进出口根茎类中药材中多种有机氯拟除虫菊酯类农药残留量的测定征求意见稿

1、中华人民共和国国家质量监督检验检疫总局 发布200-实施200-发布进出口根茎类中药材中多种有机氯、拟除虫菊酯类农药残留量的测定determination of organochlorine and pyrethroid pesticides multiresidues in rhizome of traditional chinese medicine for import and export（征求意见稿）sn/t sn中华人民共和国出入境检验检疫行业标准ics备案号： 慢慢前 言本标准的附录a、附录b和附录c均为资料性附录。本标准按照gb/t 1.1-2009标准化工作导则 第1部分:标

2、准的结构和编写、gb/t 20001.4-2001标准编写规则 第4部分：化学分析方法和sn/t 0001-1995出口商品中农药、兽药残留量及生物毒素检验方法标准编写的基本规定的要求起草的。本标准采用气相色谱检测方法。检测时应根据检测对象及其限量的规定，选用与其相适应的检测方法。本标准由国家认证认可监督管理委员会提出并归口。本标准起草单位：中华人民共和国重庆出入境检验检疫局。本标准主要起草人：本标准为首次发布的出入境检验检疫行业标准。进出口根茎类中药材中多种有机氯、拟除虫菊酯类农药残留量的测定1范围本标准规定了根茎类中药材中六氯苯、-六六六、五氯硝基苯、-六六六、七氯、五氯苯胺、艾氏剂、-六

3、六六、-六六六、环氧七氯、三唑酮、-硫丹、p,p-滴滴伊、狄氏剂、异狄氏剂、op -滴滴涕、-硫丹、p,p-滴滴滴、p,p-滴滴涕、异狄氏剂醛、联苯菊酯、甲氰菊酯、胺菊酯、氯菊酯、氯氰菊酯、氰戊菊酯、溴氰菊酯农药残留量的气相色谱检测方法。本标准适用于人参、半夏、山药、葛根、柴胡、党参等根茎类中药材中27种有机氯、拟除虫菊酯类农药残留量的测定。2规范性引用文件下列文件对于本文件的应用是必不可少的。凡是注日期的引用文件，仅所注日期的版本适用于本文件。凡是不注日期的引用文件，其最新版本（包括所有的修改单）适用于本文件。gb/t 6682 分析实验室用水规格和试验方法3方法提要试样用丙酮-正己烷（4:

4、3,v/v）提取，凝胶渗透色谱和弗罗里硅土固相萃取柱净化，毛细管气相色谱柱分离后，微电子捕获（-ecd）检测器检测，外标法定量。4试剂和材料除另有规定外，所用试剂均为分析纯，水为符合gb/t 6682规定的一级水。4.1丙酮：色谱纯。4.2乙腈：色谱纯。4.3二氯甲烷：色谱纯。4.4正己烷：色谱纯。4.5乙酸乙酯：色谱纯。4.6环己烷：色谱纯。4.7氯化钠。4.8无水硫酸钠。4.9标准物质：六氯苯、-六六六、五氯硝基苯、-六六六、七氯、五氯苯胺、艾氏剂、-六六六、-六六六、环氧七氯、三唑酮、-硫丹、p,p-滴滴伊、狄氏剂、异狄氏剂、op-滴滴涕、-硫丹、p,p-滴滴滴、p,p-滴滴涕、异狄氏剂

5、醛、联苯菊酯、甲氰菊酯、胺菊酯、氯菊酯、氯氰菊酯、氰戊菊酯、溴氰菊酯（纯度99.0%，均来自国家标准物质中心，27种有机氯、拟除虫菊酯类农药的化学分子式等信息见附录a）。4.10各种农药标准储备溶液：分别准确称取适量的农药标准品，用正己烷配制100 mg/l的单标储备液，于4 冰箱中保存。 4.11 混合标准工作溶液：分别准确移取适量的上述单种标准储备溶液，用正己烷稀释配制成2 mg/l的混合标准储备溶液，根据检测需要用正己烷稀释成相应浓度的混合标准工作溶液，于4 冰箱中保存。4.12 弗罗里硅土固相萃取柱：1 g，6 ml，使用前用5ml正己烷活化。4.13 滤膜：0.22m ，有机系。5仪

6、器和设备5.1气相色谱仪，配-ecd检测器。5.2凝胶渗透色谱仪。5.3分析天平：感量为0.0001 g和0.01 g。5.4组织捣碎机。5.5旋涡混合器。5.6具塞塑料离心管：50 ml。5.7振荡器。5.8超声水浴仪。5.9冷冻离心机。5.10旋转蒸发仪。6试样的制备与保存6.1试样的制备取代表性样品500 g，将表皮尘土除净后于60干燥4h，用捣碎机将样品粉碎后过0.45 mm 粒径筛，装入容器内，密闭并标明标记。6.2试样的保存人参、半夏、山药、葛根、柴胡、党参等根茎类中药材试样于室温下保存。7 样品处理7.1提取准确称取5.0 g 均匀试样（精确到0.01 g）于50 ml离心管中，

7、加入少量水润湿、5g氯化钠和3g无水硫酸钠，再加入20ml丙酮-正己烷（4:3,v/v）溶液，于旋涡混合器上混匀，振荡器上震荡5min后，超声提取10 min，于6500 r/min 离心5 min，将上清液转入旋蒸瓶中，再用20ml丙酮-正己烷（4:3,v/v）提取两次，合并提取液于旋蒸瓶中，将其旋转蒸发至近干（t40），加10ml乙酸乙酯-环己烷（1:1，v/v）溶解残渣，溶液待净化。7.2山药、葛根的净化方法7.2.1凝胶渗透色谱（gpc）净化1）凝胶渗透色谱条件a) 净化柱：400 mm25 mm，内装bio-beads，s-x3，38 m75 m填料,或相当者；b) 流动相：环己烷：

8、乙酸乙酯（1:1, v/v）；c) 流速：5 ml/min；d) 进样体积：5 ml。2) 凝胶渗透色谱净化步骤山药、葛根的提取液旋蒸近干后经10ml乙酸乙酯-环己烷（1:1，v/v）溶解、滤膜过滤后，转移至凝胶渗透色谱上净化，收集8-15 min流出液，旋蒸至近干，用1ml正己烷溶解定容，经0.22m滤膜过滤后，供气相色谱分析。7.3 柴胡、半夏、人参、党参的净化方法7.3.1 凝胶渗透色谱净化1)凝胶渗透色谱条件（同7.2.1）2)凝胶渗透色谱净化步骤柴胡、半夏、人参、党参的提取液旋蒸近干后经10ml乙酸乙酯-环己烷（1:1，v/v）溶解、滤膜过滤后，转移至凝胶渗透色谱上净化，收集8-15

9、 min流出液，旋蒸至近干待进一步净化。7.3.2 固相萃取 (spe) 净化步骤用2ml正己烷溶解残渣后待弗罗里硅土固相萃取柱进一步净化。用5ml正己烷活化弗罗里硅土柱，把待净化液加到已活化好的固相萃取柱上，使其逐滴流下，用8 ml正己烷:二氯甲烷(2:8，v/v)洗脱液少量多次洗涤旋蒸瓶后加到柱头上，用10 ml刻度离心试管收集，40水浴氮吹浓缩至近干，用1ml正己烷溶解定容，经0.22m滤膜过滤后，供气相色谱分析。8测定8.1 气相色谱条件a) 色谱柱：db-1701毛细管柱 (30 m 0.25 mm0. 25m) ；b) 载气：氮气，纯度 99. 999%；c) 柱温: 90保持1

10、min，以40/min升至150，保持5 min，再以2/min升至210 ，最后以10/min升至280，保持20 min；d) 柱流速：1.0 ml/min，恒流；e) 进样口温度：250 ；f) 检测器：微电子捕获检测器；g) 检测器温度：300 ；h) 进样量：1l。8.2 气相色谱测定按照8.1气相色谱测定条件对标准工作溶液及样液等体积进样测定。样品中待测物含量应在标准曲线范围之内，如果含量超出标准曲线范围，应进行适当稀释后测定。在7.1气相色谱条件下，27种有机氯、拟除虫菊酯类农药标准溶液的色谱图参见附录b。8.3 空白试验除不加试样外，均按上述操作步骤进行。9结果计算试样中各有机

11、氯、拟除虫菊酯类农药的含量利用数据处理系统计算或按式（1）计算：式中：xi试样中各农药含量，单位为毫克每千克（mg/kg）；ci从标准工作曲线中查得的各农药的浓度，单位为毫克每升（mg/l）；v样液最终定容体积，单位为毫升（ml）；m最终样液所代表的试样量，单位为克（g）。注：计算结果应扣除空白值。10测定低限和回收率10.1 测定低限气相色谱法的测定低限：有机氯农药：0.01mg/kg ，拟除虫菊酯类农药：0.01mg/kg。10.2 回收率不同基质中添加浓度水平下的回收率范围参见附录c。附录a（资料性附录）27种农药的化学分子式等信息表1 27种有机氯及拟除虫菊酯类农药的中英文名、cas号

12、、分子量序号农药名称英文名称cas.no.化学分子式相对分子量1六氯苯hexachlorobenzene118-74-1c6cl6284.782-六六六-hcb319-84-6c6h6cl6290.833五氯硝基苯quintozene82-68-8c6cl5no2295.334-六六六-hcb58-89-9c6h6cl6290.835七氯heptachlor76-44-8c10h5cl7373.326五氯苯胺pentachloaniline527-20-8c6h2cl5n265.357艾氏剂aldrin309-00-2c12h8cl6364.918-六六六-hcb319-85-7c6h6cl6

13、290.839-六六六-hcb319-86-8c6h6cl6290.8310环氧七氯heptachlorepoxide1024-57-3c10h5cl7o389.3211三唑酮triadimefon43121-43-3c14h16cln3o2293.7512-硫丹-endosulfan115-29-7c9h6cl6o3s406.9313p,p-滴滴伊p, p-dde72-55-9c14h8cl4318.0314狄氏剂dieldrin60-57-1c12h8cl6o380.9115异狄氏剂endrin72-20-8c12h8cl6o380.9116op-滴滴涕op-ddt789-02-6c14h

14、9cl5354.4917-硫丹-endosulfan33213-65-9c9h6cl6o3s406.9318p,p-滴滴滴p, p-ddd72-54-8c14h10cl4320.419p,p-滴滴涕p, p-ddt50-29-3c14h9cl5354.4920异狄氏剂醛endrin aldehyde7421-93-4c12h8cl6o380.9121联苯菊酯bifenthrin82657-04-3c23h22clf3o2422.8722胺菊酯tetramethrin7696-12-0c19h25no4331.4123甲氰菊酯fenpropathrin64257-84-7c22h23no3349

15、.4224氯菊酯permethrin52645-53-1c21h20cl2o3391.2925氯氰菊酯cypermethrin71697-59-1c22h19cl2no3416.326氰戊菊酯fenvalerate51630-58-1c25h22clno3419.927溴氰菊酯deltamethrin52918-63-5c22h19br2no3505.2附录b（资料性附录）27种有机氯、拟除虫菊酯农药混合标准溶液的气相色谱图（10 g/l）1.六氯苯12. -硫丹23.甲氰菊酯2. -六六六13. p, p-滴滴伊24.胺菊酯23.五氯硝基苯14.狄氏剂25.氯菊酯14. -六六六15.异狄氏

16、剂26.氯菊酯25.七氯16. op-滴滴涕27.氯氰菊酯16.五氯苯胺17. -硫丹28.氯氰菊酯27.艾氏剂18. p, p-滴滴滴29.氯氰菊酯38. -六六六19. p, p-滴滴涕30.氯氰菊酯49. -六六六20.异狄氏剂醛31.氰戊菊酯110.环氧七氯21.联苯菊酯32.氰戊菊酯211.三唑酮22.胺菊酯133.溴氰菊酯附录c（资料性附录）27种农药在6种中药材中各添加水平的回收率范围表2 gc-ecd检测27种农药在6种中草药中各添加水平的回收率范围农药添加水平(g/kg)山药回收率( % )葛根回收率( % )人参回收率( % )半夏回收率( % )柴胡回收率(%)党参回收率

17、(%)六氯苯1078.597.780.096.070.986.674.286.779.798.981.2103.22081.0108.282.2107.072.389.470.985.482.7104.493.7109.620080.988.282.192.680.889.780.492.682.3102.380.294.4100080.490.180.393.880.391.280.991.391.7104.280.289.5-六六六1072.585.976.496.871.379.571.582.173.390.876.486.02090.7105.685.9103.277.189.270

18、.480.480.8101.983.591.520082.289.184.3103.280.795.280.489.282.2108.780.2107.4100082.192.283.093.288.796.3100.8109.583.4106.380.4101.5五氯硝基苯1076.486.584.094.570.076.279.686.680.087.171.287.22090.5106.584.6108.870.483.872.583.076.695.898.1109.320080.989.085.4106.082.797.981.189.090.9101.983.190.8100083

19、.9104.985.596.382.799.284.094.083.0108.680.389.9-六六六1076.189.983.291.274.298.372.980.582.3108.771.287.22084.799.983.199.271.793.471.381.581.9106.782.0105.620083.794.081.4104.288.794.7100.9107.681.6108.180.188.6100087.4107.782.796.081.896.483.592.990.1109.581.696.4七氯1072.489.881.693.970.588.277.586.2

20、81.6101.1100.8108.52077.4101.380.7105.882.194.893.3107.787.8108.387.9105.420081.987.488.0107.083.2107.889.6101.288.9103.283.1109.8100083.6104.780.4103.886.7101.481.295.182.8109.085.797.8五氯苯胺1073.291.678.891.273.489.978.886.982.0102.792.299.22079.9107.085.5105.670.598.876.283.680.5102.986.1102.520080

21、.187.985.6108.080.3106.384.291.281.7108.386.0103.6100091.3106.386.399.082.4108.384.7108.689.1108.184.295.2艾氏剂1080.392.684.496.176.398.673.086.781.5109.480.496.42080.393.385.398.870.298.175.380.480.2102.183.2107.820081.089.685.596.880.3101.187.194.991.7107.480.893.6100081.1105.184.396.981.4108.481.29

22、0.691.2103.883.897.6-六六六1083.594.786.6101.270.899.170.685.686.0103.290.7109.22080.293.983.796.471.985.181.786.882.297.296.7105.820081.589.182.693.584.9105.096.5105.087.4109.976.598.2100080.490.684.094.086.2106.880.189.883.2108.580.689.5-六六六1075.786.581.597.671.587.274.387.181.799.6101.2109.42083.210

23、7.484.193.472.490.980.688.483.9103.880.397.420081.893.883.796.282.488.582.395.784.2101.180.889.9100081.298.486.093.584.095.984.498.288.7109.685.395.4环氧七氯1074.993.081.56102.872.085.671.486.382.397.996.3101.22087.5104.284.5109.473.292.482.388.484.4105.683.993.720080.795.982.7100.085.994.897.6107.897.4

24、108.683.993.7100091.6107.484.297.287.1107.381.699.092.6108.880.491.6三唑酮1076.298.082.293.170.585.273.896.880.597.373.579.22085.5107.285.095.783.895.495.2108.484.4109.083.196.420082.993.983.295.784.395.295.8108.287.8108.796.4108.4100080.288.180.793.386.796.198.5109.289.8105.180.694.7-硫丹1078.286.881.58

25、9.472.498.671.282.382.7105.972.286.42080.9104.883.490.870.896.274.980.480.9109.985.6100.420083.195.881.792.080.899.280.590.083.3108.680.296.0100084.2104.980.095.981.793.683.699.387.0106.981.699.5p,p-滴滴伊1075.585.883.292.871.097.272.185.681.0108.988.4102.42085.2106.386.4102.681.394.880.389.485.6108.48

26、3.8105.820083.0597.785.197.484.991.981.396.887.3104.593.1102.7100089.5106.284.2109.380.693.591.6106.286.8102.790.8104.5狄氏剂1084.496.580.096.170.789.076.383.680.8101.781.3104.82086.3108.583.2102.671.979.281.790.082.190.5100.5108.420083.095.385.995.780.696.786.697.586.599.085.397.8100090.4108.185.3106.

27、484.394.795.7107.690.0108.283.690.6异狄氏剂1077.092.084.793.271.189.175.186.981.3101.897.6109.42081.292.885.491.981.394.792.3107.688.3108.294.6109.520083.3107.484.493.181.689.286.8101.487.0101.980.0108.8100085.191.486.698.880.098.882.690.987.4106.893.0109.6op-滴滴涕1075.687.485.194.170.689.272.286.680.6101

28、.988.4104.82075.3100.683.3100.679.193.689.9106.490.3104.1102.7108.620082.6100.984.3102.682.494.184.095.694.1107.581.289.3100092.2109.581.3103.380.795.180.392.182.2108.685.7109.3-硫丹1072.487.986.194.973.383.871.187.383.795.891.2107.32085.7106.583.896.870.877.780.488.381.588.884.491.520079.1102.984.895

29、.880.296.783.7104.981.797.887.2103.9100089.6107.784.594.280.596.580.194.885.4109.282.4105.6p,p-滴滴滴1073.486.285.294.872.099.372.883.382.396.093.2108.82094.8109.481.394.272.088.177.281.981.1100.780.589.420082.097.983.992.883.697.483.688.489.3109.093.6104.4100086.3105.087.6106.280.497.380.0102.386.2108

30、.383.094.8p,p-滴滴涕1084.297.485.590.772.489.877.588.783.9102.685.3108.82085.2106.386.594.478.491.989.1104.481.3106.083.292.620083.793.985.799.186.994.698.7108.884.2109.482.689.0100095.5108.982.392.281.0106.880.799.189.6106.798.9108.6异狄氏剂醛1074.188.480.893.570.380.274.891.180.391.673.283.22072.183.384.5

31、93.171.179.778.684.780.591.189.699.720081.196.184.594.382.297.081.487.588.2107.680.689.4100080.195.382.294.180.797.681.491.882.2109.782.8106.6联苯菊酯1075.889.277.292.073.494.783.5107.683.9108.272.097.22073.996.983.693.672.689.570.979.083.0102.382.493.720084.995.880.391.780.296.180.691.281.7104.583.292.

32、1100080.189.284.293.081.595.792.6108.793.1109.380.094.1胺菊酯1074.089.185.299.670.684.080.295.480.695.987.2107.62077.190.584.8102.678.489.475.478.988.2102.189.7106.520084.197.084.293.681.198.280.888.892.7107.798.3109.6100084.4103.883.994.684.996.496.5109.680.1108.6100.5108.4甲氰菊酯1073.195.484.495.770.686

33、.773.587.880.699.074.285.32086.4104.283.193.274.594.984.789.880.3108.486.298.820083.195.984.898.584.996.496.5109.685.2109.080.388.7100080.4103.383.596.481.697.485.7104.083.3104.580.487.6氯菊酯1081.295.389.299.073.989.178.588.783.0101.880.689.62082.993.391.496.572.378.282.288.882.696.181.998.520083.398.

34、585.498.280.189.888.1102.091.5102.699.4106.7100082.494.393.5107.781.395.681.0108.789.1109.290.4109.6氯氰菊酯1076.388.584.091.872.289.274.984.480.6101.992.0109.82080.786.484.8102.282.492.893.7105.485.1106.086.95107.920080.698.481.2105.184.4104.084.6101.480.5109.780.588.0100084.497.980.995.484.5107.481.29

35、7.789.4106.080.787.0氰戊菊酯1072.885.981.496.570.888.380.486.480.9100.983.3109.82084.8105.386.0106.680.587.391.499.375.599.886.399.420080.996.184.2101.088.994.6101.0107.582.7107.584.987.0100080.296.783.5103.580.597.980.297.887.1100.686.3103.5溴氰菊酯1078.999.188.4107.270.589.576.089.980.4102.287.8109.22073.

36、795.386.8103.873.197.376.485.183.5101.296.1108.620080.494.781.9693.690.994.5103.6107.487.2105.080.486.4100080.390.783.093.788.293.9100.3106.783.8107.282.198.4forewordannex a, annex b and annex c of this standard are informative annex.this standard is accordanced with gb/t 1.1-2009 standardization gu

37、ide part 1: structure and preparation of the standard, gb/t 20001.4-2001 standard writing rules part 4: chemical analysis and sn/t 0001-1995 the basic provisions of standard test methods prepared for pesticides, veterinary drugs residues and biological toxins in export goods requirements drafted.the

38、 standards use gas chromatography. the choice of compatible detection methods shall be based on detection of objects and detection limit of their requirements.this standard was proposed by and is under the charge of the certification and accreditation administration of the peoples republic of china.

39、this standard was drafted by the chongqing entry-exit inspection and quarantine bureau of the peoples republic of china.this main drafters of this standard are .this standard is the first release of the industry standard for entry-exit inspection and quarantine.note: this english version, a translat

40、ion from the chinese text, is solely for guidance.determination of organochlorine and pyrethroid multipesticide residues in rhizome of chinese herbal medicines for import and export1 scopethis standard specifies the method of sample determination and confirmation of hexachlorobenzene, -hcb, quintoze

41、ne, -hcb, heptachlor, pentachloaniline, aldrin, -hcb, -hcb, heptachlor epoxide,triadimefon,-endosulfan,p, p-dde, dieldrin, endrin, op-ddt, -endosulfan, p, p-ddd, p, p-ddt, endrin aldehyde, bifenthrin, tetramethrin, fenp ropathrin, permethrin, cypermethrin , fenvalerate, deltamethrin by gas chromatog

42、raphy.this standard is applicable to the determination of 27 organochlorine and pyrethroid pesticides in common yam rhizomes, radix puerariae lobatae, radix ginseng, ternate pinellia, chinese thorowax root and pilose asiabell root.2 normative referencethe following normative documents contain provis

43、ions which, through reference in this text, constitute provisions of this standard. for dated references, subsequent amendments to, or revisions of any of these publications do not apply. however parties to agreements based on this standard are encouraged to investigate the possibility of applying t

44、he most recent editions of the normative documents indicated below. for undated references, the latest edition of the normative document referred to applies.3 principle the test sample is extracted with acetone-n-hexane (4:3, v/v), after being concentrated, purified by gel permeation chromatography

45、and florisil solid phase extraction column，and determined by gas chromatography with micro-electron capture detector, quantified by external standard method.4 reagents and materialsunless otherwise specified, all the reagents used should be analytically pure, water is complied with gb/t 6682 provide

46、s.4.1 acetone: hplc grade.4.2 acetonitrile: hplc grade.4.3 dichloromethane: hplc grade.4.4 n-hexane: hplc grade.4.5 ethyl acetate: hplc grade.4.6 cyclohexane: hplc grade.4.7 sodium chloride.4.8 anhydrous sodium sulfate.4.9 standard material: hexachlorobenzene, -hcb, quintozene, -hcb, heptachlor, pen

47、tachloaniline, aldrin, -hcb, -hcb, heptachlor epoxide, triadimefon, -endosulfan, p, p-dde, dieldrin, endrin, op-ddt, -endosulfan, p, p-ddd,p, p-ddt, endrin aldehyde, bifenthrin, tetramethrin,fenp ropathrin, permethrin, cypermethrin, fenvalerate, deltamethrin (purity 99.0%. from the national institut

48、e of standards substances center，detail refer to annex a).4.10 standard stock solution of 27 pesticides: accurately weigh an adequate amount of every 27 pesticide standard and dissolve in a small volume of n-hexane, dilute with n-hexane to make the standard stock solution of 100 mg/l . it should be

49、stored in a refrigerator at 4 for 12 months.4.11 mixed standard stock solution: volume the single species of standard stock solution, dilute with n-hexane to make the mixed standard stock solution of 2 mg/l. dilute the mixed standard stock solution with n-hexane to the required concentration to make

50、 the standard working solution. it should be stored in a refrigerator at 4 for 12 months.4.12 lc - florisil spe tubes (1g, 6ml) : before use 5 ml of n-hexane activated.4.13 membrane: 0.22m, 0.45 m, the organic solvent film. 5 instruments and equipment5.1 gas chromatograph (gc), equipped with electron capture detector.5.2 gel permeation chromatography5.3 analytical balance: a sensitivity of 0.0001 g and 0.01 g