【商检行业标准(SN)】 进出口水产品中喹赛多残留量的检测方法 液相色谱－质谱/质谱法

中华人民共和国出入境检验检疫行业标准SN/T 1927—2007
进出口水产品中喹赛多残留量的检测方法液相色谱-质谱/质谱法
Determination of cyadox residues in aquatic products for import and export-LC-MS/MS method
2007-05-23发布
华人民！和国
国家质量监督检验检疫总
2007-12-01实施
本标准的附求A、附求B为资料性附录前言
本标准由医家认证认可监督管理委员会提出并力口：SN/T1927—2007
本标滩起草单位：中华人民共和国福建出人境检验恰疫局食品安全分析与检测技术教育部重点实验案(祸州大学)
本标滩主起草人:杨方、刘才、黄虏蓉,李翘平余孔捷,林永湃,陈祥财、除国南，本标准系首次发布的出人境检验检疫行业标准。1范围
进出口水产品中喹赛多残留量的检测方法液相色谱-质谱/质谱法
本标准规定广水产品中赛多残留量的凌相色谱-质谱/质谱测定利裤证方法：本标准适压虾、發鱼及制号、真鱼中睦赛多残留的测定和确证2 规范性引用文件
SN/T 1927—2007
下划文件中的条款通过本标的引用而成为本标推的条歇。川是注H期的引用义件，H随后所有的修改单（不包拆勘误的内容)或修订版哟不适出于本标准，然而,鼓励根据本标准达成协议的各方评究是否可使用这些文作的最新版本，凡足不注明期的引而文件，儿最新版本适而本标准，（3/16882分析实验案用水规格和试验方法3方法提耍
来用羧性乙摘-市醇混合辫剂提收试样中的残留物，提攻液经（s却和擎收栏净化后，相色谱-质谱/质谱法测定,外标法定量，
4试剂和材斜
除非刃有说明,所月试剂均为芬析纯水为GB/T 6582规定的-级水4.1乙睛：色谱结，
4.2 甲醇:色谱纯,
4.3市酸。
4. 4二中业磁。
4.5.15峻溶浚：移取1m峻，以水定容1.4.6币酸甲醇1乙情提液（2「19·88，体积比）：4.73.1中水溶液—乙溶液7—3,体积比）.4.85关干醇水溶液:移取5 ml,甲掠.以水容 1G0 rml.混句4.9标准物质：唑寒多标准物质（cyaeox.分广式CII.N..CAS号 65884-26-0,分广量271.36）,纯度大于等丁8%。
4.1C标准诺备液（10)：谁确称敢适量的喹赛多标滩品：先用少量二中业剂落解痛以甲醇定容至100ImL.置于4℃冰箱巾,避光保存二个月。4.11标滩1作液；根据要坂适尿标雅此备液，以℃%甲酸水济液「7情（1.7)稀释战适浓度的标准工作液，配告过理避光，标准二作液要现配现压。4.12（1固相萃或小杜：j00 mig-3 ml.或相当并,用前以 ml.甲醇、3 ml.水活化,保柱体壶润。4.13滤膜:C.22 uIm.水系滤膜
5仪器和设备
5.1液相色谱质谱/质谱联而仪，配有喷募(ESI)源。5.2离心机：4ocor/mit:
SN/T 1927—2097
5.3年织捣率机
5.4均质器：转速大」10c09+/min5.5满旋混合器
5.6趋市波消洗器，
固相萃攻装置，
5.8氮吹仪，
试样制备和保存
6.1试样制备
鳗色连支的色肉，将支，肉分离后爬色皮置丁微波灿凸以中高功率加热30$后连同肉、鳗鱼制品取所有可食部分放入红织捣痒机沟质，充分混匀，装人清洁容器内，并殊明标记。虾、鱼类或叫食部分首丁高速组织揭伴机为质，充分混匀-装人清洁容器内，并标明标记，制栏操件选轻中必须防止样品受到污染或发牛残智物含量的变化，6.2试样保存
诚样于一18℃以小保存新鲜或冷冻的组织样品可在2℃~-6℃些存72h：7测定步骤
7.1提取
称取g试样（精确至0.C）g）置于5Cml.聚内烯离心管守.加人20ml.中股：中醇1乙睛混台溶剂（4.s）以均质器十_00c0r/nir均质提取305,4060/mir:离心5min，「:清液转移至支50 rm比色管中，男取一 50 rmL聚丙烯离心管加人15rmI.一巾酶一艺猎提取浚(4.6),洗涤均质猎J头10≤,洗涤液移人前一离心管牛，用坡样觉动残整，旋涡振荡提取1 min,超,li板振荡提取5in,1 3cc r/:nin离心5 min,合并上消液至50n:l.比色管，残洽店人15 ml.上述提取液，凝涡振荡提1min.1 o0cr/rim离心min,合并「清至m.比色节,以「述提取液定容至.m.,摇勾后取「o. t:.告于洁净玻璃离心巾，于35%下水浴氮吹近干，加入1ml.5中停水溶液（4.8)，旋涡振荡30.待净化7.2净化　
在1的提最滋尔人1 让山已燃派荡后弃山已缆厚，下层溶液以约1/i的流个部过C固相萃孜小杆以2×3mL5关甲醇水溶液（.8)洗涤离心管后淋洗固相萃取小柱,继续拙十约10 min,以3 ml.中醇洗脱,a5下氮吹至近,以0.1%H酸水率液7.摘溶(1. 7)定容至1ml,过C. 22 m 滤骥,供测定
7.3测定
7.3.1色谱条件
色谱柜：YMCFPzck ProCx柱,5μm15℃×3.C nm内径)，或相当名：a）
杆温:30:
流动相:0.1%中峻荠液「7(78,体积比）流速：100p/rin；
进样量:10 μL
7.3.2质谱条件：
离子源：电喷筹源(ESI),正离子模式：a
h）措方式：多反应监阅(MRM)：其他参考质谱条外参见附录A
7.3.3液相色谱-质谱/质谱测定
根据试样中被测物的会量请况，选最响应值适方的标准二作液进行色谱分机。标准工作液和得测2
SN/T 1927—2007
样波中喹寒多萄渤的响应俏应在仪露线性响应范周内，标「作液与待测样等木独逛样。上述色语条件下，喹赛彩的参孝保留制间为:in：标油物政的多反成蓝测（VRM色谱图参见附求7. 4 定性标准
7. 4. 1 保留时间
得测样品中化合物谱峰的保留时而与标准溶液比变化范国应在二2,5%之内。7.4.2信噪比
得测化合物的定性离了的客反应监测（MRM)色谱降的信噪比应人于等于3（$/N整3)·定量高了的多皮应蓝测（MRM)色谱峰的信噪比应大1等」_0S/N0)。7. 4. 3定量离子、定性离子及子离子丰度比待测化合物的质谱是烂离子成山现至少成包括一个时离子和两个子离子,而Ⅱ同一检测批次,对同一化合物，样品中日标化合物的两个子离于的和刘半度比与浓度柜的标雅溶液和比，具允许偏差不超过表1规定的范册，
定性确证时相对离子丰度的最大允许偏差表1免费标准bzxz.net
双离了度双)
充许的在对偏差（)
8结果计算和表述
用数船处评软作中忙外标法，按式(1)计算试样中峰赛多药物的战留最：X=AxxV
我中：
诚样中喹赛多残留量的数慎，并莅为毫克每千克（g/kg)；样液户唑赛多的峰山积
标雅二作液喹赛多的峰血积：
标雅二作液牛座赛多的浓度,单位为微克科升（)：样品最终定容体积,单位为衰升（rnl）：测定用分的样液体积位为毫升（rnL）；样品提最液体底.单位为毫升（rml)；称最试样品，单信为克（g)
9测定低限、回收率
9.1本方法的测定低限为：10ug/kg9.2回收率：
9.2.1唑赛多的加浓度为10总/k时.回收率的实验效惑妇下鳗鱼中唑寒多的四妆率在74.9关～1C1. C%：烤中唯密多的西孜率在 73. 3%~1C1. C%：虾中唯赛多的可收率在76，1光·97.8兆：黄色中咋赛多的四收率在75.2%~95.1%。9.2.2喹赛多的添加浓度为25 g/kg时,川收率的实验数港好下：鳗负睡赛多的尚妆率在78.1%~.1%;烤毁小啥赛多的向收率在79.5%~~06.5%虾噬赛多的可收率在 78,C%~-98.,C死c
SN/T 1927—2097
黄鱼中噻赛多的而收率在82.5%~97.9%。9.2.3赛多的添川浓度为40μ/kg时,同收率的实验效整妇下：鳗色小唯赛多的向妆率在.8%~05.2%；烤毁小唾载多的回收率在76.8%~97.3%；虾中座赛多的回收率在80.5~-9.1.8%：黄血中哗赛多的收率在86.9次~162.℃%。质谱条件：
附录A\:
(资料性附录）
质谱条件
雾化气(VEB),12. 00 1/mir(氮气);a)
气帘气(CUR):14.09 L/nin(氮气);喷募且压(IS)：30CO V;
去溶剂温度：450
去溶剂流&.co 1/mi:n(氮)：
撞(CAD):6. nTtnint 氮气);
驻留时间：15ctmin：
共他质谱参数见表A.1..
表A1喹赛多的主要参考质谱参数化合彻
$N/T 1927—2007
为定虽离广;对于人族增仪端，仅群参数可能存在茎异,测定前应将质谱参数优化到最住，CX
附录A所列质谱件足有A113100型没质联用仪上完成的.此处列高试验用仪器坚号仅为提供参与,并不泌1
及商业目的，教励标准独用者尝试不同厂家或型号的技器，3
SV/T 1927—2097
附录Ｈ
(资料性附录）
喹赛多标准物质的多反应监测(MRM)色谱图2.50
272.0/143.2
2Y2. 0/: 88. 2
喹赛多标准物质的多反应监测(MRM)色谱图Foreword
Annax A and Anncx B of this standard arc informativc annexcsSN/T 1927—2007
This standard is proposed by and was under the charge of the Certification and Accreditation admin.istrationof thePeoples Republic of China.This standard is dralted by Fujian Entry-Exit Inspection and Quarantine Bureau ol the People's Re-public of China, Key Laboralory of Arialysis & Deteclion Technology for Food Safely(Fuzhou University Ministry of Education
The standard is mainly drafted by Yang Fang,Liu Zhecai,Huang Xiaarang,Li Yaoping,Yu Kongjie,LinYonghui,ChcnXiangming,Chcn Guonan.This standard is a professional standard for Entry-Exit Inspection and Quarantine promulgated for thefirst time.
Nule: This Erglish versiori is trarislalion frurtl the Chirese lext.is solely for guidarice7
SN/T 1927—2097
Determination of cyadox residues in aguatic productsfor import and export LC-MS/MS methodScope
The standard specifies the method of determination af cyadox residues in auatic products for im-port and export by liquid chromatography-tandem mass spectrometry.This standard is applicable to the determination of cyadox residues in shrimp,eel and eel product andyellowtail fish.
2 Normative references
The following normative documents contain provisions which.through reference in this text,consti-tute provisions ol this Prolessional Standard. For dated references, subsecuent amendments to, orrevisions uf.any of these publications do not apply. However, parties to agreermerits based in thisProfessional Standard are encouraged to investigate the possibility of applying the mast recent edi-tions of the normative documents indicatecd below. For undated references,the latest edition of thenormative document referred to applies.GB/T 6682 Water for analytical laboratory use Specificatian and test methods3Principle
Extraction ofthc cyadoxrcsiducs with acidicacetonitrilc-mcthanol mixcd solvants,and thcn purifica-tion with Cis solid phase extraction (SPE) cartridges,followed by liquid chromatography-tandemmass spectrometry analysis
4 Reagents and Materials
All reagents should be of aralytical grade uriless specified.4.1Acetonitrile:HPLC grade.
4.2 Methanol:HPLC grade.
4. 3Formic acid.
4.4Dimcthyl sulfoxidc
SN/T1927—2007
4. 5 0, 1% Formic acid solution: Accurately measure 1 mL formic acid into 950 mL water and diluteta the volume with water,then mix well.4. 6 Formic acid - methanol + actonitrile(2 - 10 +88, V/ V) 4.7 0. 1% [ormic acid solution+acetonitrile (7+3, V/ V).4,8 5% methanol solution:Accurately measure 5 mL methanol into 95 mL water and mix well.4.9Standard of cyadax: purity98%.4.10 Stock solutions of cyadox(100 mg/L):Weigh 10. 0 mg cyadox starndard materials.dissolvewith dimcthylsulfoxidc and thcn dilutc with mcthanol to a volumc of 100 mL,and storc at approxi.mately 4c and protect from light for a maximum periad of 1 months.4. 11 Calibration solutions of cyadox far LC-Ms/MS: Dilute appropriate volume af stock solutions toa intended concentratian with dilute solutian and mix well. These solutians should be prepared be-fore use.
4. 12 C solid phase exlraction(SPE)cariridge: 500 mig/3 mL, the extraction cartridge is conditionedwith 3 mL mcthanol,3 mL watcr before usc,prcvcnt the columns from runing dry.4.13Membrarie filter:0.22 μm5Apparatus
5. 1 High Performance Liquid Chrormalography-Mass Speclrameler equipmenl: Equipped with elec-trospray (Esl) LC interface
5. 2Centrifuge:4 000 r/min.
5.3 Tissues homogenizer.
5.4Homagcnizcr:10 0op r/min or cquivalcnt.5.5Vortex mixer.
5.6 Ulirasanic equipmenl.
5.7 Solid phase extraction equipment5.8PressuredgasblawingconccntratorSV/T1927—2097
6Samplepreparation and storage6.1Samplepreparation
For eel samples. which are combined the muscle tissues and skins heated by microwave oven andmixed well by homogenizer. For eel products, which are combined all the edible portion and mixedwell by homogenizer,then sealed in clean containers and markedFor shrirnp sarmples and other fishes, which are combined the edible parlions and mixed well by ho-rnogerizer, theri sealed in clear containers arid marked.Precautious measures should be taken to avoid contamination or other factors which may cause thechango of residues conccntration in samplas.6. 2 Sample storage
Samples should be stored at - 18' . fresh or frozen tissues may be stored at 2 - 6'c for 72 h.7Method of Determination
7.1Extraction
Weigh 5 g of the prepared test sample (accurate to 0. 01 g) into a 50 mL stoppered polypropyleneplastic centrifuge tube, then add 20 mL formic acid 1 methanol : actonitrile extract solutions(4. 6) ,homogenize at 10 000 r/min for 30 s, then centrifuge at 4 000 r/min for 5min. transfer the superna-tant to a 50 mL calorimctric tubc. 15 mL cxtract solutions (4. 6) is uscd to wash thc dispcrscd stick,then added into the former centrifuge tube and mixed with the solid residues. The tube is vortexedfor 1 min and then extracted the analyte with ultrasonic for 5 min, centrifuged at 4 oo0 r/min for5 min.the supematant is transferred to the colorimetric tube. Another 15 mL extract solutions(4, 6)is added to tlie residues and vortexed for 1 min,cetrifuged at 4 000 r/min for 5 min. Combine the su-pernatant to the colorimetric tube and diluteto 50 mL with the extract solutions(4. 6). Measure10 mL and evaporate to dryness at 35c under a stream of nitrogen. The residue is redissolved in1 mL 5% methanol solution(4.8).The dissolulion is achieved using vorlex for 30 s.7.2Clean-up
Load extract through Cia sPE cartridges at a flow rate ca 1 mL/min,discard the elution, then the car-tridges are washed with 2 × 3 mL 5%. methanol solution(4. 8) after which is used ta prewash thetubc,dricd undcr vacuum,and thc cyadox rcsiduas arc clutcd with 3 mL mcthanol. Conccntratc theelution to near dryness at 35'c under a stream of nitrpgen,dissolve with solution(4.7) and dilute to1 mL. This solution is filtered with a 0, 22 μm filter prior to LC-Ms/Ms analysis,10
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