SN T 3768-2014 出口粮谷中多种有机磷农药残留量测定方法气相色谱-质谱法.pdf

1、中人共和出入境检瞌检瘟行业标准SN/3768-2014 代替SN0133-1992 ,SN 0136-1992等出口粮谷中多种有机磷农药残留量测定方法气相色谱E质谱法Determination of organicphosforus residues in cereal grains for export-GC/MS method 2014-01-13发布2014-08-01实施中华人民共和国发布国家质量监督检验棱疫总属SN/T 3768-2014 目。吕本标准按照GB/T1.1-2009给出的规则起草。本标准代替SN0133-1992(出口粮谷中工嗦磷、倍硫磷、杀膜硫磷、对硫磷、稻丰散、苯硫

2、磷残留量检验方法、SN0136-1992 (出口粮谷中敌敌畏、二嗦磷、倍硫磷、马拉硫磷残留量检验方法、SN 0137-1992(出口粮谷中甲基嘀睫磷残留量检验方法、SN0144一1992(出口蔬菜及蔬菜制品中敌敌畏、二嗦磷和马拉硫磷残留量的检验方法、SN/T0351一2009(进出口食品中丙线磷残留量检测方法、SN0495-1995(出口粮谷中乙暗硫磷残留量检验方法上SN 0522-1996(出口粮谷中特丁磷残留量检验方法、SN0585-1996(出口粮谷及油籽中乙酷甲胶磷残留量检验方法、SN0591-1996(出口粮谷及油籽中二日恶硫磷残留量检验方法、SN0651一1997(出口粮谷中甲基乙

3、拌磷残留量检验方法和SN/T 1017.2-200150 2050 1020 运10土20口口。/十一士30土508 结果计算和表述用色谱数据处理机或按(1)式计算试样中农药残留量，计算结果应扣除空白值:X , =Ai X正iX V 1 000 v _ _ Ai只Xm 1 000 . ( 1 ) 式中:Xi一一牛试样中农药1残留量，单位为毫克每千克(mg/kg); A 样液中农药的峰面积(或峰高); Ai吨标准工作液中农药i的峰面积(或峰高); Ci一一标准工作液中农药1的被度，单位为微克每毫升(g/mL); v 样液最终定容体积，单位为毫升(mL); 1 最终样液所代表的试样质量，单位为克(

4、g)。9 测定低限和回收率9.1 测定低限本方法的测定低限见表2。9.2 添加浓度范围及回收率本方法添加浓度及回收率见表2。表2本方法添加浓度范围及回收率药品名称样品种类!定低限/Cmg/kg)添加水平/Cmg/kg)1m收率范围/%0.010 80.0102.。玉米0.01 0.040 79.095.。0.400 78.497.3 0.010 82.0104.。敌敌畏糙米0.01 0.040 76.099.。0.400 81.696.4 0.010 80.0102.。大米0.01 0.040 75.091.。0.400 77.394.8 4 SN/T 3768一-2014表2(续)药品名称样

5、品种类测定低限/Cmg/kg)添加水平/Cmg/kg)回收率范围/%0.010 76.010Z.0 莽麦0.01 0.040 76.09Z.。0.400 79.899.1 敌敌畏0.010 8Z.010Z.0 小麦0.01 0.040 84.097.。0.400 75.99Z.3 0.010 76.095.。玉米0.01 0.040 8Z.597.5 0.400 85.398.3 0.010 76.09Z.。糙米0.01 0.040 83.5104.0 0.400 83.195.Z 0.010 80.010Z.0 乙航甲胶磷大米0.01 0.040 8Z.010Z.。0.400 81.494.

6、6 0.010 75.095.。莽麦0.01 0.040 8Z.510Z.。0.400 84.998.7 0.010 79.095.。小麦0.01 0.040 83.0104.5 0.400 8Z.795.。0.005 74.093.。玉米0.005 0.010 82.010Z.0 0.100 79. 79Z.8 0.005 79.0106.。糙米0.005 0.010 8Z.099.5 0.100 84.698.6 0.005 78.09Z.。丙线磷大米0.005 0.010 83.0101.0 0.100 81.994.7 0.005 75.094.。养麦0.005 0.010 80.59

7、3.5 0.100 81.495.4 0.005 78.096.。小麦0.005 0.010 8Z.098.5 0.100 84.699.Z 5 SN/T 3768-2014 表2(续)药品名称样品种类测定低|浪/Cmg/kg)添加l水平/Cmg/kg)|卫|收率范罔/%0.010 79.096.0 玉米0.01 0.040 79.593.。.110082.798.1 。.01075.093.。0.040 85.5101.5 0.400 78.290.3 0.010 76.096.0 甲基乙J丰磷0.040 82.599.5 0 .11 00 79.292.5 0.010 75.091.。O.

8、O C! O 84.5100.5 0.1 00 78.191.9 0.010 77.095.。0.040 83.0 100.0 0.400 82.292.1 0.010 77.096.。0.040 8，l.599.。0.400 83.1 96.2 0.010 79.095.。0.040 81.5103.0 。.40082.394.5 0.010 79.095.。二n恶硫磷大米0.01 0.040 87.0104.0 0.4 00 82.996.9 0.010 79.0101.。养麦0.01 0.040 79.594.5 0.4 00 84.6100.2 0.010 79.091.。小麦0.01

9、 。.0408fl.O97.0 0.400 78.892.。6 SN/T 3768-2014 表2(续)药品名称样品种类测定低限/(mg/kg)添加水平/(mg/kg)回收率范围/%0.005 77.0100.。玉米0.005 0.010 84.099.5 0.100 84.698.8 0.005 75.093.。0.010 86.5109.5 0.100 80.893.7 0.005 78.0100.。特丁磷0.010 80.094.5 0.100 84.797.9 0.005 86.099.。0.010 77.0102.5 0.100 82.795.。0.005 75.095.。0.010

10、 79.5102.5 0.100 81.294. 7 0.010 79.0100.0 0.040 84.097.。0.400 84.998.8 0.010 75.093.。0.040 89.01l1.0 0.400 80.993.8 0.010 73.0103.0 二嗦磷大米0.01 0.040 82.592.5 0.400 84.997.7 0.010 85.099.。养麦0.01 0.040 78.0102.5 0.400 82.795.。0.010 79.095.。小麦0.01 0.040 82.5107.5 0.400 82.294.7 7 SN/T 3768-2014 表2(续)药品

11、名称样品种类测定低限/(mg/kg) 添加水平/(mg/kg)阴收率范围/%0.010 81.096.。玉米0.01 0.040 84.5107.5 0.400 82.492.8 0.010 81.099.0 糙米0.01 0.040 77.597.。.40084.798.8 。.01076.098.0 乙略硫磷大米0.01 0.040 83.5102.0 0.4 00 82.295.2 0.010 82.0 105.0 莽麦0.01 0.040 8，1.5 108.5 0.4 00 83.496.6 0.010 74.093.。小麦0.01 0.0/10 78.093. 0.400 8/1.

12、798.。0.010 73.095.。玉米0.01 0.040 76.586.5 0.400 82.796.7 0.010 83.097.。糙米0.01 0.040 78.592.。.40085.998.4 0.010 74.097.0 甲基略q定磷大米0.01 0.040 84.0 102.5 0.400 84.196.3 0.010 79.094.。养麦0.01 0.040 84.5104.0 0.4 00 84.597.6 0.010 75.089.。小麦0.01 0.040 79.592.5 0.400 84.8 108.5 8 SN/T 3768-2014 表2(续)药品名称样品种类

13、测定低限/Cmg/kg)添加水平/Cmg/kg)回收率范围/%0.010 75.092.0 玉米0.01 0.040 83.599.5 0.400 83.7105.5 0.010 79.0100.0 糙米0.01 0.040 77.592.。0.400 84.697.3 0.010 80.01l0.。杀蟆硫磷大米0.01 0.040 86.5102.。0.400 82.995.6 0.010 79.098.。莽麦0.01 0.040 86.5108.5 0.400 84.897.9 0.010 75.096.。小麦0.01 0.040 84.597.。0.400 78.392.2 0.010

14、79.099.。玉米0.01 0.040 84.0108.0 0.400 80.693.2 0.010 78.098.。糙米0.01 0.040 77.099.5 0.400 84.598.2 0.010 79.099.。马拉硫磷大米0.01 0.040 82.597.5 0.400 78.591.6 0.010 80.099.。莽麦0.01 0.040 78.592.。0.400 83.097.4 0.010 75.091.。小麦0.01 0.040 88.0102.5 0.400 78.692.9 9 SN/T 3768一2014表2(续)药品名称样品种类测定低限/(mg/kg) 添加水平

15、/Cmg/kg)回收率范用/%。.01087.0105.0 玉米0.01 0.010 78.091.5 0.400 77.6 1();.6 0.010 79.098.。糙米0.01 0.040 88.0102.5 。.，0093.6 109.3 0.010 81.099.。倍硫磷大米0.01 0.040 75.592.。0.400 77.1102.5 / 0.010 79.099.。、养麦0.01 0.040 78.595.5 、0.400 83.196.7 协0.010 77.594.5 小麦0.01 飞d、.、气、0.040 85.299.4 / 九立0.400 78.993.5 3 飞飞

16、1 I之一飞0.005 73.093.。F 玉米笠、83.0 104.5 0.4 00 78.391.1 / 79.095.0 糙米I 0.040 78.0103.0 -J 一一 0.4 00 79.197.3 0.005 80.095.。对硫磷大米0.005 0.040 88.5108.5 0.400 82.395.4 0.005 77.099.。莽麦0.005 0.040 87.5103.0 0.400 84.297.8 0.005 79.091.。小麦0.005 0.040 87.0104.5 0.4 00 82.294.。10 SN/T 3768-2014 表2(续)药品名称样品种类测

17、定低限/Cmg/kg)I添加水平/Cmg/kg)回收率范围/%0.010 74.094.。玉米0.01 0.040 80.093.0 0.400 79.191.9 0.010 79.099.。75.59Z.5 79.893.7 79.096.。稻丰散大米8Z.599.5 79.393.7 84.0 11Z.。86.0103.5 81.194.7 75.089.。8Z.098.5 8Z.094.3 。74.094.。80.093.。79.191.9 79.099.。75.59Z.5 79.893.7 0.010 79.096.。丁胶磷大米0.01 0.040 8Z.599.5 0.400 79.

18、393.7 0.010 84.0l1Z.0 养麦0.01 0.040 86.0103.5 0.400 81.194.7 0.010 75.089.。小麦0.01 0.040 8Z.098.5 0.400 8Z.094.3 11 SN/T 3768一2014表2(续)药品名称样品种类测定低限/Cmg/kg)添加水平/Cmg/kg)因l/史率范罔/%0.010 74.094.0 玉米0.01 0.040 80.093.。0.4 00 79.191.9 0.010 79.099.。糙米0.01 0.040 75.592.5 。.40079.893.7 0.010 79.096.。苯硫磷大米0.01

19、0.0/10 82.599.5 0.400 79.393.7 0.010 84.0 112.0 养麦0.01 0.040 86.0 103.5 。AOO81. 1 9/1.7 0.010 75.089.。小麦0.01 0.040 82.098.5 0.4 00 82.094.3 12 SN/T 3768-2014 附录A(规范性附录)敌敌畏等16种有机磷类农药种类表表A.1敌敌畏等16种有机磷类农药种类表序号农药名称英文名称CAS No. 化学分子式l 敌敌畏Dichlorvos 62-73-7 C, H7Cl,O,P 2 乙眈甲胶磷Acephate 30560-19-1 C, HlON03P

20、S 3 丙线磷Ethoprophos 13194-48-4 C8Hl90 ,PS, 4 特丁磷Terbufos 1307l明79-9C9HlO,PS3 5 甲基乙拌磷Thiometon 640-15-3 C6Hl50 ,PS3 6 二嗦磷Diazinon 33341-5 C1，日IN，03PS7 二略硫磷Dioxathion 7834-2 C1, H26 0 6 P, S4 8 乙略硫磷Etrimfos 38260叩54-7ClO H17 N, 0 4 PS 9 甲基略院磷Pirimiphos-methyl 29232-93-7 Cll H,o N3 03 PS 10 杀螺硫磷Sumithio

21、n 122-14-5 C9H1,N05PS 11 马拉硫磷Malathion 121-75甲5ClO Hl9 0 6 PS, 12 f音硫磷Fenthion 55-38-9 ClO Hl5 0 3 PS, 13 对硫磷Parathion 56-38-2 ClO H I1 0 5 NSP 14 稻丰散Phenthoate 2597-03-7 C1, Hl7 0 , PS, 15 丁胶磷Butamifos 36335-67-8 C13 Hl N, 0 PS 16 苯硫磷EPN 2104-64-5 CI1 H I1 NO PS 13 SN/T 3768 2014 附录B(资料性附录)敌敌畏等16种有

22、机磷类农药GC-MS定量和定性选择离子及测定低限表1)表B.1敌敌畏等16种有机磷类农药GC-MS定量和定性选择离子及测定低限表保网时间/特征碎片肖子/amu测定低限/序号农药名称mm 足豆问定性丰!豆比(g/g) 敌敌畏6.13 185卢rOg;T87;222 37 : 100 : 12 : 07 0.01 2 乙自Jt甲胶磷8.68 136 94 ,125;142 11100: 46: 21: 22 0.01 J 3 内线磷9.90 242 ,168 , 200. 23 : 100 : H : 40 0.005 特丁磷11. 54 231 / 186 , 203 100 : 14 : 10

23、 : 11 。.0055 吁l基乙拌磷11. 60 24V 19: 18: 51 100 。.016 二I垛磷11. 78 304 1币，276，28962 : 100 : 29 : 11 O.C) 7 乙暗硫磷12.61 292 /俨r1月1.?. 717 100 : 65 : 11 : 33 0.01 8 二H恶硫磷12.83 271 125 , 53, 197:; 94: 100 : 81 : 29 。.019 吁!基I骆驼磷H.91 290 262 , 276 , 305 100: 25 : 82: 73 。.0110 马拉硫磷J 5.62 285 158 , 173 , 256 07

24、 : 40 : 100 : 10 0.01 11 杀虫罢硫磷15.75 卢2，247挝、100 : 10 : 06 : 54 0.01 12 对硫磷J 5.89 29 ! 2.62、100:19:21:l6 0.005 13 倍硫磷16.58 27: 二刊以100: 18: 08: 06 。.0114 稻丰散18.18 274 j 剂弘卢必绘图4寻斗100: 49 : 22 : II O.C) 15 丁胶磷18.59 i J 286 , 232 , 100: 82: 41: 22 0.01 16 苯硫磷24.80 157 , 16 : 100 : 60 : 33 0.01 3 三户1) 附录B

25、所列定量和定性选择离子是在安捷伦气相色活质谱仪上完成的，此处列出试验用仪器型号仅是为了提供参考，并不涉及商业目的。鼓励标准使用者尝试采用不同厂家或型号的仪器。14 Abundance 30 000 25 000 20 000 15 000寸10 000 5 000 说明:1 敌敌畏;2一一乙毗甲胶磷;3一一丙线磷;4 特丁磷;附录C(资料性附录)敌敌畏等16种有机磷类农药气相色i普选择离子色i昔圈飞。M 硫磷;SN/T 3768-2014 r. ,.; t/min 15 SN/T 3768-2014 For母wordThis standard was drafted according to

26、GB/丁1.1-2009.This section of the original11 standards (SN 0133-1992、SN0136-1992、SN0137-1992、SN0144-1992、SN/T0351-2009、SN0495-1995、SN05221996、SN0585-1996、SN0591-1996、SN0651-1997 & SN/T 1017.2-2001) was revised and consolidated index: -Use the range , including the original 11-related standards. -Usin

27、g GC/MS method , increase positive confirmation of content , integration of pretreatment conditions. 一Thescope of application of this standard includes the original 11 standar白s.This standard adopts GC/MS. but the original 11 standards adopt GC method. The lower limit of this standard are lower than

28、 the original 11 standards s. Please note that some of the content of this document mainvolve patent. This file is not responsible for the publishing sector recognizes the responsibility of these patents. This standard was proposed band is under the charge of Certification and Accreditation Administ

29、ration of the People少sRepublic of China. 丁hisstandard was drafted by the Jilin Entry-Exit Inspection and Ouarantine Bureau of the People s Republic of China 、TonghuaEntry-Exit Inspection and Ouarantine Bureau of the People s Republic of China. This main drafter of this standard is Li Aijun , Wang Mi

30、ngtai , Mu Jun , Lu Li jun , Zhou Xiao. Shi Xiaoli. 丁hisstandard replaced the previous version of release of the standard as follows: -SN 0133-1992; 一SN0136-1992; 一SN0137一1992;-SN 0144-1992; -SN 0351-1995.SN/T 0351-2009; 16 -SN 0495-1995; -SN 0522-1996; -SN 0585一1996;一SN0591-1996; -SN 0651-1997; -SN

31、j了1017.2-2001.Note: This English version , a translation from the Chinese text , is solely for guidance SNjT 3768-2014 17 SN/T 3768-2014 Det自rmination of organicphosforus residues In c白白algrains for export-GC/时Smethod Scope This standard specifies a multiply testing method by GC-MS for determining 1

32、6 pesticide residues including dichlorvos、acephate、pi ri m i phos-methyl、sumithion，malin cereal grains for export. diazinon etc. in corn , brown rice , rice , 2 Normat ive references to applies. GB/丁6682Water for laborato 3 Principle Dichlorvos、acephate、etmethyl 、sumithion、malathion，fenth iazinon、di

33、oxathion，etrimfos、e、butamifos、EPN(AnnexA. 1) efereces ,only dated editions shall the normative document referred ioxathion , etrimfos , pirimiphos fos、EPNin the test sample are extracted with wate卜acetone.The extract is partitioned with dichloromethane. Cleaned up by passing through on GPC、activecar

34、bon column and florisil solid phase. The elutes solution is evaporated and made up to a definite volume. Determination and confirmation is made bGC-MS， using external standard method. 4 Reagents and materials nless otherwise specified , all the reagents used should be analticallpure， water is the fi

35、rst grade water prescribed bGB/T 6682. 4.1 n-Hexane: pesticide grade. 18 SN/T 3768-2014 4.2 Cclohexane: pesticide grade. 4.3 Acetone: pesticide grade. 4.4 Ethyl acetate: pesticide grade. 4.5 Oichloromethane: pesticide grade. 4.6 Anhydrous sodium sulfate: Ignite at 650 oC for 4 h, and keep in a tight

36、ly closed container. 4.7白凹M川hy川协门h(门1十圳U川V/扩/旷/V川):川川:八J飞Volu川f汀Tmix them.、;/ / 4.8 EthI acetate-cyclohexane C 1 + 1 , V / V) : Volume 100 mL e位叭acetateinto 250 mL erlenmeyer / flask , then add 100 mL cclohexane， mix them. 4.9 Sodium chloride aqueous solution:20 g/L. f / / 4.11 Oichlorvos etc.16 org

37、anophosphrous standarq/stock solution: Accurately weigh an adequate amount of Organophosphrous pesticiJes standard .( see annex A) .a到ddissolve in a small volume of acetone.Oilute with acetone to fdrm a standard stock solution f飞100阳/mL1 000阳/mLin concentratlon. .12 Oichlorvos etc.16 orc solution wi

38、th acetone to the r I二二74.13 ENVI-Carb SPE column: ENVICa巾，250mg ,6 mL,or Efquivl吼、/ 4.14 Florisil SPE column: Florisil ,500 mg;6.rLor equival8f 4.15 Membrane fi Iter: 0.45m. 5 Apparatus and equipment 5.1 GC-MSO: Equipped with electro-impact source (ED. 5.2 Electronic balance: Accurate to 0.000 1 g.

39、 5.3 Gel permeation chromatographCGPC) equipped with isocratic pump and fraction collector. 19 SN/T 3768-2014 5.4 Homogenizer. 5.5 Rotary vacuum evaporator. 5.6 Conical flask:250 mL,with stopper. 5.7 Separator funnel: 250 mL. 5.8 Concentrate bottle:250 mL. 5.9 Centrifuge:4000 r/min. 6 Preparation an

40、d storage of test sample 6.1 Preparation of test sample Take approximatel500 9 of representative sample.Smash thoroughly by a chopper.Mix thoroughly. Put into clean containers.Seal and label them. 6.2 Storage of test sample Test samples shall be stored at a temperature ranged from 0 oC 4 oC. In cour

41、se of sampling and sample preparation , attention shall be taken to avoid contamination or an factors which may cause the change of residues content. 7 Procedure 7.1 Extraction Weigh about 20 9 (accurate to 0.01 g) of the test sample into a 250 mL conical flask with stopper, add 20 mL of water and 1

42、00 mL of acetone ,extract for 3 min on a high speed homogenizer.Filter the extract into a 250 mL concentrate bottle.Extract the residue with 50 mL of acetone once more, filter and combine the washings in the same concentrate bottle,evaporate to 20 mL in a rotary evaporator with a bath temperature be

43、low 40 oC. 7.2 Cleaning-up 7.2.1 Dichlorvos etc.16 organophosphrous pesticides cleaning-up Transfer the concentrated solution into a 250 mL separator funnel , add 150 mL of sodium chloride 20 SN/T 3768-2014 aqueous solution and 50 mL of dichloromethane, shake for 3 min and set aside for separating.C

44、ollect the dichloromethane phase. The water phase is again extracted with 2 x 50 mL of dichloromethane. Combined the dichloromethane phases ,and let pass through a column of anhydrous sodium sulfate to remove the water.Collect the effluent in a 250 mL concentrate bottle and evaporate to near dryness

45、 in a rotary evaporator with a bath temperature below 40巳.Dissolve the residue with 5 mL of cyclohexane-ethyl acetate (1十1), and filter through 0.45m membrane filter. p u nuu n n 50 2050 1020 10 permitted tolerances/% 土20士25土30士5022 SN/T 3768-2014 8 Calculat ion and expression of the resul t Calcula

46、te the content of Trichlorfon residue in the test sample by GC-MS data processor or according to the followed formula. where , X i -the residue content of milligram per kilogram.mg/kg. A i -the peak area (or the peak heigh of 16 solution. working solution. C，一-theconcentration of 16 Unit is microgra

47、m per milli V -the final diluted volume. m -the corresponding mass gram ,g. Note , The result of calculation shall be 9 Detection limit and recover 9.1 Limit of determination See Table 2 to find the limit of determination of the method. 9.2 Range of fortification and recovery . ( 1 ) in the test sam

48、ple. Unit is resmethrin etc. in the standard in the standard working solution. final sample solution. Unit is The ranges of fortification and recovery of this method are shown in table 2. 23 SN/T 3768-2014 了able2 Range for fortification and recovery of this method Li mit of determination Fortified level/ Range of recovery / Compound sample and confirmation/ (mg/kg) % (mg/kg) 0.010 80.0102.0 Corn 0.010 0.040 79.0