1、5 中华人民共和国出入境检验检疫行业标准SN/T 1984-2007 进出口可乐饮料中有机磷、有机氯农药残留量检测方法气相色谱法Determination of organophosphorus and organochlorine residues in cola drink for import and export-GC method 2007-08-06发布2008-03-01实施结在:中华人民共和国发布吧?7国家质量监督检验检疫总局本标准的附录A为资料性附录。. 牟目。-E司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:中华人民共和国深圳出入境检验检疫局。SN/T 1
2、984-2007 本标准主要起草人z肖来龙、唐少冰、靳保辉、林秀云、何军、陈沛金、蓝芳、林黎、吴卫东。本标准为首次发布的出入境检验检疫行业标准。SN/T 1984-2007 进出口可乐饮料中有机磷、有机氯农药残留量检测方法气相色谱法1 范围本标准规定了可乐饮料中11种有饥磷、有机氯农药残留莹的气相包i昔测定方法。本标准适用于iT乐饮料中敌敌畏、毒死舰、马拉硫磷、对硫磷、七氯、六氯苯、六六六及其异构体(六六六、六六六、Y六六六、3六六六)、五氯硝基苯等11种有机磷、有机氮农药残留量的检测。3 试剂材料除另有说明外，所用试剂均为分3. 1 正己炕2色i古纯。3.2 fp醇=色i古纯。3.3 乙酸乙
3、i1l，优级纯。、一1川3.4 元水硫酸纳:经650C灼烧4h，直3. 5 q;化的。M 氮氧化锅。Ij I /, 3.7 浓硫酸z优级纯。，l I 1 3.8 fjl醇+水溶液(5+95)，量取51L1111(3. 2)岛95叫，水混合i川T 3.9 甲醇+水溶液(O十90)，量取11. m L lf.享(3;2)与90mL水混合。I3. 10 氮氧化纳浓浓，1mol/L，称20氮氧的，m水1寄并定在军至500tlL。3. 11 农药标准物质z敌敌畏(C.CI20，P， CAS恬.62-17l、毒E蝉(C9HCI, NO, PS, CAS NO.2921创-2)、马拉硫磷(C1oHO，PS次
4、ASNo. 121-.75-5)、对范院(c，HNO，PS，CASNo. 56-38-2) -._ ，飞/-_. 0, 为固体标准，纯度大于96.0%;七氯(C，H，Cti可(:ASNo.76-44-11阿穴氮苯(C，ClCASNo. 118-74-)、六六六(C，I!，Cl钮，CASNo. 319-84-6)、严六六六(C，H，ClCASNo. 319-85-7)、Y六六六(C，H,Cl CAS No. 55963-79-6) JJ六六六(C，H, CI, , CAS No. 319-86-8)、五氯硝基苯(C，CIoN02, CAS No. 82-68 8)为标准液体，体积1m!.浓度为1
5、00mg!L。3. 12 有机磷农药标准溶液a) 有机磷农药标准储备溶液2准确称取适量质量的敌敌畏、毒死牌、马拉硫磷、对硫磷，分别用丙酣溶解并定容至棕色容量瓶中.浓度相当于1000 mg/L，储备液于18C以下保存。b) 有机磷混合标准中间济液g准确吸取适量敌敌畏、毒死蝉、马拉硫磷、对硫磷标准储备溶液于棕包容最瓶巾，用丙丽定容至刻度，各种有机磷农药标准溶液的浓度为10mg/L，此中间溶液于18C以下保存。c) 有机磷混合标准工作溶液用乙股乙酣将混合标准中间溶液按需要运级稀释，配制为4种有机磷农药混合标准工作溶液.混合标准工作溶液在OC4 C保汗。- SN/T 1984-2007 3. 13 有
6、机zi农药标准溶液za) 有机氯农药混合标准巾l可;在液z移取适量体积的七氮、六氯苯、六六六混合标准溶液、五氯硝基苯标准溶液于棕缸容量瓶中，用正己J:，t定容至刻度，各种有机氯农药标准溶液的浓度为10 mg/L，此中间溶液于一18C以下保存。b) 有机氯混合标准工作溶液z用正己炕将混合标准中间溶液按需要逐级部释，配制为有机氯农药混合标准工作溶液，混合标准工作溶液于0C4C保存。3.14 HLB团相萃取小柱，60mg , 3 mL或相当者。4 仪器和设备4. 1 气相包谱仪，自己电子俘获检测器(ECDl和火焰光度检测器(FPDl磷il光片，波长525nmo 4.2 旋涡混合器。4.3 离心机。4
7、.4 吹氮浓缩仪。4.5 固相萃取装置。4.6 旋转蒸发装置。4.7 分液漏斗，500mL。4.8 靡口玻璃回底烧瓶，500mL。4.9 破璃砂芯漏斗。4. 10 聚丙烯具寒离心管，15m!.。5 测定步骤5. 1 有机磷、有机氨农药的提取取可乐样品于烧杯中，放置60mn，并用玻璃棒搅拌tlr气。准确称取150g(和确至O.01 g)在可乐样品中加入1mol/L的氮氧化纳溶液调节溶液pH值至7左右。将调节至中性的可乐样品转移至500 mL分液漏斗中，加入15g氧化的相乙自主乙陆100mL，!:!振荡2min并不时tlr气.mt置10min 后，取上层有机徊，过预先填充的无水硫酸纳柱(在玻璃砂芯
8、漏斗中装入15g左右元水硫酸的，并用20 mL乙酸乙四EI悻洗)，收集于500mL因底烧瓶中。在分液漏斗中分两次加人200mL乙股乙阳，每次100 mL，重复以上提取步骤，合并提取液于40C水浴下旋转蒸发至3mL4 mL.转移至15mL离心管中，用9mL正己炕分三次洗涤困底烧瓶.合并洗涤液于15mL离心管中.40C水浴下吹氮近干。5.2 净化5.2. 1 有机磁农药测定样品溶液净化HL日固相萃取柱使用前分别用乙民主乙陆3mL淋洗一次.3mL甲醉和3mL lj(预处规两次，保持住体湿润。将5.1中提取?在用5mL 10%甲醇水溶液洛解，以每秒1淌速率过HLB肉相萃取柱.弃去流出液，再用10mL
9、5%甲醇水溶液润洗离心管并上HLB柱.弃去从HLB柱流出的泪洗液，真空刊干小柱10mi口。用9mL乙酸乙自.!t行i先脱，收集i先脱液于15mL离心管中，加入3g无水硫酸纳，振荡3 min, S 000 r/min条件下离心2min，将溶液转移至另一离心管中，于40C水浴巾吹氮浓缩近干，111乙酸乙目吕定容至1.0 mL.供气悦色i芹FPO测定，5.2.2 有机氯农药测定样品溶液净化将5.1中提取j应用1mL正己统治解.加入0.5mL浓硫酸，手动轻摇i昆匀，5000r/min离心5min 后，取上层有机相进气相色i苦ECO测定，如净化效果不充分，可再加入浓硫酸净化一次。5.3 imlj定5.3
10、. 1 气相色i曹电子俘获检测仪器条件a) 包诸位，OB-5石英毛细管柱，30mXO. 32 mm(内径).膜J!J.O. 25 l1.m，戎相当者;2 SN/T 1984-2007 30 C /min _ 3吃/mnb) 色i苦柱温度，80C(1 min)一一一一180C一一一205C(4 min)一一:21OC(1 min) , pos-trun,280C( min) , c) 进样口温度，250C，d) 检测器温度，300C，e) 载气z氮气，纯度99.999%，恒压0.135MP的。进样量，L;g) 进样方式g分i流进样.分流比12 1, 5.3.2 气相色谱火焰光度检测仪器条件a)
11、色谱柱，D3-1701石英毛细管柱，30mXO. 32 mm(内径)，膜厚0.25m，戎相当者:30(:/01in _ _ _ IO C /min b) 色i吉柱温度，90C(min)一一一一210C(8min)一-一一:240C，po，号trun，280C(5min) , d 进佯口温度:2S00C;d) 检测器温度，250C，e) 载气:氮气，纯度99.999%，但压0.071MPa , f) 迸样量，2L;g) 进样方式:不分流迸样.1.0 min后打开分流阀，吹扫流量50mL/min。5.3.3 色谱测定f斗视溶液分别进气相色i常电子俘获检测手u气相色i苦火焰光度检测，根据样液中被测有
12、机磷或有机氯残留的含fit情况，选定峰面积相近的标准工作溶液.标准工作溶液和样液中有机磷或有机氯残留的响应值均应在仪器的检测线性范围内。对混合标准工作溶液和样液等体积分组分参差进样测定，外标法定景。在5.3.1色i吉条件下，敌敌畏、毒死抑、马拉硫磷、对硫磷的保留时间分别约为4.750 min、11. 246 min、12.028min、13.250min , 5.3.2包谱条件下r六六六、六氯苯、严六六六、沪六六六、五氯硝基苯、8六六六、七氯的保留时间分别约为9.657 min、9.924 min、10.378 min、10.591 min、10.749 min、11.284min、13.07
13、2min , I011g/L有机磷和有机氯混合标准工作溶液色i普图分别参见附录A图A.1.图A.2，5.3.4 空白试验除不加标样外，按上述测定步骤进行。5 结果计算和表述按式()+:算试样中有机磷、有机氯农药化合物的含量，计算结果需扣除空白值。) l ( . . . . . . . . . . . . . . . . . . . . . . . . . . 式中zX 样品中有机磷、有机氯农药化合物含RT.单位为主吉克每千克(mg/kg), A 样液中有机磷、有机氯农药化合物峰jfi积:A, 标准工作溶液中有机磷、有机氯农药化合物峰商积;c 标准工作溶液巾有机磷、有机氯农药化合物浓度，单位为毫
14、克每升(mg/U，m 称取的试样景，单位为克(g)，V 样液最终定容体积，单位为毫刑(mU，7 方法的测定低限、回收率7. 1 测定低限本方法有机磷、有机氮农药测定低限均为O.000 1 mg/kg, 7.2 回收率不同样品回收率数据见表1。3 SN/T 1984-2007 表1可乐中有机磷、有机氯农药不同添加水平回收率范围样品添加水平j(mg/kg)回收卒范围/%0.000 1 72.0-105.0 敌敌畏0.000 2 76.0-99.5 0.000 5 72.8-102.4 0.000 1 78.0-98.0 毒死蝉0.000 2 79.0-95.5 0.000 5 75.8-91. 2
15、 0.000 1 64.0-88.0 马拉硫磷.币，口。077.0-87.0 O.毛O-:;75.4-86.2 b事-辄牛O.号)1J 75.0-87.。对硫磷/ O. 000 2 ,i/ 81. 0-92. 0 / C.EE, 。且一J 77.4-89.4 f v .,.iY:OO 1 82.0-98.0 六六六- 81. 5-95.。句，C.CO3户在九邸.2-99.。0.000:.1 92.0-106.0 -俨萨.咀【咀-六氯苯O.J)lj品85.0-104.5 / 叮/0.0川军 89.0-106.0 / / 。:rcQ.I 飞73.0-98.0 乒六六六O. O_J.T乍飞飞82.0
16、-90.0 ,;/ c, hoo 5 83.4-91. 2 o 0I 8 1. 0-101. 0 y.六六六1./ 40/ 84.5-100.5 飞, 血。00/ 89.8-104.6 ,/ 0.000 / 85.0-98.0 五氯硝基苯k甲J0.000，_/. 8 1. 5-97. 5 0.000 5 84.6-97.8 0.000 1 79.0-97.0 六六六0.000 2 76.0-90.0 0.000 5 76.2-91. 0 。.0001 81. 0-109. 0 七氧0.000 2 88.5-107.0 0.000 5 94.8-104.2 4 附录A(资料性附录)标准溶液色谙图
17、FPOl (COLA-PRE飞COLA-P2006-12-16 22-51-40,SI.0) 。150 pA 60 40 20 。20 h N .,. 1一一敌敌畏$2 毒死脾s3 马拉硫磷s4 对硫磷.2 ECDJ A(SZ2SLD) H, 220 200 180 160 140 120 100 80 60 9.5 10 l-a-六六六$2 六氯苯33 严六六六，2 4一一五氯硝基苯$5-Y-六六六g6-8-六六六$7一一七氯.std-lOppb SN/T 1984-2007 2 3 4 -剧唱-协.12 14 mm 7 13 13.5 mm 图A.210 f1g/L有机氯农药标准溶液色诺固
18、5 SN/T 1984一2007Foreword Annex A of this standard is an informative annex. This standard was proposed by and is under the charge of the Certification and Accreditation Admin istration of the Peoples Republic of China. The standard was drafted by Shenzhen Entry-Exit Inspection and Quarantine Bureau o
19、f the People s Republic of China. The main drafters of this standard are Xiao Lailong. Tang Shaobing. Jin Baohui. Lin Xiuyun.He Jun, Chen Peijin , Lan Fang , Lin Li and Wu Weidong. This standard is an Entry-Exit inspection and quarantine professional standard of the People s Repub lic of China promu
20、lgated for the first time. Note: Ths English version. a translation from the Chinese text. is solely for guidance. 6 SN/T 1984-2007 Determination of organophosphorus and organochlorine residues in cola drink for import and export -GC method 1 Scope This standard specifies the methods of determinatio
21、n of 11 organophosphorus and organochlorine residues by gas chromatography in cola drink This standard is applicable to the determination of organophosphorus and organochlorine residues of dichlovos, chlorpyrifos , malathion , parathion，-666.-666. Y卢666.-666.heptachl町.hexachloro benzene. pentachloro
22、nitrobenzene in cola drink. 2 Principle The residues of organophosphorus in the test sample are extracted with ethyl acetate. After cleaned up by passing through a HLB cartridge. the residues ate determined by a gas chromatograph with FPD detector usihg external standard method. The residues of orga
23、nochlorine in the test sample are extracted with ethyl acetate. After cleaned up by sulfuric acid treatment. the residues are determined by a gas chromatograph with ECD detector u sing external standard method 3 Reagents and materials Unless otherwise specified. all reagents should be of analytical
24、grade, water is the redistilled water. 3.1 Hexane: Grade for GC residue analysis. 3.2 Methanol: Grade for GC residue analysis 3. 3 Ethyl acetate, GR. 3.4 Anhydrous sodium sulfate, Ignite at 650C for 4 h. and keep in a tightly closed container. 3. 5 Sodium chloride. 3.6 Sodium hydroxide. 7 SN/T 1984-
25、2007 3.7 Concentrated sulphuric acid. GR 3.8 Methanol-water solution(5 + 9日.3.9 Methanol-water solution (10+90). 3.10 Sodium hydroxide solution , 1 mol/L: Accurately weigh 20 9 sodium hydroxide, dissolve and dilute with water to 500 mL. a) stock s川c) 3. 13 Organochlorine pesticides standard solution
26、: a) Mixture midst solution: accurately measure organochlorine pesticides standard solution , dilute with acetone to form a standard working solution of 10 mg/L in concentration. The solution can be preserved in the temperature below -18t. b) Standard working solution: according to the requirement.
27、accurately measure an adequate vol ume of organochlorine pesticides mixture midst solution , dilute with n-hexane and prepare a standard working solution of appropriate concentration. The solution can be preserved in the temperature at ot -4t. 8 SN/T 1984一20073.14 HLB cartridge: 60 mg. 3 mL or equiv
28、alent. 4 Apparatus and equipment 4.1 Gas chromatograph equipped with ECD and FPD in phosphorus mode. 525 nm. 4.2 Mechanical shaker. 4.3 Centrifuge. _电-4.4 Nitrogen evaporator. r 阳电严宿叩a叫_._._;丰且事世可4.5 Solid phase extraction. 4.6 Rotary evaporator. 4.7 Separating Funnels: 5 4.8 Evaporative flask. K.Q.
29、，_5.mL.-.由甲午一一吨，担4.9 4.10 Filter funnel. 叫ropylene町r阳tlJbi215j y 5 Procedure L. withrew cup: / j f r飞、5. 1 Organophosphon品ol:aanochlo阳epest_jcides ，xtracti叫飞II j I._ / Ii -f 丁._. . , l. j7 Transfer Cola samples in a beakr.foC6min with p也iodcstiring by a glass stick to discharge CO, and adjust pH val
30、ue of cola sample to 7 by adding 1 mol/L NaOH. Accurately weigh 150 9 of the sam. ple(accurate to 0.01 g). Transfer the sample to a separating funnel. add 15 9 NaCI to the samp恼，seal. and shake to dissolve sal t. Add 100 mL ethyl acetate to the separating funnel. seal. and shake 2 min vigorously wit
31、h periodic venting to release excess pressure. Allow the organic layer to sepa. rate from the water phase for a minimum of 10 min. The organic layer is passed through 15 9 anhy. drous sodium sulfate to remove residual water. Add a second 100 mL volume of ethyl acetate to the separating funnel and re
32、peat the extraction procedure a second time. combining the extracts in the evoperative flask Perform a third extraction in the same n回nner.Evaporate the sample extract to 3 mL-4 mL on a rotary evaporator using a water bath at 4OoC. Transfer the extract to a 15 mL graduated test tube. Rinse flask 3 m
33、ore times with 9 mL n.hexane and transfer each rinse to the same test tube. Evaporate the extract to near dryness in a water bath at 40t under a gentle stream 9 SN/T 1984-2007 of nitrogen 5.2 Cleanup 5.2. 1 Cleanup for determination of organophosphorus residues Precondition HLB cartridge by 3 mL eth
34、yl acetate, 3 mL methanol and 3 mL water. Reconstitute the sample residue of 5. 1 with 5 mL of 10% methanol-water solution , allow the sample to pass through HLB cartridge at the rate of about 1 drops. Oiscard the column eluate. Rinse the test tube 3 times with 10 mL 5% methanol-water and transfer e
35、ach rinse to HLB cartridge. Oiscarb the rinse and dry the cartridge for 10 min. Elute the analytes into a clean 15 mL test tube with 9 mL ethyl acetate. Add 3 9 anhydrous sodium sulfate into ethyl acetate solution , blend for 3 min in vortex mixer. centrifuge for 2 min (5000 r/min). Transfer organic
36、 solution into another 15 mL centrifuge tube. Concentration the organic phase to near dryness in a water bath at 40t under a gentle stream of nitrogen. Oissolve the residues and dilute exactly to 1.0 mL with ethyl acetate. The solution is determined by GC-FPO 5.2.2 Cleanup for determination of organ
37、ochlorine residues Reconstitute the sample residue of 5. 1 with 1 mL of n-hexane, add O. 5 mL concentrated sulphuric acid ,shake gently,and centrifuge for 5 min(5 000 r/min). The upper organic solution is determined by GC-ECO. 5.3 Oetermination 5.3. 1 GC-ECO operating conditions a) Column , OB-5 cap
38、illary column , 30 m X O. 32 mm X O. 25m or equivalent; 30t/min .o.-. 3C /min _ ,. ., 2t/min b) Column temperature , 80t (1 min) _:一一-180t一-一205t(4 min)一:21Ot(1 mir忡，postrun ,280t (1 min); c) Injection port temperature,250t. d) Oetector temperature,300t e) Carrier gas;Nitrogen，Purity二三99.999%,consta
39、nt pressure O. 135 MPa; f) Injection volume; 1L. g) Injection mode,Split ratio is 12 1. 10 SiljT 1984-2007 5.3.2 GC-FPD operating conditions a) Column ,DB-1701 capillary column ,30 m X O. 32 mm x O. 25m or equivalent; 30t/min _ _O ,_ 10C /min b) Column temperature ,90C (1 min)一一一2100C(8 min)一一一一2400
40、C, postrun ,280 C (5 min); c) Injection port temperature, 2500C ; d) Detector temperature,250oC; e) Carrier gas ,Nitrogen.Purity?99. 999% .constant pressure O. 071 MPa; f) Injection volume, 2L; 日)Injection mode, Splitless. purge on after 1.0 min, purge Ilow is 50 mL/min. 5.3.3 GC determination Accor
41、ding to the approximate concentration 01 organophosphorus and organochlorine residues in the test sample solution. the standard working solution is selected with similar peak area to that 01 sam ple solution. The response 01 pesticides in the standard working solution and sample solution should be i
42、n the linear range 01 the instrumental detection. The standard working solution should be injected randomly in between the injections 01 sample solution 01 equal volume. Under the above 5. 3. 1 chro matograph condit旧用.the retention time 01 dichlovos. chlorpyrilos, malathion. parathion is about 4.750
43、 min. 11.246 min , 12.028 min. 13.250 min respectively. Under the above 5.3.2 chromato graph conditions. the retention time 01-666， hexachlorobenzene，卢-666.r -666. pentachloronitro benzene ,8.666. heptachlor is about 9. 657 min. 9.924 min. 10.378 min.10. 591 min , 10.749 min , 11.284 min. 13.072 min
44、 respectively. The chromatogram 01 10g/L organophosphorus and organo chlorine pesticides standard solution can be lound in annex A(ligure)A. 1 and ligure A. 2 5. 3. 4 Blank test The operation 01 the blank test is the same as that described in the method 01 determination. but with omission 01 sample
45、addition. 6 Calculation and expression of result The calculation 01 organophosphorus and organochlorine residues content in the sample is according to the lollowing lormula (门.the blank value should be subtracted Irom the result 01 calculation , X=A:cV 一二As.m . ( 1 ) 11 SNjT 1984-2007 where X-the re
46、sidue content of organophospnorus or organochlorine residues in the test sample.mg/kg; A -Peak area of organophos口horusor organochlorine residues in the sample solution; A ,-Peak area of organophosphorus or organochlorine residues in the standard working solution; C the concentration of organophosph
47、orus or organochlorine residues in the standard working solu tion. mg/L; V-the final volume of sample solution. mL. m一thecorresponding mass of test sample in the final sample solution.g. 7 Limit of determination and re奴曹77.1 Limit of determination一丁;/ 二/，.fTr少时ormeThe limit of determination of testi
48、ng 0.000 1 mg/kg 叫m s刊川SI川川m川川n川川巾t怕阳仙he阳e盯r7.2 Recovery According to the experimental data f sample 明f创centr.手。n/(时/kg)L recovery range I % t7二二飞0.00 fr、172.0-105.。dichlovos f 76.0-99.5 72.8-102.4 /J 78.0-98.0 chlorpyrifos 79.0-95.5 飞:- 0.0005/ !J 75.8-91.2 飞飞正LOOO1drzfJ 64.0-88.0 口回国thion0.0口0277.0-87.0 0.000 5 75.4-86.2 0.000 1 75.0-87.0 parathion 0.0002 81.0-92.0 口.000577.4-89.4 口.000182.0-98.0 .666 0.0002 81. 5-95. 0 0.0005 88.2-99.0 12 SN/T 1984-2007 Table 1 (continued) sample fortified concentration/ (mg/kg) recovery range! % 0.000 1 92.
