1、SF 中华人民共和国出入境检验检疫行业标准SN/T 1983-2007 进出口食品中丙烘氟草肢残留量检测方法气相色谱-质谱法Determination of f1 umioxazin residues in food for import and export GC-MS method 2007-08-06发布2008-03-01实施J 中华人民共和国发布主爵王国家质量监督检验检夜总局飞担担/SN/T 1983-2007 前言本标准附录A为资料性附录。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2中华人民共和国深圳出入境检验检疫局、中华人民共和国山东出入境检验检疫局、中华人民共
2、和国辽宁出入境检验检疫局负责起草。本标准主要起草人:蓝芳、林黎、i射丽琪、叶同IJ、侯乐锡、王建华、卫峰、靳保辉。本标准系首次发布的出入境检验检疫行业标准。1 范围进出口食品中丙快氟草股残留量检测方法气相色谙-质谱法本标准规定了食品中丙快氟草胶残留量的制样和气相色i百质i苦检测方法。SN/T 1983-2007 本标准适用于苹果、波菜、姜、鱼、鸡肉、猪肉、大豆、大米、杏仁和猪肝中丙烘氟草胶残留莹的检测。2 样品制备与保存2. 1 大豆、大米及杏仁1. . J 取代表性样品500g.粉碎并使或全部通过孔径为2.0mm的样品慨。混合均匀后均分成两份，装入洁净容器内，密封并标识啤-4C吉它琛有?斗-
3、;.2.2 菠菜、苹果和姜/r / 取代表性样品至少500g.取可食邵阳!何制、块，乒组织捣碎机将样品匀浆.混合均匀后分成两份，装入洁净的样品袋内，密闭并衍r，R;京已lSC进光保汗。2.3鱼、鸡肉、猪肉和猪肝俨占胃取代表性样品至少500g.取可食ttf，分切碎并m组织捣碎机将样品匀浆，混合均匀后分成两份，装人洁净的样品袋内，密闭并标识;在1St:地光保存。在制样的操作过程巾，应防止样d古莱或n残留物古1ll:Ij变化工3 方法提要 试问乙脂或乙酸乙黯提取氨础附阳阳柱峨阳沈州阳脱毗阳液敝浓帕缩脯后气采町色阳子监测模式进行测定，外标法定量。4试剂和材料瞥j/I I I 手殊规24. 1 乙脂:色
4、谱纯。4.2 叩苯s色i苦纯。4.3 乙酸乙赔。4.4 正己烧。/ 4.5 丙快氟卒胶(Flumioxazin.CHFN20 , .CAS. No: 103361-09-7)标准品=纯度大于99%。4.6 元水硫阪纳:650C灼烧4h.贮于密封容器中备用。4.7 乙脐饱和正己烧g取少是乙精加入正己;院中.剧烈振摇，并继续加入乙腊至出现明显分层，静置备用。4.8 LC-NH，氨基因丰n萃取性:3mL.0.5日或相当者。4.9 丙烘氟草胶标准溶液s准确称取适量的丙快氛草胶标准品，用乙肪配制成浓度为100g/mL的标准储备液，此洛液保存在棕色容量瓶中，在OC4C条件下保存。根据需要再用乙脂稀释储备液
5、，配制成适当浓度的标准工作液，在OC4C条件下保存。4. 10 基质标准工作溶液s基质标准工作溶液是将适量的丙烘氟草胶标准使用液，用空白基质提取液配成适当浓度的基质标准工作溶液。基质标准工作溶液应现用现配。SN/T 1983-2007 5 仪器和设备5. 1 气相色H-质谱仪2配有电子轰击源(Ell。5.2 旋转蒸发仪。5. 3 团相萃取装置.5.4 吹氮浓缩仪。5.5 旋涡混合器.5.6 离心机。5. 7 高速组织捣碎机。5.8 浓缩瓶，250m 1. o 5.9 离心管，15mL.50 m1. o 5. 10 微量注射器，101.06 测定步骤6. 1 提取6. 1. 1 大豆、大米及杏仁
6、称取5g试祥(精确到0.01g)于50m1.离心管中，用15mL乙精提取，充分振荡3min.于4000 r/min 离心3mn，将提取液移入另离心管中，分别用15mL, 10 mL乙脂重复上述操作一次，合并提取液到离心管中，加人5m1.乙脂饱和正己统(4.7)，振荡2min，于4000 r/min离心3min后，弃去正己炕层。将乙脂层转移至250mL浓缩瓶中，在450C水浴巾诚压浓缩至近干，加入2mL乙脯十甲苯(3+1)济解残渣，待净化。6. 1. 2 菠菜、苹果和姜称取5g试样(精确ilJO. 01 g)于50m1.离心官中，加入5g元水硫自主例，用15时，乙酸乙Mll提取，充分振荡3min
7、，于5000r/min离心3min，重复上述操作两次，合并上层irt液到250mL浓缩瓶中，在450C水浴巾减压浓缩至近干，加入2mL乙脂+甲苯(3十1)溶解残渣，待净化。6. 1. 3 鱼肉、鸡肉、猪肉和猪肝称取5g试样(精确到0.01g)于50mL离心管中，加人5g无水硫股钩，月115时，乙腊提取，充分振荡3min，于4000 r/min离心3min，将提取液移人另一离心管中.分别用15mL和10mL乙脂重复上述操作一次，合并提取液，在离心管中加入5mL乙H饱和正己烧(4.7)，振荡2min，于4Cr/min离心3 min后，弃去正己烧层。将溶液转移至250mL茄形瓶中，用5mL乙脂洗涤离
8、心管两次，并将洗涤液合并至浓缩瓶中，在450C水浴中减压浓缩至近干，加入2mL乙脂+甲苯(3十1)溶解残渣，待净化。6.2 净化用5m1.乙黯十甲苯(3+1)预淋t1.C-:，/H，氨基因相萃取柱，将提取液全部倾人萃取柱巾，再用12 mL乙脂+甲苯(3+1)分次注入萃取柱中进行洗脱，收集洗脱液。于45(:水浴中月1氮气吹去溶剂，用甲苯溶解并定容至1.0mL.供气相色谱一质谐和l定。6.3 气相色i昔-质i昔il!定条件6.3. 1 气相色i昔条件2 a) 包诸位，DB-5MS石英毛细管柱，30mXO.25 mm(内径)X 0.25m，或相当者;b) 载气:氮气，纯度大于等于99.995%;t直
9、流模式，流速1.0 m1./min; c) 包i吉柱程序升温条件260(2min旦旦旦3000COOmin); d 进样口温度，3200C;e) 进样方式z元分流进样.1 min后打开分流阀;SN/T 1983-2007 f) 进样量，2L。6.3.2 质谱条件a) 离子源温度，230C;b) 传输线温度;300C ; c) 电离方式:EI;d) 电离能是:70eV; e) 选择监测离子(rn/z):259，287，325，354.6.3.3 测定6.3.3. 1 定性测定在上述色谱条件下，丙快氟草胶的保臼时间约为19.9min，待测样品中化合物色谱蜂的保留时间与标准溶液相比变化范围应在土0.
10、25rnin之内。在扣除背景后的样品质谱图中，选择监测离子的丰度比与丙快氟草胶标准样品相关离子的相对丰度应一致，相似度在允差之内.见表1。丙;快氟草胶标准品的谱图参见附录A中图A.l、图A.2.表1丙烘氟草肢定性离子相对丰度比和最大允许偏差化合物定性离于(m/z)相对丰度比/%允许的相对偏差1%354.00 100 325.00 10 :!:50 287.00 33 士25259.00 18 土306.3.3.2 定量测定本方法采用外标法定量.定量离子为rn/z354;为减少基质对定量的影响，需用空白样液来配制所使用的基质标准工作溶液，根据样液中丙;快氟萃胶出峰悄况，选定响应值相近的基质标准工
11、作溶液进行定茧，标准工作液和样液等体积参插进样测定.标准工作溶液和样液中丙快氟萃胶的响应值均应在仪器检测的线性范围内。6.4 空白实验除不加试样外，按上述测定步骤进行。7 结果计算7. 1 计算公式及表述用色i苦工作站或按式()计算试样中丙;快氟草胶的含量，汁算结果须扣除空白值2式中2X=A.XCXV 一二一AsX m X一一试样中丙烘氟草胶含量，单位为毫克每于克(rng/kg); A 试样中丙;快氟革胶峰面积;A, 基质标准溶液中丙烘氟草胶峰面积，c 基质标准1在浓浓度，单位为毫克每升(mg/L); V一一样品溶液最终定容体积，单位为毫升(rnL); m 样品称样嚣，单位为克(g)。B 测定
12、低限、回收率8. 1 测定低限本方法的测定低限为:0.01rng/kg. ( 1 ) 3 SN/T 1983-2007 8.2 回收率丙快氟草胶添加浓度及回收率的实验数据见表20表2丙快氟草肢添加回收率数据样品名称添加浓度!(glkg)回收率1%10 84.5-98.6 大米20 91. 0-102.。200 95.0-102.5 10 80.3-88.6 大豆20 83.5-95.5 -.-Z5飞88.0-94.5 1可73.4-89.6 菠菜2 币; 亏一94.0-100.5 _/ 200 ry a3bi / 88.0-100.5 / 13 , /. 88.1-99.6 苹果/ JZ5 9
13、1. 5-97. 0 / / ?OO 90.5-99.5 10 78.5-92.2 如杏仁2(一1 87.5-95.0 2年叮M200 86.0-92.。问/, 10 87.8-94.3 猪肉/ / 2号气92.5-105.0 M侈(;飞内南飞，卢 嘎86.0-93.5 J。85.6-94.1 鸡肉户。90.5-107.0 1-1 200 ./ 88.5-94.0 ! 10 I 75.8-92.8 鱼/ 20 I / 96.5-105.5 /. 200 L/ 94.5-100.0 10 74.1-82.1 猪肝20 82.5-91. 5 200 87.0-95.。10 73.4-82.3 姜2
14、0 82.5-90.5 200 78.5-87.5 4 SN/T 1983-2007 附录(资料性附录)标准晶离子流色谱图A m Abundance 800 FEBEEBEL 700 600 500 26.00 24.00 22.00 20.00 400 300 200 100 丁，m，一-吾国件届600 550 ，二吁A咽hB与自吧。鬼附伯当41im-22，咱AE哥国1a5-E守-zfa-JAwptrAbundance 4000 1 1 000 I 500 3 500 2 000 1 500 3000 2 500 450 400 350 oo 250 100 50 。m/z_ 5 芮烘氟草肢
15、标准品EI全扫描质谱图面A.2SN/T 1983-2007 Foreword Annex A of this standard is an informative annex. This standard was proposed by and is under the jurisdiction of the Certification and Accreditation Administration of the Peoples Republic of China. This standard was drafted by Shenzhen Entry-Exit Inspection and
16、 Ouarantine Bureau ,Shandong Entry Exit Inspection and Ouarantine Bureau , Liaoning Entry-Exit Inspection and Ouarantine Bureau of the People s Republic of China. The main drafters of this standard are Lan Fang , Lin Li, Xie Liqi , Ye Gang , Hou Lexl , Wang Jianhua, Wei Feng and Jin Baohui. This sta
17、ndard is a professional standard for entry-exit inspection and quarantine of the Peop怡sRe public of China promulgated for the first time. Note: This English version.a translat旧nfrom the Chnese text. is solely for guidance 6 SNjT 1983一20071 Scope Determination of flumioxazin residues in food for impo
18、rt and export GC-MS method This standard specifies the method of determination of flumioxazin residue in foods by gas chroma tography-mass spectrometry. This method is applicable to determine and confirm flumioxazin residue in apple. spinach. ginger. fish.chicken.pork.soybean.rice.pork liver and alm
19、ond for import and export. 2 Sample preparation and storage 2. 1 Cereals. seeds and nuts Take 500 9 sample. grind thoroughly. and let them pass through 2.0 mm sieve.日lenduniformly and seal. then store them in - 4C blow. 2.2 Fruits. vegetables and ginger Take 500 9 sample.get the edible parts of the
20、frui饵.vegetablesand ginger to prepare.blend uniform Iy and seal as test samples. Mark and store them in -lBC refrigerator 2.3 Animal-source foods Take 500 9 sample.get the edible parts of the animal-source food and mash to pieces with the high speed grinder. Blend uniformly and seal. then store them
21、 in - lBt refrigerator. In the course of sample preparation. precautions should be taken to avoid contamination or any fac tors which may cause the change of residue content 3 Principle The flumioxazin residue in the test sample is extracted with solvent. After cleaned up by a LC-NH, solid phase car
22、tridge. the residue is determined by gas chromatography-mass spectrometry. and quantified by external standard method. 7 SN/T 1983-2007 4 Reagents and materials Unless otherwise specified, all reagents used are analytical grade Or higher one. water is distilled water. 4.1 Acetonitrile.chromotography
23、 grade. 4.2 Methylbenzene.chromotography grade 4.3 4.4 4.5 4.6 4. 7 4.8 Ethyl acetate. .1 Hexane.! I Flum刷azin(CH15FN，CAS No. ，1阴6(09-7)阳ndard:Pu川囚%.f /F/J Anhydrous s币diumsulfate,lgnife at 650 C for4 h.and keep in a tight closed container. F ., Acetonitrile-methylbenzne 99.995%;flow rate,1.0 mL/min
24、; 15t/min c) Column temperature,60t (2 min)一一一一300t(10 min); d) Injection port temperature,320t; e) Inject mode,split less.open the split valve after 1 min; f) Injection volume，2L 6.3.2 MS operating conditions a) lon source temperature,230t , b) Transferline temperature,300t , c) lonization mode,EI
25、, d) lonization energy, 70 eV , e) Selected monitoring ions (m/z) ,259.287.325.354. 10 SN/T 1983-2007 6.3.3 Determination 6.3.3. 1 Oualitative determination As the conditions above. the referenced retention time of flumioxazin is 19.9 min; Annex A is the chromatogram of the standard solution. The st
26、andard deviation of the flumioxazin retention time in sample and the one in standard solution. should be :t O. 25 min. After subtracted background noise. the Selected monitoring ions should be appeared in spectrum. the relative standard deviation of the relative abundance ratios of sample ions and t
27、he ones of standard must meet the demand as table 1. Table l-Maximum permitted tolerance for relative ion intensities using a range of mass spectrometric techniques Selected monitoring ions (m/z) relative abundance ratios/% Maximum permitted tolerance/ % 354.00 1口。325.00 10 :t 50 287.00 33 士25259.00
28、 18 :t 30 6.3.3.2 Ouantitative determination Prepare matrix calibration solutions containing fiumioxazin at ap口ropriateconcentrations using blank sample extracts. The calibration solutions should be injected in between the inject旧nsof sample so lution of equal volume. The responses of calibration so
29、lutions and sample solutions should be within the linear range. The quantitative ion of fiumioxazin is m/z) 354目6.4 81ank test The operat旧nof the blank test is the same as that described in the method of determination. but with omiss旧nof sample addition. 7 Calculation and expression of result The ca
30、lculation of herbicide content in the sample is carried out by GC/MS data processor or accord ing to the following formula 1) the blank value should be subtracted from the result of calcula tion) , X=A_XCXV As X m ) 1 ( . . . . . . . . . . . . . . . . . . . . . . . . . . 11 SN/T 1983一2007where X-the
31、 residue content of flumioxazin in the test sample.mg/kg; A -Peak area of flumioxazin in the sample solution; As-Peak area of flumioxazin in the matrix calibration solution; c-the concentration of flumioxazin in the matrix calibration solution.mg/L; V the final volume of sample solution. mL; m-the w
32、eigh of the test sample.g. 8 Limit of determination and recovery 8. 1 Li mit of determination The limitid is O. 01 mg/lcg 才-iJenes of flumioxazi Sample name pike can白nt削onl阳g!kg)Recove叩/%1且一-_J 84.5-98.6 nce 20 / 91. 0-102. 0 L_ i 200( 95.0-102.5 / j 80.3-88.6 soybean 2手f叫183.5-95.5 i 200 J 88.0-94.
33、5 ,.0 J j 73.4-89.6 spinach 、马.-20J 94.0-100.5 飞200 F r f 88.0-100.5 10 / F 88.1-99.6 apple 20 91. 5-97. 0 200 90.5-99.5 10 78.5-92.2 almond 20 87.5-95.0 200 86.0-92.0 10 87.8-94.3 pork 20 92.5-105.0 200 86.0-93.5 12 SN/T 1983-2007 Table 2 (continued) Sample n刽meSpike concentration/ (g/kg) RecQve叩/%
34、10 85.6-94.1 chicken 20 90.5-107.0 200 88.5-94.0 10 75.8-92.8 fish 20 96.5-105.5 200 94.5-100.0 10 74. 1-82. 1 liver .20 82.5-91.5 1 200 87.0-95.0 10 73.4-82.3 一20/ gmger 82.5-90.5 _.oO ./ 78.5-87.5 f 、1311/ / fii p飞i飞飞11 、飞二、地、马-=-13 SN/T 1983-2007 Annex A ( Informative) Total lon Chro町、atogra1of s
35、tandard Abundance flumio:xazin 800 700 600 500 400 300 200 100 Time _ 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.()O 26.00 Figure A. 1-Total lon Chromatogram of flumioxazin standard Abundance 4000 I 354 3 500 3 000 2 500 2 000 1 000 1 500 。且-mz-.I归8卢50 100 150 200 250 300 350 400 450 500 550 m!z Figure A 2 Mass spectrogram of fiumioxazin standard 14 中华人民共和国出人挠检验检疫行业标准迸出口食品中丙抉氟草肢残留量检测方法气相色谱，质谱法SJ/T 1983-.2007 据中国标准出版社出版北京复兴门外三里河北街16号邮政编码:100045 网址电话，6852394668517548 中国标准出版社秦皇岛印刷广印刷4幡开丰880X1230 1/1 6 印张1.25 字数28千字2007年11月第一版2007年11月第一次印刷印数1-2000晤书号，155066 2-18268 定价12元
