772.
[6]孔祥吉,马山山,单正军,等.二硫代氨基甲酸盐类(EBDCs)杀菌剂残留检测及降解动态综述[J].农药科学与管理,2013,34(12):23-30.Kong XJ,Ma SS,Shan ZJ,et al.Review on the detection and degradation of bismuth carbamide residues(EBDCs)[J].Pesticide Sci Manag,2013,34(12):23-30.
[7]胡秀卿,李振,吴珉,等.紫外分光光度法检测黄瓜中丙森锌的残留[J].农药,2005,44(11):519-520.Hu XQ,Li Z,Wu M,et al.Determination of propylene zinc in cucumber by UV spectrophotometry[J].Pesticide,2005,44(11):519-520.
[8]庞作正,薛健,孙晖,等.中药材中二硫代氨基甲酸盐类农残测定方法研究[J].时珍国医国药,2011,22(9):2283-2285.Pang ZZ,Xue J,Sun H,et al.Determination of dithiocarbamate pesticides in chinese medicinal materials[J].Lishizhen Med Mater Med Res,2011,22(9):2283-2285.
[9]马婧玮,潘灿平,张玲,等.二硫代氨基甲酸盐类(DTCs)杀菌剂残留分析方法综述[J].农药学学报,2010,12(1):22-30.Ma JW,Pan CP,Zhang L,et al.Summary of analytical methods for residues of dithiocarbamates(DTCs)[J].J Chin Pet Sci,2010,12(1):22-30.
[10]马恒麟,纪然,张永刚.西瓜、瓜叶及土壤中代森锰锌残留气相色谱分析方法的研究[J].农药学学报,2000,2(2):63-70.Ma HL,Ji R,Zhang YG.Gas chromatographic analysis of mancozeb residues in watermelon,melon leaves and soil[J].J Chin Pest Sci,2000,2(2):63-70.
[11]胡秀卿,李振,吴珉,等.番茄中丙森锌残留分析方法研究[J].浙江农业学报,2004,16(5):282.Hu XQ,Li Z,Wu M,et al.Study on the analysis method of zinc Zn residue in tomato[J].Acta Agric Zhejiangensis,2004,16(5):282.
[12]石利利,单正军,金怡,等.荔枝中代森锰锌及其代谢产物乙撑硫脲残留量的气相色谱测定[J].分析测试学报,2005,24(2):92-94.Shi LL,Shan ZJ,Jin Y,et al.Determination of mancozeb and its metabolite ethylene thiourea residues in Litchi by gas chromatography[J].J Instrum Anal,2005,24(2):92-94.
[13]王远,王宏庆,王结成,等.代森锰锌废水中乙撑硫脲的高效液相色谱分析[J].农药,2007,46(2):116-117.Wang Y,Wang HQ,Wang JC,et al.High performance liquid chromatography analysis of ethylene thiourea in mancozeb wastewater[J].Pesticide,2007,46(2):116-117.
[14]王娟,尚立成,仇文轩,等.水果中二硫代氨基甲酸酯类农药残留情况调查[J].疾病预防控制通报,2017,32(4):77-79.Wang J,Shang LC,Qiu WX,et al.Investigation on the residues of dithiocarbamate pesticides in fruits[J].Bull Dis Control Prev,2017,32(4):77-79.
[15]O.LópezFernández,Rialotero R,C.GonzálezBarreiro,et al.Surveillance of fungicidal dithiocarbamate residues in fruits and vegetables[J].Food Chem,2012,134(1):366-374.
[16]Abakerlia RB,Sparrapana R,Sawayaa ACHF,et al.Carbon disulfide formation in papaya under conditionsof dithiocarbamate residue analysis[J].Food Chem,2015,188:71-76.
[17]GB 2763-2016食品安全国家标准食品中农药最大残留限量[S].GB 2763-2016 National food safety standards-Maximum residue limits for pesticides in food[S].
[18]GB/T 21132-2007烟草及烟草制品二硫代氨基甲酸酯农药残留量的测定分子吸收光度法[S].GB/T 21132-2007 Determination of residues of dithiocarbamate pesticides in tobacco and tobacco products-Atomic absorption spectrophotometric method[S].
[19]SN 0139-1992出口粮谷中二硫代氨基甲酸酯残留量检验方法[S].SN 0139-1992 Method for the determination of dithiocarbamate residues in exported grains[S].
[20]SN 0157-1992出口水果中二硫代氨基甲酸酯残留量检验方法[S].SN 0157-1992 Method for the determination of dithiocarbamate residues in exported fruits[S].
[21]SN/T 1541-2005出口茶叶中二硫代氨基甲酸酯总残留量检验方法[S].SN/T 1541-2005 Test method for total residual amount of dithiocarbamate in tea leaves[S].
[22]刘阳,宋宁慧,刘济宁,等.气相色谱测定不同基质中二硫代氨基甲酸酯类农药残留[J].农药,2016,55(7):510-513.Liu Y,Song NH,Liu JN,et al.Determination of dithiocarbamate pesticide residues in different matrices by gas chromatography[J].Pesticide,2016,55(7):510-513.
[23]邵辉,刘磊,李辉,等.溶剂吸收-气质联用法测定蔬菜和粮谷中代森铵残留[J].食品安全质量检测学报,2017,8(8):2966-2972.Shao H,Liu L,Li H,et al.Solvent absorption-gas chromatography-mass spectrometry for the determination of dexamenium residues in vegetables and grains[J].J Food Saf Qual,2017,8(8):2966-2972.
[24]GB/T 27404-2008.实验室质量控制规范食品理化检测[S].GB/T 27404-2008 Laboratory quality control specification-Food physical and chemical detection[S].
[25]Mujawar S,Utture SC,Fonseca E,et al.Validation of a GC-MS method for the estimation of dithiocarbamate fungicide residues and safety evaluation of mancozeb in fruits and vegetables[J].Food Chem,2014,150(5):175-181.
[26]张秋萍,王春民,马晓艳.气相色谱法测定水果中二硫代氨基甲酸盐(酯)类农药残留[J].中国卫生检验杂志,2016,26(24):3524-3526.Zhang QP,Wang CM,Ma XY.Determination of dithiocarbamate(ester)pesticide residues in fruits by gas chromatography[J].Chin J Health Lab Technol,2016,26(24):3524-3526.
[27]张平,郑志安,赵祖松颖,等.我国食用菌生产布局变迁及影响因素分析[J].北方园艺,2017,(22):167-174.Zhang P,Zheng ZA,Zhao ZSY,et al.Analysis of the changes in the production layout of edible fungi in China and the influencing factors[J].Northern Hortic,2017,(22):167-174.
[28]朱鲁生,王明林,胡庆永,等.代森环在黄瓜、大白菜及土壤中的残留分析[J].农药,1993,(4):30-31.Zhu LS,Wang ML,Hu QY,et al.Residue analysis of Daisen ring in cucumber,Chinese cabbage and soil[J].Pesticide,1993,(4):30-31.
[29]石利利,单正军,金怡,等.荔枝中代森锰锌及其代谢产物乙撑硫脲残留量的气相色谱测定[J].分析测试学报,2005,(2):92-94,97.Shi L,Shan ZJ,Jin Y,et al.Determination of residues of manganese zinc and its metabolite ethylene thiourea in litchi by gas chromatography[J].J.Instrum Anal,2005,(2):92-94,97.
[2]Wysocki K,Banaszkiewicz T.The effect of selected fungicides on the chemical composition of strawberry fruits and contamination with dithiocarbamate residues[J].Folia Hortic,2014,26(2):125-132.
[3]张秋萍,王春民,马晓艳.气相色谱法测定水果中二硫代氨基甲酸盐(酯)类农药残留[J].中国卫生检验杂志,2016,(24):3524-3526.Zhang QP,Wang CM,Ma XY.Determination of dithiocarbamate(pesticide)residues in fruits by gas chromatography[J].Chin J Health Lab Technol,2016,26(24):3524-3526.
[4]李伟华,胡小宁,吕雪霞,等.比色法快速测定小麦中福美双的残留量[J].农药,2011,50(3):213-214.Li WH,Hu XN,Lu XX,et al.Rapid determination of thiram residues in wheat by colorimetry[J].Pesticide,2011,50(3):213-214.
[5]鲁晋南,王丽,张国平,等.溶剂萃取-气相色谱法测定水果中二硫代氨基甲酸盐类农药残留方法研究[J].中国卫生检验杂志,2016,(19):2770-2772.Lu JN,Wang L,Zhang GP,et al.Determination of dithiocarbamate pesticide residues in fruits by solvent extraction-gas chromatography[J].Chin J Health Lab Technol,2016,(19):2770-2772.
[6]孔祥吉,马山山,单正军,等.二硫代氨基甲酸盐类(EBDCs)杀菌剂残留检测及降解动态综述[J].农药科学与管理,2013,34(12):23-30.Kong XJ,Ma SS,Shan ZJ,et al.Review on the detection and degradation of bismuth carbamide residues(EBDCs)[J].Pesticide Sci Manag,2013,34(12):23-30.
[7]胡秀卿,李振,吴珉,等.紫外分光光度法检测黄瓜中丙森锌的残留[J].农药,2005,44(11):519-520.Hu XQ,Li Z,Wu M,et al.Determination of propylene zinc in cucumber by UV spectrophotometry[J].Pesticide,2005,44(11):519-520.
[8]庞作正,薛健,孙晖,等.中药材中二硫代氨基甲酸盐类农残测定方法研究[J].时珍国医国药,2011,22(9):2283-2285.Pang ZZ,Xue J,Sun H,et al.Determination of dithiocarbamate pesticides in chinese medicinal materials[J].Lishizhen Med Mater Med Res,2011,22(9):2283-2285.
[9]马婧玮,潘灿平,张玲,等.二硫代氨基甲酸盐类(DTCs)杀菌剂残留分析方法综述[J].农药学学报,2010,12(1):22-30.Ma JW,Pan CP,Zhang L,et al.Summary of analytical methods for residues of dithiocarbamates(DTCs)[J].J Chin Pet Sci,2010,12(1):22-30.
[10]马恒麟,纪然,张永刚.西瓜、瓜叶及土壤中代森锰锌残留气相色谱分析方法的研究[J].农药学学报,2000,2(2):63-70.Ma HL,Ji R,Zhang YG.Gas chromatographic analysis of mancozeb residues in watermelon,melon leaves and soil[J].J Chin Pest Sci,2000,2(2):63-70.
[11]胡秀卿,李振,吴珉,等.番茄中丙森锌残留分析方法研究[J].浙江农业学报,2004,16(5):282.Hu XQ,Li Z,Wu M,et al.Study on the analysis method of zinc Zn residue in tomato[J].Acta Agric Zhejiangensis,2004,16(5):282.
[12]石利利,单正军,金怡,等.荔枝中代森锰锌及其代谢产物乙撑硫脲残留量的气相色谱测定[J].分析测试学报,2005,24(2):92-94.Shi LL,Shan ZJ,Jin Y,et al.Determination of mancozeb and its metabolite ethylene thiourea residues in Litchi by gas chromatography[J].J Instrum Anal,2005,24(2):92-94.
[13]王远,王宏庆,王结成,等.代森锰锌废水中乙撑硫脲的高效液相色谱分析[J].农药,2007,46(2):116-117.Wang Y,Wang HQ,Wang JC,et al.High performance liquid chromatography analysis of ethylene thiourea in mancozeb wastewater[J].Pesticide,2007,46(2):116-117.
[14]王娟,尚立成,仇文轩,等.水果中二硫代氨基甲酸酯类农药残留情况调查[J].疾病预防控制通报,2017,32(4):77-79.Wang J,Shang LC,Qiu WX,et al.Investigation on the residues of dithiocarbamate pesticides in fruits[J].Bull Dis Control Prev,2017,32(4):77-79.
[15]O.LópezFernández,Rialotero R,C.GonzálezBarreiro,et al.Surveillance of fungicidal dithiocarbamate residues in fruits and vegetables[J].Food Chem,2012,134(1):366-374.
[16]Abakerlia RB,Sparrapana R,Sawayaa ACHF,et al.Carbon disulfide formation in papaya under conditionsof dithiocarbamate residue analysis[J].Food Chem,2015,188:71-76.
[17]GB 2763-2016食品安全国家标准食品中农药最大残留限量[S].GB 2763-2016 National food safety standards-Maximum residue limits for pesticides in food[S].
[18]GB/T 21132-2007烟草及烟草制品二硫代氨基甲酸酯农药残留量的测定分子吸收光度法[S].GB/T 21132-2007 Determination of residues of dithiocarbamate pesticides in tobacco and tobacco products-Atomic absorption spectrophotometric method[S].
[19]SN 0139-1992出口粮谷中二硫代氨基甲酸酯残留量检验方法[S].SN 0139-1992 Method for the determination of dithiocarbamate residues in exported grains[S].
[20]SN 0157-1992出口水果中二硫代氨基甲酸酯残留量检验方法[S].SN 0157-1992 Method for the determination of dithiocarbamate residues in exported fruits[S].
[21]SN/T 1541-2005出口茶叶中二硫代氨基甲酸酯总残留量检验方法[S].SN/T 1541-2005 Test method for total residual amount of dithiocarbamate in tea leaves[S].
[22]刘阳,宋宁慧,刘济宁,等.气相色谱测定不同基质中二硫代氨基甲酸酯类农药残留[J].农药,2016,55(7):510-513.Liu Y,Song NH,Liu JN,et al.Determination of dithiocarbamate pesticide residues in different matrices by gas chromatography[J].Pesticide,2016,55(7):510-513.
[23]邵辉,刘磊,李辉,等.溶剂吸收-气质联用法测定蔬菜和粮谷中代森铵残留[J].食品安全质量检测学报,2017,8(8):2966-2972.Shao H,Liu L,Li H,et al.Solvent absorption-gas chromatography-mass spectrometry for the determination of dexamenium residues in vegetables and grains[J].J Food Saf Qual,2017,8(8):2966-2972.
[24]GB/T 27404-2008.实验室质量控制规范食品理化检测[S].GB/T 27404-2008 Laboratory quality control specification-Food physical and chemical detection[S].
[25]Mujawar S,Utture SC,Fonseca E,et al.Validation of a GC-MS method for the estimation of dithiocarbamate fungicide residues and safety evaluation of mancozeb in fruits and vegetables[J].Food Chem,2014,150(5):175-181.
[26]张秋萍,王春民,马晓艳.气相色谱法测定水果中二硫代氨基甲酸盐(酯)类农药残留[J].中国卫生检验杂志,2016,26(24):3524-3526.Zhang QP,Wang CM,Ma XY.Determination of dithiocarbamate(ester)pesticide residues in fruits by gas chromatography[J].Chin J Health Lab Technol,2016,26(24):3524-3526.
[27]张平,郑志安,赵祖松颖,等.我国食用菌生产布局变迁及影响因素分析[J].北方园艺,2017,(22):167-174.Zhang P,Zheng ZA,Zhao ZSY,et al.Analysis of the changes in the production layout of edible fungi in China and the influencing factors[J].Northern Hortic,2017,(22):167-174.
[28]朱鲁生,王明林,胡庆永,等.代森环在黄瓜、大白菜及土壤中的残留分析[J].农药,1993,(4):30-31.Zhu LS,Wang ML,Hu QY,et al.Residue analysis of Daisen ring in cucumber,Chinese cabbage and soil[J].Pesticide,1993,(4):30-31.
[29]石利利,单正军,金怡,等.荔枝中代森锰锌及其代谢产物乙撑硫脲残留量的气相色谱测定[J].分析测试学报,2005,(2):92-94,97.Shi L,Shan ZJ,Jin Y,et al.Determination of residues of manganese zinc and its metabolite ethylene thiourea in litchi by gas chromatography[J].J.Instrum Anal,2005,(2):92-94,97.