本标准规定了食品中α-硫丹、β-硫丹、硫丹硫酸盐残留量的气相色谱-质谱检测方法。本标准适用于鳗鱼、泥鳅、鲶鱼、黄鳝、牛肉、大豆、蘑菇、毛豆、菠菜、蒜薹、西红柿、甘蓝、苹果、柑橘、茶叶中硫丹残留量的测定。

中华人民共和国出入境检验检疫行业标准SN/T 1873—2007
进出口食品中硫丹残留量的检测方法气相色谱-质谱法
Determination of endosulfan residues in food for import and export-GC-MS2007-04-06发布
华人民！和国
国家质量监督检验检疫总局
2007-10-16实施
本标准录A为资料性附求：
本标准由中华人民共和国国家认证认可益督管委会提出并灯口SN/T1873—2007
本标滩山中华人民共和国大津人境恰验检接局、中华人民共和国广东出人境检验检局、中华人民共和国上海山人境检验检疫局负责起草。本标准主要起草人：葛定坤、十云风、常谷吞艳、陈捷、陈其归、刘培，郭德华、焦红、蔚则。本标准系首次发布的检验检疫行业标准。范围
进出口食品中硫丹残留量的检测方法气相色谱-质谱法
SN/T 1873—2007
本标准刚定了食品单丹、已硫牙,硫丹硫酸盘戏留量的气相色谱质谱检测方法，木标淮一鳗鱼、泥鳅，鲶鱼、黄鳝、牛：肉、人麟帖、毛、被菜、蒜学、四红柿、七、苹果、柑橘、茶叶牛硫为残留虽的测是
2测定方法
2.1方法提要
品经溶剂提取、凝胶层析托或硅镁吸附剂净化，采用气相色谱质谱别定，外标法定员2.2试剂和材料
除另有规定外,所有的有机试剂为色谱纯，水为二次蒸溜水。2.2.1啊，
2.2.2乙酸乙酯
2.2. 3 坏已烷。
2.2.4油谜：沸程30-.60℃
2.2.5后水梳俊纳：分析纯，650℃灼烧1h，作下焕器内冷却丝究温，购下密其瓶中备用。2.2.6氯化钠：分析继。
2.2.7洗脱液：乙酸之酪-环口烷（1：1.体页比）浪合溶液，2.2.8凝胶及溶胀:Bio Beads X3 290 H~-20) H或相当名;凝胶的溶张接每克凝胶加4,6 nL乙酸乙酯坏已烷（1：1,体积比)的滤合溶液没池，溶胀6H以1而。2. 2. 9凝胶层析柱:柱长20 crri、内径2. 0 crm H活皱璃层析杆,杆底垫少许玻璃棉。用洗脱剂Z羧乙配-环已烷(1：1，体积比)游张的凝胶以湿法转人装杜，检床高约)Ⅲ，胶床始终保持在洗税剂中：洗脱流速约1L/in，「样前用洗脱液以两分之，-的洗脱流速淋洗个柱体积：2.2.15国些最代：础铁吸附剂.9.或相当名：用前分别用5=让丙止二烷（1：9.体积上）、5=nL正己烷淋洗活化小柱：
2.2. 11α硫片:CA$缩钙 959 98 8.纯度大J 99. 5 -2. 2. 123-硫片:CAS编码 332[3-6-9,纯度大于 9、%2.2. 13α-硫丹—3-硫片混含物:CA5编码 115-29-7.纯度(65. 1%—33. 4%),硫丹硫酸盐:CAS编码 1031 07 8.纯度人于 99,5头2.2. 14
2.2.15硫丹标诺备被:症确称最适景的硫左标链品网少员巾本溶解后，以正已烧稀释战一定滚度的豁备液球箱侏存，
2.2.16硫丹标准1.作液：娘-量的标准储备液：用止己烷稀释成适当浓度的标准1作液。2.3仪器和设备
2.3.1气柏色谱质谱仪，配备负化学源(NC1)2.3.2旋转蒸发装置
2. 3. 3 效次仪,
2.3.4组织勾浆机。
2.3.5植物粉摔机。
2.3. 6 振萄器.
SN/T 1873—2097
2.4测定步骤
2.4.1样品的制备
动物产品妆鞭鱼、泥，鲶鱼、黄鳞，牛肉产品收川食部分590用红织捣碎机充分捣碎均匀a）
均分成两份，分别装人活净器中，密封标记、一18冷冻保荐.植物品：取大豆、蘑菇、毛亚、被案、蒜苔、西红种、山蓝、苹果、柑橘、茶叶，纠织粉碎机)
粉碎,分别装人治净容器中，密封.标记、汇冷藏保存-2. 4. 2
样品的提收
动物品：称取试样20g（精确到0.0lg），于10ml.具寒三角瓶中，加水5ml（视样品水分含呆灿水使总水量药水品的肉追常在%在，水6m.即可）4肉酮浆1min,加氯化钠6g.充分部匀.引加30ml.个趾醚，振摇a0mn，最35ml.有机层：清液-终无水硫酸钠于疑转蒸发筑巾，浓缩至约1，加2mL乙酸乙酯-环已烷溶液再浓缩，如此重复次，浓缩至药2ml.。
水果蔬桌：称取试样精确2.01)于.烧杯,.乙脂.勾奖1min转移h)
至族先加人 6 g氯化钠的 100 ml,的H塞量简中,烈掠荡2 min,静暨20 m-in,圾 1C ml,上清液」10 rmL此色管中,在 43℃水浴中氮吹仪干,2 ml 正己烷溶解，粮谷、茶叶等：称取粉降试样.0（精确到C.0：9），」109)ml.一璇中，漆班2)m正凹烷，派荡a0 min，过滤,吸最2ml.f清液」10ml比色管中，2.4.3样品的净化
）对2,1,2.1 的提最样品上焕胶层析乱并以乙酸乙蕲环巨烷溶液洗脱弃去0 mI.~3 ㎡-1,流分，收集l.～0ml.流分。将其旋转蒸发浓跪约？ml.,再经胶层析正币复净化次、收集35 ml70 ml.流分,蒸发浓缩,用氮吹仪恢除济剂(10℃).以正已烷定容至5 ml,留待GC/MS分析
刘2.=.2.2和24.2.3的浓缩液个部[.固枯萃取杜，再用0 rml.内酮-止正己烷洗脱,将盛有淋h）
洗液的离心管昏于氮吹仪」4℃水浴氮吹近干，端类、水果类用止亡碗谁确定容5=让：粮谷类用正已烧准确定容至」ml.在旋混台器上泥，移人样品瓶宜待测2. 4. 4
2. 4. 4. 1
气相色谱-质谱条件
色谱柱:B 17G1 代.30 ×0,25 II1×0,25 I1·或当名：袋气氮气，纯度个低下99.959%，流速：1.3 ml./rim;柱温：40保持1rzir.以30℃/rmin速度升至130r：，卡以5℃/nin升至269℃，保持1rmin进样口溢度：250°C;
进栏方式:不分流：
开阀时间：0.75nin
近样呆;2 μl:
电离方式:NCI,30 eV;
接1度：28C℃：
反成气:甲烷气,CH:
离子源混度：15GC:
[)溶剂延遇：lの min;
离了检测模试：选择离了监测(SIM).监测离了皮其析对卡度比见表1，表1选择离子和相对丰度
被测汁分
相对丰度在
α-硫上-磷
372.22106（定至）-108.1
28 : 47 : 100 4 8. : 32
硫丹硫酸节
351.356(定量),385,30C
62 : 1:: 72 : 50
2.4. 4.2量测定
SN/T 1873—2007
根据样液中被测硫的个员情况，选定浓度相近的标准工作液，其向应值应在为法检测的线性范圈内，在1:述气相色谱 质谱条件下,保留时间分引为 α 硫丹 23. 7 nill、3硫丹 27. 7 rLir,硫丹硫酸盐30. 4 tmm,选择离了色谱图和质谱图见附录 A [的 A. ~-图A. 5：2.4.4.3定性测定
按照色谱质谱条件测定样品和标准二作溶液，如果检测的质员色谱泽的保留时与标准导一效；相对丰度允许慵差小20关.则叫判断样品中存在对应的被测物。2.4.4.4空试验
除不加试样外，均按还步骤进行。2. 4.5结呆算与表述
按式(:)算试栏中硫丹为含量(以α 疏丹、3硫丹、流丹硫酸盐的总员计);X_AxrxV
戏中：
试样户硫丹的含量，单位为毫克得下克（mg/g）；A
试样户硫的白谱峰面积：
标准二作溶液硫丹的浓变，详位为微克每毫升（/m)：样液最终定容体积,单位为老升（mI.)：标准一作落液它硫丹的色谱峰面识；最终样液所代表的量，单位为克（g)，2. 4. 6 测定低限,可收率
2. 4. 6. 1 测定低限
本方法的测定低限：动物品.001ng/kg、植物产品c.0：ng/kg。2. 4. 6.2-收率
动物产品,梢物产品样品添加匹收率见表2表2动物产品、植物产品样品添加回收率洋品
添水平（mg/kg）
同收率范周）
67.3--77. 5
71.1--79, 11
70. 1 --88. 11
70. t:--35.
79. G --- 37. 4
78 C--21.
70, C --- 50, 9
72.--55. 0
80. C.-20, 8
76.c.-87.0
73. C--92. 5
86. C.-97. 0
70.c--7G. 5
70.G---50. C
77. G --53. 0
深如水平/（mg/kz）
同收率范周（兴）
70 --82. 5
77,---87. 5
78.11-~31. :1
75. 1-37. 6
81. t-~ 88. 3
99. C-~ 26. 3
71. G-~ 58, 3
72. 5-20, 2
80, C -26, 3
70.c....3
70. 0.-- 82. 5
79.0.-- 89. 5
74. 6- 88. 3
72. 3~-90. 3
93.0~97. 9
SV/T 1873—2097
1809071
8607334 253 (27.556)
附录A
（资料性附录）
标准品质谱图
2:N[R n? h thannes tl-
I:s[R o:t Channe.s C!
(-硫丹、险硫丹、硫丹硫酸盐选择离子色谱图2:SIR ts (annel rl-
406:00
2C-硫丹,β硫丹选择离子质谱图图4.2
0610015 209 (30. 762)
2: 51R ur4 hannel, t-
图A.3硫丹硫酸盐的选择离子质谱图60801:1120(38.539)
348.21、
1e3b1. 20
Seanci
硫丹硫酸盐全扫摧质谱图
0627194 13R8(37.1R6)
234 28-20.24
219.18、
uitarnkn
l+limrm Tlure
Ferrhhr
图 A,5-丹、阝硫丹全扫描质谱图SN/T1873—2007
SN/T 1873—2097
Foreword
AnnexA of this standard is an information annex.This standard was proposed by and is under the charged of certification and accreditation administa-tion of thc Pcople's Rcpublic of China.This standard was drafted by Tianjin Entry-Exit Inspection and Quarantine Bureau,and GuangdongEntry-Exit Inspection and Quarantine Bureau and Shanghai Entry-Exit Inspection and Quarantine Bu-reau.
The standard was rnainly drafted by Ge-bao Kuni, Wang-yun Feng. Chang- chun Yan, Chen-jie.Chenqi Yony.LiuPei,Guo-deHua,Jiao-hong,Han-li.This standard is professional standard for entry-exit inspection and quarantine promulgated for thefirst timc.
SN/T 1873—2007
Determination of endosulfan residues in foodfor import and export -Gc-MsThis standard specifies the determination and confirmation of α-endosulfan, 3-endasulfan and en-dosulfan sulfate in food by gas chromatography-mass spectrum.This slandard is applicable for the deteminalion and confirrnalion of endosulfan in eel,loach. caifish.rice field eel.beef, soybeanl, mushroorn.green soy bean, spinage.garlic.tomato,cabbage.apple.orange and tea samples.
2Method of determinatian
2. 1Principle
Endosulfan in the test sample are extracted with the solvent, then cleaned up with gelatin chromato-graphic column. Determination by gas chromatography - mass spectrum and quanyified by using theexternal standard,
2.2Reagents and materials
Unless otherwise specified. all the reagent used should be chromatograph pure, and \water\ is dei-onized water.
2.2, 1Acetone,
Ethyl acelate.
Cyclhexane
Petraleum ether: boils the regulation.2.2. 4
2. 2. 5 Anhydrous sodium sulfate; ignite at 650℃ for 4 h. and store in air-tight container.2. 2. 6wwW.vv99.Net
Sodium chloride (analytical pure)2. 2.7 Elute solvet: cthyl acetatc-cyclohexanc(1 : 1).子
SV/T1873—2097
2. 2. 8 Gcl and swelling : Bio - Beads(R) S-X3 2a0 mcsh-400 mcsh or cquivalcnt: Thc swalling of gclthrough every 4 g gel adding 4. 6 mL Ethyl acetate - cyclohexane(1 : 1 imrmersion. The gel to beused when swelling 6 h.
2.2.9Gelatin chromatographic column; the length of the column is 20 cm, Inside diameter 2.0 cmwith a piston, and the material quality is glass. Put some glass wool in the base of the column. Putthe gelatin soaks with Ethyl acelale-cyclohexane(1 : 1) in the calurmn by aqueous method. Thelernigthi of the Culumi bed is nearly 20 cmi, gelatin bed throughout in the Ethyl acetate-cyclohexarie(1 : 1): The elute flow rate is about 1 mL/min, Elute the column use 1 column volume elute solutionat a flow rate of 0. 5 mL/min before pour extract solution2. 2. 10 sPE cartridge: florisil, 1 g, or ecquivalent. It was conditioned with 5 mL acetone-n-hexane(10 + 90) followed by 5 mL n-hexan,2.2. 11α-endosulfan; CAs code 959-98-8, purity99. 5%.2.2. 12β-endasulfan: CAs code 33213-65-9, purily99. 5%.2. 2. 13The mixture of c-encdasulfan and 9-endosulfan; CAs code 115-29-7.2.2. 14 Endosulfan sulfatc: CAs code 1031-07-8, purity.:99.5%.2.2. 15 Stock standard solution of endosulfan: accurately weigh adequate amounts of endosulfan standard. dissolution by a little toluene, then dissolved in N - hexane to make up standard stock so.lution of the density, should be stored at 4' in refrigeratory.2.2. 16 Working slandard splution of endosulfan: dilule the slock slandard salulian wih n-hexaneta 1. 0 μg/rnL as working standard solution.2.3Apparatusand equipments
2.3.1 Gas chromatograph combined with negative chemical ionizatian mass spectragram (GC-MS).2.3.2Rotaryvacuumevaporator
2. 3. 3 Nitrogen evaperator.2.3.4High-speed homogenizer.2. 3. 5 Plant disintegrator.2.3. 6Oscillators.
2. 4 Procedure
2.4.1Samplepreparation
SN/T1873—2007
Creatural sample: Take the edible part of original sample is taken and homogenized, thien it is di-a）
vided in two angd sealed, labeled For lab test. The test sample is stored in - 18'C relrigeratory.b) Bolanic sample: Take original sample is laken and homogenized. then it is divided in [wo angdsealed, labeled for lab test. The test sarnple is stored in 4℃ refrigeratory2.4.2SampleExtraction
Creatural sample: Weight 20 g(accurate to 0. 01 g) pf the test sample into 1c0 mL conical flask.a
accurately adding 6 mL water, adding 40 mL acetone. homogenize 1 min and add 6 g of sodiumchloride, mix well. Adding 30 mL petroleum ether. shake 30 min. Taking the upper liquid 35 mLflask, combine extracted solution and evaporate to nearly 1 mL, adding 2 mL of ethyl acetate-cyclahexane (1 : 1),combine thrice according to above process, combine the extract solutionnearly 2 rm
b) Fruit and vegetable: Weight 25 g(accurate to 0. 01 g) of the test sarnple into 200 mL beaker. ac-curately adding 50 mL acetonitrile, homogenize 1 min and transfer into the graduated cylinderswith stopper, then add 6 g af sodium chloride into the graduated cylinders, Shake vigorously2 min, taking the upper liquid into 10 mL ccntrifugo tubc, bclow it to dryncss with nitragenflow at 4o'c water-bath, dissolve with 2 mL petraleum ether.c）
Grain and tea: Weight 10 g(accurate to 0, 01 g) of the test sample into 100 mL conical flask.adding 20 mL n-hexane, shake 30 min. then filter and taking the 2 mL upper liquid into 10 mLcentrifuge tube.
2.4.3Samplecleanup
a) Wash the extract sample solution of 2, 4, 2, 1 with Ethyl acetate-cyclohexane(1 : 1) by gelatinchromatographic column, discarding 0~35 mL effluent, collect 35 mL~70 mL elution, comhinethe clution and cvaporatc to ncarly 2 mL, clcan up twicc according to above procoss. Combineall the elution and evaporate to dryness under nitrogen flow.make up to 5 mL with petroleum e-ther.The solution is used for Gc-MS determination.b)Pour the sample solution of 2.4. 2. 2 and 2.4.2.3 into the cleanup column, elute with 5 mL ace-tone-n-hexane (10 + 90). Repeat again according to above process. Evaporate to dryness undernitrogen flow at 40' , then make up to 5 mL with n-hexane in [ruit and vegetable and make uplo 1 mL with n-hexane in grain; mix well. The salutiar is used for Gc-Ms deiermination.2. 4. 4Determination
2. 4. 4. 1 GC-Ms opcrating conditionsSV/T1873—2097
Column:DB-1701,30 mx0.25 mm×0.25 μm or equivalent:Carricrgas:Hc(purity.99.999%),flow rateofcarricrgas:1.3mL/min;Temperature program: 40 C (keep 1 min) 30'C /min to 130'℃ 5'℃ /min to 260℃ (keep 1 min) ;Injection temperature: 250'c :Injection mode: splitless:
Purge time: 0. 75 min:
Injection volume; 2 μL;
Electron modc: NCl, 30 cV;
Interface temperature:280℃:i)
j) Reaction gas; CH4;
lon source temperaturet 150'℃ :Solvet delay: 10 min;
Detcction modc:SiM: Selection ions (m/z) and ralativc intcnsity(%) scc tablc1,Table TSelected ions and relative intensityAnalyte
Selected ions m/z
Relative intensity/( % )
2GC-MS determination
2. 4. 4. 2
a-endosulfan α,β-enclosulfan374.404.406( quanititative) .408,41028 : 4/ : 100 : 84 : 32
endosulfan silfate
384.386( quantitative) ,388.39062 : 100 : 72 : 30
According to the values ol endosullan in sample, select the standard working solution with similarpeak area to that of samiple solutior. The responses of eridosulfan in the standard working ard thesample solution should be within the liner range of the instrumental detection, Under the above GC-Ms operating cancition. The retentian time of for chramatogram of α-endosulfean is 23. 7 min. 3 -en-dosulfan is 27.7 min and endosulfan sulfate is 30, 4 min. The chromatogram and mass spectrum ofthe standard. see Figure A. 1 ~ Figure A. 5. of annex A.2. 4. 4, 3Confirmation of GC-MSUndcr Gc-Ms conditions, thc working solution and salutian is injected., If the retention times ofsample chromatogram peaks are consistent with the standards. and the deviation of the abundanceratio between sample and standard within 20% . according to the selected ions and relative intensityta conlirmate.
2.4. 4. 4 Blank test
The operation of the blank test is the same as the described in the method of determination. but withthe omission of sample addition.5 Calculation arnid expression of result2. 4. 5
Calcuilation thc content of cndosulfan rcsiduc in thc tcst sample according thc formulat1) ,( thc result10
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