【商检行业标准(SN)】 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

中华人民共和国出入境检验检疫行业标准SN/T1984—2007
进出口可乐饮料中有机磷、有机氯农药气相色谱法
残留量检测方法
Determination of organophosphorus and organochlorineresidues in cola drink for impori and export-GC method2007-08-06发布
中华人民共和国
数码防钠
国家质量监督检骑检疫总局
2008-03-01实施
本标准的附录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推起革单位：中华人民共和国深圳出人境检验检疫局。SN/r1984—2007
本标准主要起草人：肖来龙、店少冰、靳保辉、林秀云，何军，陈浦金、蓝芳、林黎、是卫东。本标推为首次发布的出人境检验检疫行业标准。1范围
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
本标雅规楚了可乐饮料中11种有机磷,有机氮农药残留量的气相色谱测定方法。SN/T 1984—2007
本标催透用于可乐饮料中敌敌畏、毒死蜱、马拉硫磷、刘破磷、七氮、六氮苯,六六六及其异构体（α-六六六、六八、？六六、8穴八六）、五氯基苯等11种有机磷、有机氟农药残留量的检洲。2方法提要
试样中有机磷残留经乙酸艺脂萃取，无水琉設链脱水，旋转蒸发后转移至离心管中，吹氮近于.10%甲醇水溶液溶解，过II1.I3柱净化，气相色谱火焰光度检测器测定，外标祛定氧。试样中有机残留经乙酸乙脂萃取，光水硫酸钠水，旋转茶爱后转移至离心管中，吹氮近下，正己烷定穿，磺化净化，气相色谱电子俘获检测器测处，外标法定量3试剂材料
除另有说明外，所用试剂均为分析纯，水为重然水。3.1正己烧：色谱纯。
3.2 伊醇:色谱纯。
3.3乙酸乙酯：优级纯。
3. 4无水硫酸钠:经 650℃灼烧4 h,置3.5叙化钠。
3.6氢氧化钠。
3.7浓硫酸：优级纯
特伊多
3.8醇+水溶液(5+95),盘取5 许印醇(3.2)毒5 ml.水混金3.9中醇+水溶液（10+90，量取L典配（3/2）与90mL水混合3.10氢氧化钠溶液，1mbl/L;称20鼠氧花衡，用水溶郁并定磨室 500hL。3. 11农药标推物质： 敌敌畏(C,H,CI,O,P,CAS N6. 62-T3-7)、毒死蜱(C,Hu C1.NO,PS,CASNo. 2921-88-2),马拉硫磷(CnII,0),FS.,CA$ No. 321-75-5).对磷(C,H,N(,PS,CAS No. 56-38-2)为固体标准.纯度大下 96. 0%,七氟(C.H,C1,ASNo. 7G-41-8六兴氯苯(C,Cl.,CAS No,118-74-1)、r-六六六(C H,TI ,CAS No. 310-84-6) ,3六六六(C HC):-CAS No. 319-85-7),-六六六(C, HCl CAS No. 55963-79-6),8-A六(C,H,Cl,CAS No. 319-86-8),H氯硝基(CCI,NO,,CAS No. 82-68-8)为标准液体，体积1ml,浓度为100mg/l.。3.12有机磷农药标准辫液：
a）有机磷农药标准储备溶液：准确称取适最质最的敌敌皮、声死蜱，马拉硫磷、对碰磷，分别用闪谢游解并定容至棕色容辈瓶中，度相当于1000 m/1,储备液于--18℃以下保存。有机磁混合标准中间溶液：准确吸取适鼓敌敌畏、毒死摔、马拉硫磷、对硫磷标雄储备溶被于by
棕色容抵瓶中,用内酮定容至刻度.齐种有机磷农药标准溶液的浓度为10 mg/L.此中间溶護于—18℃以下保存，
有机磷混合标准工作游液：用乙酸乙酯将混合标中间溶液按需要逐级稀释，配制为4种有机e
磷农药混合标准工作液.混合标准工作溶液在0℃～~4保存。1
SV/T 1984--2007
3.T3有机筑农药标准获液：
）有机氧农划混合标推中间溶液：移取适量作积的主鼠、六氛来、六六六混合标准落液、氧硝基苯标准游液于标包容量瓶中，用正已烧定容至刻度，各种有机氯农药标准渐液的浓度为10mg/1..此中间溶被于—18℃以下保存。b）有机氯混合标准工作溶液：用正已烷将混合标准中间溶液按需要逐级稀释，配制为有机氯农药据介标准工作溶液，混合标准工作溶液于0保存。3.14HLB固相萃取小柱：60mg.3ml.或相当者4仪器和设备
4.1气相色谱仪，配电了伴获控测器（ECD）和火焰光度检测器（FFD）磷滤光片-波长525nm。4.2施涡混合器。
4.3离心机。
4.4吹氮浓缩仪。
4.5開相举最装置。
旋转蒸发装置。
分液溺斗：500mL。
4.8磨口玻璃阈底烧瓶：500ml.。4.9玻璃砂芯溺斗。
4.10聚内烯具寒离心管：15mL。5测定步骤
5. 1有机磷、有机氯农药的提取可乐样品于烧杯牛放置60min.并用戒璃摔揽拌排气。准微称收150（精确0.01g）在可乐样品中加人1ml/1.的氧化钠溶液调节溶液pH值至了左有，将调节轻中性的可乐样品转移至500ml分波游斗中，加人15g氧化钠和乙酸艺酯100ml刷烈振荡2min并不时排气，静置10min质、玻上层有机扣，过预先填充的无水硫散钠柱（在玻璃砂芯渐斗中装人15名左右死水疏酸钠，并用20m1.乙酸乙酷淋洗），收集于500ml.圆底烧班。在分液斗中分两次加人2001ml.乙数乙，每次100mL，重复以1提取步骤，合并提取液于40%水浴下旋转蒸发至3ml.~4ml转移至15ml离心管中，用9ml正己烷分三次洗涤圆底烧瓶，合并洗涤波于15ml.离心管中，40℃水浴下吹氮近干。5.2净化
5.2.1有机磷农药测定样品溶液净化H1.F固柑萃取柱使用前分别用乙酸乙醋3ml.淋洗一次.3mI.年醇和3mL水预处现两次：保持杜体湿润。将5.1中提取液月5m1.10%甲醇水溶被溶解.以每秒1滴速率过H1.13阅相萃取杜奔法流出液，再用1OmI5光甲醇水溶液润洗离心管并上HL3杜、弃去从HLB扯流出的润洗没，其空排T小柱10mi。用9ml.乙酸乙酯进行洗脱，收集洗脱滚于15ml.离心管中，加人3无水硫酸钠·振薦3min.5000r/min条件下高心2min将溶液转移至另--离心管巾于40%水浴中氮浓缩近于，排乙酸乙酯定容至 1. 0 mL,供气相色谱 FPD 测定。5.2.2有机氯农药测定样品溶液净化将5.1中提吸液用1ml.正已烷溶解，加人0.5ml.浓硫酸，下动轻据泥句，5000r/min离心5uin后，取上层有机相进气相色谱ECD测定，如净化效果不充分，可再加人浓硫酸净化一次。5.3测定
5.3.1气相色谱电子俘获检测仪器条件R）增柱：DB-5石英毛细管柱：30m×0.32mm（内径），膜购0.25μm，或机当者：2
SN/T 1984--2007
b)包诺柱度:80(1 mia),30r /gm-180c=t/-205℃(4 min)2/-210℃:(1 min),postrun:280C(l min):
进样口度：250%
检测器温度：300℃；
载气：氮气，纯度99.999%，恒压0.135MPa;进样量:1 μL
进样方式;分流进样,分流比12：1.气相色谱火焰光度检测仪器条件5.3.2
色谱柱：力R-1701石英毛细管柱:30 mX0.32 Mm(内径).膜厚0,25 1m,或相当者色谱柱泻度:90℃(1 min）
样口溢度：250℃，
检测器度：250℃：
sot/min
+210c(8min)-
240%.postrun;280℃(5min)
载气：氮气，纯度99.999%，恒压0.071MPa：进样量:2:
进样方式，不分流进样,1.0 min后打开分流阀，吹扫流量50 tnl,/1nin。g
5.3.3色谱测定
待测溶分别进气相色谱电子俘获检测和气相色谱火焰光度检测，根据拌液中被测有机磷或有机氯残留的舍量情况·选定峰面积相近的标滩工作溶液。标雅工作落寂和样液中有机磷或有机氣残留的响应值均应在仪器的检测线性范国内。对混合标准工作溶液和样液等体积分组分参差进样测定，外标法定射。在5. 3.1 色谱条件下，敌敌畏、葬死蜘、马拉硫麟、对硫磷的保留时间分别约为 4.750 min。11.246 min,12.028 min,3. 250 min。5. 3. 2 色谱条作下 a-六六六、六氯苯,序六六六、7-六六穴、五氯确禁荣、-六六六、七氯的保留时间分别约为9.657min、9.924 min、10.378min、10.591min、10.749 tnin、H1.234 min13.072 min。10 μg/L有机磷和有机氯混合标准工作溶液色谱图分别参见附录A图A1.图A.2。
5. 3. 4空自试验
除不加标样外,按[述测定步躲进行,结果计算和表述
按式（1)计算试样中有机磷、有机氯农药化合物的含最，让算结果需扣除空白值。 =
式中·
样品中有机磷,有机氧农药化合物含，单位为毫克每干克(mg/kg);A
样液中有机、有机氧农药化合物峰面积：标维下作溶液中有机癣、有机氧农药化合物峰面积标工作溶液中有机避，有机氯农药化合物浓度.单位为毫克每升(mg/)；称取的试样量，单位为克(g)：
V一·-推液最终定容体积，单位为宰升（ml.).7方法的测定低限，回收率
7.1测定低限
本方法有机磷，有机氧表药测定低限均为0.00011m多/k只：7.2回收率
不同样品回收率数见表1，
.（1)
SV/T1984—2007
敌敌畏
表1可乐中有机磷、有机氢农药不同添加水平回收率范围加水平/(mg/kg）
马拉硫碳
对硫磷
六六六
#六六六
六六六
卫氢硝基苯
品六六六
.c.fcos
回收率范围/%
72. 0:~105, 0
76. 0 ~-99, 5
72. 8---102, 4
78.0--08. 0
79. 0--95. 5
75. 8 91. 2
64. 0 --88. 0
77, 0 -87. 0
75. 0--87. 0
81, 0---92, 0
77.4--80. 4
82. 0-98. 0
81.5---95,0
88. 2 ~ 99, 0
92. 0-~106, 0
83.0--104.5
89.0--106.0
73.0~-98.0
82.0~00. 0
83. 4-~ 91. 2
81.0101.0
8-1. 5--100. 5
89.8--101. 6
85. 0-98. 0
81.5-.97.5
8L. 6~97.8
79. 0 -- 97. 0
76.0~90.0
76.2~-91.0
81.0--109.0
83. 5-- 07. 0
94. 8~-J01. 2
附录A
（资料性附录）
标准溶液色谱图
FPD1 B (CX1L.A-PRE>CXILA-P 2006-12-16 22-51-40:S1,D)150pA
-敌敌畏：
雄死蜱，
·马拉瓷磷；
对硫磷，
HCDIA(S2SIE)
α-六六六：
六素苯；
P入六六，
·五醋基苯；
r-六六六：
命六A
七氮。
std-10ppb
10s/1.有机磷农药标准溶液色谱图12.5
图 4. 210 μg/1. 有机氯农药标准溶液色谱图12
SN/T 1984—2007
SN/T1984—2007
Foreword
AnnexAofthis standard is an informativeannex.This standard was proposed by and is under the charge of the Certification and Accreditation Admin-istration of the People's Republic of China.The standard was drafted by Shenzhen Entry-Exit Inspection and Quarantine Bureau of the People'sRepublicof China.
The main drafters of this stardard are Xiao Lailong. Tang Shaobing. Jin Baohui, Lin Xiuyun,He Jun.Chen Peijin, Lan Fang. Lin Li and Wu WeidongThis standard is an Entry-Exit inspection and quarantine professional standard af the People's Repub-lic of China prormulgated for the first time.Note; This English version, a translation from the Chinese taxt. is sofely for guidance.6
SN/T 1984—2007
Determination of organophosphorus and organochlorineresidues in cola drink for import and export GC method1scope
This standard specifies the methads of determination of 11 organophosphorus and organochlorineresidues by gas chromatography in cola drink.This standard is applicable to the determination of organophosphorus and organochlorine residues ofdichlovos,chlorpyrifos,malathion,parathion,a-666.β-666,-666,8-666.heptachior,hexachloro-benzene, pentachlaronitrobenzene in cola drink.2Principle
The residues of organophosphorus in the test sample are extracted with ethyl acetate, After cleanedup by passing through a HLB cartridge, the residues ate determined by a gas chromatograph withFPD detector using external standard method.The residues of organochlorine in the test sample are extracted with ethyl acetate. After cleaned upby suifuric acid treatment,the residues are determined by a gas chromatagraph with EcD detectoru.sing external standard methad.3Reagents and materials
Unless otherwise specified, all reagents should be af analytical 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
3.4Antydraus sodium sulfate: lgnite at 650'c for 4 h, and keep in a tightly clased container.3.5 Sodium chlaride.
3.6 Sodium hydroxide.
SN/T 1984—2007
3.7 Concentrated sulphuric acid, GR.3. 8 Methanol-water solution(5 + 95).3. 9 Methanol-water solutian (10+90).3. 10 Sodium hydroxide solution, 1 mol/L: Accurately weigh 20 g sodium hydroxide, dissolve anddilutewithwaterto500mL
3. 11 Organophasphorus and argangchlorine,pestjcides_standard: dichfovos (C, H, Cl, O,P, CAs No.62-73-7), chlorpyrifos (C, H,/ClaNO,PS, CAS No. 2921-8B-2), malathion(Cu Hh,O,PS2. CAS No. 12175-5), parathion(C.Hi, NO,PS, CAS Na 56-38-2), Purity>96. D% : α -656(C,H.Clh :CAS No, 319-84.6), β-666(C,H,Cla, CAS No.[319-85-7) ..7 -666ICHa Che, CAS No. 55963-79-6) ,-666(C,H, CL, CASNo. 319-86-8), heptachtor (C. H, Cl, , CAs No. 76-44-8) , hexachlorobenzene(Ce Cle, CAs No, 118-74.1), pentachloronitrobenzene (CaC,NO,-CAs No. 82-6s-B) are liquid standards, whose concentra-tions are 100 mg/L and volumes arei3. 12 Organophosphorus pesticides standard solution:a) Standard stock solution:LAccurstely.weigh Pesticide.standard of dichlovos, chlorpyrifos,malathion, parathion. dissofve in acetone solvent.to-form a standard stock solution of 1 oo0 mg/L inconcentration, The solution cart be presMixture midst solution
rved in the temperature below - 18'℃.measure1 ml orgarophosphorus pesticides standard stocksolution, dilute with acetone tg: form'a standard working sdlution of 10 mg/L in concentration.Thesolution canbepreserved in theltemperdturebefaw.-igcc) Standard working solutioti: arcarting to the requifement. accurately measure an adequate vol-ume of organophosphorus pesticides mixture midst so!ution, dilute with ethyl acetate and pre-pare a standard working soutton of eppropriate concentration. The solution can be preserved inthe temperature at ot ~4℃
3.13Organochforine pesticides standard solution:a) Mixture midst solution: accurately measure organochlorine pesticides standard solution, dilutewith acetone to form a standard working solution of 1o mg/L in concentration, The solutian canbe preserved in the ternperature befaw - 18'r.b) Standard working solution: according to the requirement, accurately measure an adequate vol.ume af organochlorine pesticides mixture midst solution, dilute with n-hexane and prepare astandard working solution of appropriate concentration. The solution can be preserved in thetemperature at ot ~4'c.
3.14HLBcartridge:60mg,3mLorequivalent.4Apparatus and equipment
SN/T 19842007
4. 1 Gas chromatograph equipped with ECD and FPD in phosphorus rriode. 525 nm.4. 2 Mechanical shaker.bzxz.net
4.3 Centrifuge.
4. 4 Nitrogen evaporator.
4. 5 Salid phase extraction
4.6 Rotary evaporator.
Separating Funnets: 5do mt
4.8 Evaporative flask, K-dl..5D0.mL4. 9Filter funnel.
4.10Polypropylene centrifuge tube:15mL,with5crew cup5
Procedure
6. 1 Organophosphorus, oiganochlorine pesticides xtractionTransfer Cola samples in a keaker-for 6-min with pkriodic stiring by a glass stick to discharge CO, and adjust pH value of cola sample to 7 by adding 1 mol/L NaOH. Accurately weigh 150 g af the sam-ple(accurate to 0.01 g), Transfer the sample to a separating funnel, add 15 g NaCl to the sample,seai. and shake to dissolve salt. Add too mt ethyl acetate to the separating funnel, seal, and shake2 min vigorously with periodic venting to release excess pressure. Allow the organic tayer to sepa-rata from the water phase for a minimum of 1α min,The organic layer is passed through 15 g anhy-drous sodiurm sulfate to remove residual water. Add a second 1c0 mL votume of ethyl acetate tothe separating funnel and repeat the extraction procedure a second tima, combining the extracts inthe evoperative flask Perform a third extraction in the sarme manner. Evaporate the sample extractto 3mL~4m on a rotary evaporator using 0 water bath at 4oC.Transfer the extract to a 15 mLgraduated test tube. Rinse flask 3 moro times with 9 mL n-hexane and transfer each rinse to thesame test tube. Evaporate the extract to near dryness in a water bath at 4oc under a gentle stream9
SN/I 1984—2007
of nitrogen.
5.2Cleanup
5. 2. 1 Cleanup for determination of organophosphorus residuesPrecondition HLB cartridge by 3 mL ethyl acetate, 3 mL methanol and 3 mL water. Reconstitute thesample residue of 5. 1 with 5 mL of 10% methanol-water salution, allow the sample to pass thraughHLB cartridge at the rate pf about 1 drop's. Discard the column eluate, Rinse the test tube 3 timeswith 10 mL 5% methanol-water and transfer each rinse to HLB cartridge. Discarb the rinse and drythe cartridge for 10 min. Elute the analytes into a clean 15 mL test tube with 9 mL ethyl acetate. Add3 g anhydrous sodium sulfate into ethyl acetate solution. blend for 3 min in vortex mixer. centrifugefor 2 min <5 o0o r/min). Transfer organic solution into another 15 mL centrifuge tube. Concentrationthe organic phase to near dryness in a water bath at 4o under a gentle stream of nitrogen. Dissolvethe residues and dilute exactly to 1.0 mL with ethyl acetate. The solution is determined by GC-FPD.5.2.2 Cleanup for determination of organochlorine residuesReconstitute the sampte residue of 5. 1 with 1 mL of n-hexane, add 0. 5 mL concentrated sulphuricacid,shake gently,and centrifuge for 5 min(5 ooo r/min). The upper arganic solution is determined byGC-ECD.
5.3Determination
5. 3. 1 GC-ECD operating conditiansa) Column:DB-5 capillary column:30 m × 0. 32 mm ×0. 25 μm or equivalent:30/min.180c3c/mi-205℃（4 min)=2℃/mln-210℃(1 min),
b)Column temperature:8a(1 min)-postrun:280芒(1 min) ;
c)Injectionporttemperature:25ocd) Detector temperature:300℃ :e)Carrier gas:Nitrogen,Purity=99.999%.constant pressure 0.135MPa:f>[Injection votume,1 μL;
g)Injection mode:Split ratio is 12 : 1.10
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