SN∕T 5440-2022 出口食品中双炔酰菌胺、噻唑菌胺、吲唑磺菌胺等多种酰胺类杀菌剂残留量的测定 液相色谱-质谱质谱法[商检]

《SN∕T 5440-2022 出口食品中双炔酰菌胺、噻唑菌胺、吲唑磺菌胺等多种酰胺类杀菌剂残留量的测定 液相色谱-质谱质谱法[商检]》由会员上传分享，免费在线阅读，更多相关内容在行业资料-天天文库。

ICS67.050CCSC53中华人民共和国出入境检验检疫行业标准SN/T5440—2022出口食品中双炔酰菌胺、噻唑菌胺、吲唑磺菌胺等多种酰胺类杀菌剂残留量的测定液相色谱-质谱/质谱法Determinationofmultipleamidefungicidesincludingmandipropamid,ethaboxam,amisulbrometcinfoodforexport—LC-MS/MSmethod2022-03-14发布2022-10-01实施中华人民共和国海关总署发布

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2SN/T5440—2022前言本文件按照GB/T1.1—2020《标准化工作导则第1部分:标准化文件的结构和起草规则》要求进行编制。请注意本文件的某些内容可能涉及专利。本文件的发布机构不承担识别这些专利的责任。本文件由中华人民共和国海关总署提出并归口。本文件起草单位:中华人民共和国杭州海关技术中心。本文件主要起草人:祝子铜、谢文、雷美康、姜芝英、候建波、叶有标、章应俊。Ⅰ

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4SN/T5440—2022出口食品中双炔酰菌胺、噻唑菌胺、吲唑磺菌胺等多种酰胺类杀菌剂残留量的测定液相色谱-质谱/质谱法1范围本文件规定了出口食品中双炔酰菌胺、噻唑菌胺、吲唑磺菌胺、硅噻菌胺、吡噻菌胺残留量的液相色谱-质谱/质谱测定方法。本文件适用于葡萄、白菜、芹菜、黄瓜、番茄、草莓、花生、猪肉中双炔酰菌胺、噻唑菌胺、吲唑磺菌胺、硅噻菌胺、吡噻菌胺残留量的定量测定和确证。2规范性引用文件下列文件中的内容通过文中的规范性引用而构成本文件必不可少的条款。其中,注日期的引用文件,仅该日期对应的版本适用于本文件;不注日期的引用文件,其最新版本(包括所有的修改单)适用于本文件。GB/T6682分析实验室用水规格和试验方法3术语和定义本文件没有需要界定的术语和定义。4方法提要试样中残留的双炔酰菌胺、噻唑菌胺、吲唑磺菌胺、硅噻菌胺、吡噻菌胺经1%乙酸乙腈溶液均质提取后,采用基质分散固相萃取净化,液相色谱-质谱/质谱测定,外标法定量。5试剂和材料除特殊说明外,所有试剂均为分析纯,水为符合GB/T6682规定的一级水。5.1乙腈:色谱纯。5.2甲醇:色谱纯。5.3甲酸:色谱纯。5.41%乙酸乙腈溶液:取1.0mL乙酸,用乙腈稀释并定容至100mL。5.50.15%甲酸溶液:取1.5mL甲酸,用水稀释并定容至1000mL。5.6标准物质:双炔酰菌胺、噻唑菌胺、吲唑磺菌胺、硅噻菌胺、吡噻菌胺,纯度均大于98.0%,5种酰胺类化合物的中文名称、英文名称、CAS号、分子式和分子量参见附录A。/mL标5.7标准储备溶液:分别准确称取适量的标准物质(5.6),用乙腈分别配制成浓度为1000μg1

5SN/T5440—2022准储备液,于-18℃避光保存。/mL5.8混合标准中间液:分别准确移取适量的标准储备溶液(5.7),用乙腈稀释配制成浓度为10μg的混合标准中间液,于-18℃避光保存。5.9基质标准工作液:准确移取混合标准中间液适量(5.8),用空白样品基质溶液配制成浓度为1.0ng/mL、2.0ng/mL、5.0ng/mL、10.0ng/mL、20.0ng/mL、40.0ng/mL、60.0ng/mL的基质标准工作液,现用现配。5.10基质分散固相萃取剂:4g无水硫酸镁,1g氯化钠,1g柠檬酸钠和0.5g柠檬酸氢二钠。5.11基质分散固相净化剂:150mg无水硫酸镁,25mgN-丙基乙二胺,75mg石墨化碳黑。,有机滤膜。5.12微孔滤膜:0.22μm6仪器和设备6.1液相色谱-质谱/质谱仪:配电喷雾离子源(ESI)。6.2分析天平:感量为0.0001g和0.01g。6.3离心机:转速大于等于8000r/min。6.4均质机。6.5涡旋混合器。6.6离心管:50mL聚四氟乙烯离心管。7样品制备与保存取代表性样品部分约500g,将其可食部分先切碎,经多功能食品搅拌机充分捣碎均匀,试样均分为两份,装入洁净容器,密封,并标明标记,于-18℃以下冷冻存放。在制样过程中,应防止样品污染或发生残留物含量的变化。8分析步骤8.1提取8.1.1蔬菜、水果称取10g试样(精确到0.01g)于50mL离心管中,加入20mL1%乙酸乙腈溶液,用均质机以9000r/min均质1min,加入基质分散固相萃取剂(5.10),涡旋1min,以8000r/min离心5min,上清液待净化。8.1.2肉制品、坚果类称取5g试样(精确到0.01g)于50mL离心管中,加入15mL1%乙酸乙腈溶液,用均质机以9000r/min均质1min,以8000r/min离心5min,上清液转移至25mL比色管中,再加入10mL1%乙酸乙腈溶液至残渣中,涡旋1min,以8000r/min离心5min,上清液转移至25mL比色管中,用1%乙酸乙腈定容至25mL,待净化。8.2净化取2mL待净化液至含有基质分散固相净化剂(5.11)的离心管中,涡旋1min,以8000r/min离心,供液相色谱-质谱/质谱仪5min。取0.5mL上清液,加入0.5mL水,涡旋1min,过0.22μm滤膜2

6SN/T5440—2022测定。8.3测定8.3.1液相色谱条件如下:(内径),粒度4.0,或相当者;a)色谱柱:AccucoreXLC18柱,4.6mm×150mmμmb)流动相:A,甲醇;B,0.15%甲酸水溶液,梯度洗脱程序见表1;表1梯度洗脱条件0.15%甲酸流速/时间/min甲醇/%水溶液/%(mL/min)055.045.00.41.055.045.00.43.020.080.00.48.05.095.00.412.05.095.00.413.055.045.00.417.055.045.00.4c)流速:0.4mL/min;d)柱温:40℃;。e)进样量:10μL8.3.2质谱条件如下:a)离子源:电喷雾离子源;b)扫描方式:正离子扫描;c)检测方式:多反应监测模式;d)其他参考质谱条件参见附录B。8.3.3定性测定按照上述测定样品和基质标准工作液,样品中待测物质的保留时间与基质标准工作液的保留时间偏差在±2.5%之内;定性离子对的相对丰度与浓度相当的基质标准工作液的相对丰度一致,相对丰度偏差不超过表2规定的范围,则可判定为样品中存在相应的待测物。表2定性确证时相对离子丰度的最大允许偏差相对离子丰度/%>50>20~50>10~20≤10允许的相对偏差/%±20±25±30±508.3.4定量测定根据样液中被测物的含量情况,选取响应值相近的基质标准工作液进行色谱分析。基质标准工作液和样液中待测物的响应值均应在仪器线性响应范围内。3

7SN/T5440—2022在上述仪器条件下,5种酰胺类杀菌剂的参考保留时间参见表B.1,5种酰胺类标准溶液多反应监测(MRM)色谱图参见附录C。8.3.5空白试验除不加试样外,均按上述操作步骤进行。9结果计算和表述用色谱数据处理软件或按式(1)计算试样中药物的残留含量。计算结果需扣除空白值:ci×V…………………………()Xi=1m式中:Xi———试样中药物残留量,单位为微克每千克(μg/kg);ci———从标准曲线中测得的药物浓度,单位为纳克每毫升(ng/mL);V———样液最终定容体积,单位为毫升(mL);m———最终样液代表的试样质量,单位为克(g)。10方法的定量限和回收率10.1定量限本方法中双炔酰菌胺、噻唑菌胺、吲唑磺菌胺、硅噻菌胺、吡噻菌胺定量限均为10.0/kg。μg10.2回收率5种酰胺类杀菌剂在葡萄、白菜、芹菜、黄瓜、番茄、草莓、花生、猪肉中的回收率的实验数据参见附录D。4

8SN/T5440—2022附录A(资料性)标准物质的基本信息表A.1酰胺类标准物质的基本信息序号中文名称英文名称CAS号分子式分子量1噻唑菌胺ethaboxam162650-77-3C14H16N4OS2320.432双炔酰菌胺mandipropamid374726-62-2C23H22ClNO4411.883吡噻菌胺penthiopyrad183675-82-3C16H20F3N3OS359.414硅噻菌胺silthiopham175217-20-6C13H21NOSSi267.465吲唑磺菌胺amisulbrom348635-87-0C13H13BrFN5O4S2466.315

9SN/T5440—2022附录B(资料性)1)质谱参考条件质谱参考条件如下:a)电喷雾电压:3000V;(20b)鞘气压力:3500kpaarb);c)毛细管温度:275℃;(8d)干燥气压力:1400kpaarb);e)干燥气温度:20℃;f)其他质谱参数参见表B.1。表B.15种酰胺类杀菌剂保留时间、定性离子对、定量离子对、去簇电压和碰撞气能量化合物保留时间/min离子对/(m/z)去簇电压/V碰撞能量/V321.0/183.0*22噻唑菌胺6.6196321.0/200.026412.0/328.0*14双炔酰菌胺7.3888412.0/124.935360.0/176.9*35吡噻菌胺8.3882360.0/275.914268.0/138.9*19硅噻菌胺8.4982268.0/73.032466.0/226.7*22吲唑磺菌胺9.5181466.0/148.146*为定量离子对。1)非商业性声明:附录B所列质谱条件是在TSQVantage质谱仪上完成的,此处列出试验用仪器型号仅是为了提供参考,并不涉及商业目的,鼓励标准使用者尝试采用不同厂家或型号的仪器。6

10SN/T5440—2022附录C(资料性)标准物质的多反应监测色谱图RT:0.00-11.006.63NJ1.27E5nV^=182.50-183.50R+cES^Arr^321.00100000：[182.^9-183.0)1,噻唑菌胺（321.0/183.0*)50000:6.63NJ9.8^4nVi=1Se.5Q-2CX)!.ESI^MrT^321.CC080000：[132.^9-183.001,60oooi噻哇菌胺(321.0/200.0)40oooi20000^7,34MJ4.11E440000!mfe=327.5Q328.50F:-ESI^MrT^412CC0Lffi9-124.SOI30000^50^328.(001]MS20000;双炔酰菌胺(412.0/328.0*)10000：7.34rrV^124,40-125.40R+c250001ESI3^\/lim2412000[124.ffi9-124.901,200001327.®&328.001]MS15000;双炔酰菌胺(412.0/124.9)10oooi5000!8.34NJ1rrfz=17B.40-177.40R+C100000-ESI測n^360.CC0[176.809■17-B.S01,吡噻菌胺（360.0/176.9*)50OOO8.NJ1.16E5,34275.40-276.40R+c100000-測m2360.CCO[17B.809-176.9O1,吡噻菌胺(360.0/275.9)50000：0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0RT:0.00-11.CCTime(min)_8.45M.6_92E4|rr»5z=138.40-139.40F:60000+c田S^MITB2^二268:1030.50000：[7299&73.001,硅噻菌胺(268.0/138.9*)138.899-138.901]IVB40000;30000!20000；iooooi4.34604.305.6/；.866；i.96.34^^■^8,45fMj3.ua30000：mb=725C>73.50R+cE33^\/lrTB225000:'[72999-73.001,20OOOj硅噻菌胺(268.0/73)M38.901]15oooi10000；5000:4.916,016.339^735d+c田S^MrrB24^.CXX)300E[148.099-227.099-227.101]IVB25K200|【吲哇磺菌胺(466.0/226.7*)15$iod50j9.659.47M-1.57E2‘rrtz=147.60-■148.60F:40i+c田n*B2HI峨.00020j引哇磺菌胺(466.0/148.1)'[148.099-^00j80:60:40:20i10.0110.830.00.'51：01.52：02：53：03：54：04：55：05：56：06：57：07：58：08：^59：69：5id.OKJ.Sl'l.0Time(min)图C.15种酰胺类杀菌剂标准溶液的多反应监测色谱图(1.0ng/mL)7

11SN/T5440—2022附录D(资料性)添加回收试验数据表D.1葡萄中5种酰胺类杀菌剂回收率范围化合物添加水平/(μg/kg)回收率范围/%相对标准偏差/%1098.0~102.01.72086.0~97.04.6噻唑菌胺100102.7~107.01.6500080.0~89.64.51094.0~105.04.920104.0~115.53.7双炔酰菌胺100114.4~121.82.6500076.8~90.66.91096.0~110.05.220102.0~107.51.8吡噻菌胺100105.2~112.22.2500080.1~92.05.31092.0~105.04.42098.0~108.53.6硅噻菌胺100105.6~112.22.8500080.5~97.67.71072.0~100.014.32086.0~94.53.7吲唑磺菌胺100105.9~108.91.0500091.7~111.06.4表D.2白菜中5种酰胺类杀菌剂回收率范围化合物添加水平/(μg/kg)回收率范围/%相对标准偏差/%1084.0~95.04.62088.5~92.51.9噻唑菌胺10087.0~94.43.1500083.5~94.54.88

12SN/T5440—2022表D.2(续)化合物添加水平/(μg/kg)回收率范围/%相对标准偏差/%1078.0~83.02.42076.5~79.51.3双炔酰菌胺10077.3~85.14.3500085.6~95.34.12500080.8~91.25.01087.0~91.01.62084.5~88.52.1吡噻菌胺10083.9~94.54.9500083.8~92.74.81090.0~98.02.82087.5~94.52.9硅噻菌胺10086.3~93.02.6500081.2~88.33.41084.0~95.04.42071.0~82.56.6吲唑磺菌胺10072.8~86.97.1500092.1~99.32.9表D.3芹菜中5种酰胺类杀菌剂回收率范围化合物添加水平/(μg/kg)回收率范围/%相对标准偏差/%1092.0~102.04.22090.5~95.52.0噻唑菌胺10087.3~94.63.15000108.3~111.11.01084.0~101.06.32080.0~98.06.8双炔酰菌胺10092.1~96.21.7500085.6~92.13.01000093.1~97.42.21092.0~102.03.72090.5~99.03.0吡噻菌胺10091.6~96.12.2500084.7~92.33.22000093.3~99.52.39

13SN/T5440—2022表D.3(续)化合物添加水平/(μg/kg)回收率范围/%相对标准偏差/%1092.0~102.03.92091.5~100.03.3硅噻菌胺10092.8~96.41.7500093.9~97.31.21075.0~97.010.92081.0~99.07.2吲唑磺菌胺10087.6~98.84.9500095.3~102.02.7表D.4黄瓜中5种酰胺类杀菌剂回收率范围化合物添加水平/(μg/kg)回收率范围/%相对标准偏差/%1092.0~102.03.52093.0~97.51.9噻唑菌胺100100.2~104.61.4500083.8~92.13.510105.0~113.02.72099.0~102.51.2双炔酰菌胺10099.4~125.38.1500072.5~89.88.110102.0~112.03.320100.5~104.51.4吡噻菌胺10097.4~101.91.65000100.2~112.64.110103.0~115.04.320100.5~107.02.4硅噻菌胺100103.4~106.71.5500089.3~97.03.81096.0~122.08.72098.0~110.04.6吲唑磺菌胺100102.7~108.01.7500099.5~117.65.910

14SN/T5440—2022表D.5番茄中5种酰胺类杀菌剂回收率范围化合物添加水平/(μg/kg)回收率范围/%相对标准偏差/%1098.0~106.03.02097.0~99.00.9噻唑菌胺100100.4~103.41.1500088.9~90.80.810100.0~114.05.520101.5~106.01.8双炔酰菌胺10097.6~99.70.8500086.1~97.84.31099.0~113.05.72097.0~102.02.0吡噻菌胺10095.6~99.41.5500086.0~90.92.21098.0~107.03.22095.0~103.03.0硅噻菌胺10096.7~99.51.2500089.7~91.40.91086.0~98.06.42080.0~98.08.0吲唑磺菌胺10091.2~100.03.2500095.9~101.22.1表D.6草莓中5种酰胺类杀菌剂回收率范围化合物添加水平/(μg/kg)回收率范围/%相对标准偏差/%10108.0~115.02.320101.0~110.03.5噻唑菌胺10097.8~105.82.8500080.3~88.13.510103.0~126.06.92099.0~108.53.3双炔酰菌胺100100.9~105.61.9500085.3~100.05.811

15SN/T5440—2022表D.6(续)化合物添加水平/(μg/kg)回收率范围/%相对标准偏差/%10103.0~119.05.52099.5~104.01.9吡噻菌胺10073.4~105.213.0500076.0~86.65.610103.0~116.04.12097.5~104.02.3硅噻菌胺10089.6~101.04.1500086.3~89.71.810105.0~125.06.72099.0~108.53.5吲唑磺菌胺10077.3~102.09.5500095.1~100.62.7表D.7猪肉中5种酰胺类杀菌剂回收率范围化合物添加水平/(μg/kg)回收率范围/%相对标准偏差/%1073.0~98.010.1噻唑菌胺2087.0~99.55.410087.8~94.52.51065.0~82.08.4双炔酰菌胺2080.0~98.49.310095.1~111.26.21090.0~107.07.8吡噻菌胺2090.5~111.58.4100103.8~117.45.010100.0~115.05.0硅噻菌胺2098.5~110.04.610096.4~105.03.21059.0~83.014.2吲唑磺菌胺2064.5~82.19.310072.0~78.43.312

16SN/T5440—2022表D.8花生中5种酰胺类杀菌剂回收率范围化合物添加水平/(μg/kg)回收率范围/%相对标准偏差/%1071.0~77.05.8噻唑菌胺2077.5~83.53.010080.7~84.32.31072.0~86.05.9双炔酰菌胺2082.5~93.54.310082.5~93.14.41079.0~88.05.7吡噻菌胺2090.5~94.02.010090.2~94.71.71075.0~80.09.3硅噻菌胺2082.5~87.55.610089.2~91.82.81066.0~82.09.1吲唑磺菌胺2070.0~76.03.210072.2~76.23.513

17

18SN/T5440—2022Foreword《DirectivesThisdocumentisaccordancewithGB/T1.1—2020forstandardization~part1:rulesfor《Rulesthestructureanddraftingofstandardizingdocuments》andSN/T0001—2016forstandardsofphysicalandchemicalanalysismethodforthedeterminationinfoodandcosmeticsforexport》.Attentionisrequiredtothecertaincontentsofthistextwhichmightberelatedtosomepatents.Thisfileisnotresponsibletoidentifythese.ThisdocumentwasproposedbyandisunderthechargeofGeneralAdministrationofCustomsP.R.China.ThisdocumentwasdraftedbyHangzhouCustomsDistrictP.R.China.ThisdocumentwasmainlydraftedbyZhuZitong,XieWen,LeiMeikang,JiangZhiying,HouJian-bo,YeYoubiao,ZhangYingjun.15

19SN/T5440—2022Determinationofmultipleamidefungicidesincludingmandipropamid,ethaboxam,amisulbrometcinfoodforexport—LC-MS/MSmethod1ScopeThisstandardspecifiesthemethodofsampledeterminationofmandipropamid,ethaboxam,amisul-brom,silthiopham,penthiopyradinfoodforexportbyLC-MS/MS.Thisstandardisapplicabletothedeterminationandconfirmationofmandipropamid,ethaboxam,amisulbrom,silthiopham,penthiopyradresiduesingrape,cabbage,celery,cucumber,tomato,strawberry,peanutandporkforexportbyLC-MS/MS.2NormativereferencesThecontentsofthefollowingdocumentsconstituteessentialprovisionsofthisdocumentthroughnormativereferencesinthetext.Amongthem,thedateofthereferencedocument,onlythedateofthecorrespondingversionisapplicabletothisdocument.Nodateofthereferencedocument,itslat-(includingestversionallamendments)isapplicabletothisdocument.GB/T6682Waterforanalyticallaboratoryuse—Specificationandtestmethods3TermanddefinitionThereisnoneedoftermanddefinitioninthisdocument.4PrincipleTheresiduesofmandipropamid,ethaboxam,amisulbrom,silthiopham,penthiopyradinsampleareextractedwith1%aceticacidacetonitrilesolutionbyhomogenization,cleanedupwithdispersive(QuEChERS)solid-phaseextractionmethodanddeterminedbyLC-MS/MS,quantifiedbyexternalstandardmethod.16

20SN/T5440—20225Reagentsandmaterials“Water”Unlessotherwisespecified,allreagentsusedshouldbeofanalyticallypure,isthefirstgradewatercompliedwithGB/T6682.5.1Acetonitrile:chromatographypure.5.2Methanol:chromatographypure.5.3Formicacid:chromatographypure.5.41%aceticacidacetonitrilesolution:pipette1.0mLaceticaciddiluteto100mLwithacetoni-trile.5.50.15%formicacidsolution:pipette1.5mLformicaciddiluteto1000mLwithwater.5.6Standardsubstances:mandipropamid,ethaboxam,amisulbrom,silthiopham,penthiopyrad,purity≥98.0%,Thename,CASnumber,molecularformulaandmolecularweightof5kindofam-idefungicidesarelistedinappendixA.5.7Standardstocksolution:accuratelyweighappropriatestandard(5.6),dissolvewithacetoni-trile.Theconcentrationofthestandardstocksolutionis1000μg/mL.Thesolutionshouldbestoredat-18℃indark.5.8Mixedmediumstandardsolution:respectivelypipetteappropriatestandardstocksolution(5.7),dilutewithacetonitrile.Theconcentrationofthismixedmediumstandardsolutionis10μg/mL.Thesolutionshouldbestoredat-18℃indark.5.9Matrixmatchedmixedstandardworkingsolution:accuratelypipettemixedmediumstandardsolution,dilutewithblanksampleextracttoobtain1.0ng/mL,2.0ng/mL,5.0ng/mL,10.0ng/mL,20.0ng/mL,40.0ng/mL,60.0ng/mLofmatrixmatchedmixedstandardworkingso-lution.Thematrixmatchedmixedstandardworkingsolutionshouldbepreparedbeforeusing.(TSCD),5.10Extractagent:4gofmagnesiumsulfate,1gsodiumchloride,1gsodiumcitrate(DHS).0.5gsodiumhydrogencitrate(PSA),5.11Cleaning-upagent:150mgofmagnesiumsulfate,25mgofprimarysecondaryamine(GCB).75mgofgraphitizedcarbonblack5.12Membranefilter:0.22μm,organictype.17

21SN/T5440—20226Apparatusandequipment6.1LC-MS/MS:equippedwithelectrosprayionsource.6.2Analyticalbalance:accurateto0.0001g,0.01g.6.3Centrifuge:speedofnolessthan8000r/min.6.4Homogenizer.6.5Vortexmixer.6.6Centrifugetube:polypropylene,50mL.7PreparationandstorageoftestsampleTakerepresentativesamplesof500g,trituratethesamplewithacomminuterafterchoppingtheed-iblepart.Andthenplaceincleancontainers,sealandindicatethetag,storagebelow-18℃.Inthecourseofsamplepreparation,precautionmustbetakenavoidthecontaminationoranyfactorswhichmaycausethechangeofresiduecontent.8Procedure8.1Extraction8.1.1Vegetableandfruit(accurateWeigh10gto0.01g)ofthetestsampleintoa50mLcentrifugetube,add20mL1%ace-(5.10),ticacidacetonitrilesolutionandhomogenizeat9000r/minfor1min,addextractantvortexblendingfor1min,andthencentrifugethesampleat8000r/minfor5min.Thesupernatantisreadyforcleanup.8.1.2Meatproductandnuts(accurateWeigh5gto0.01g)ofthetestsampleintoa50mLcentrifugetube,add15mL1%aceticacidacetonitrilesolutionandhomogenizeat9000r/minfor1min,andthencentrifugethesampleat8000r/minfor5min.Thesupernatantistakenintoa25mLcolorimetrictube.Another10mL1%aceticacidacetonitrilesolutionisadded,vortexblendingfor1min,andthencentrifugethesample18

22SN/T5440—2022at8000r/minfor5min.Combinethesupernatantintothesamecolorimetrictube.Thesupernatantisreadyforcleanup.8.2Cleaning-upTransfer2mLofthesupernatantintoa10mLcentrifugetube,add150mgofMgSO4,25mgofPSA,75mgofGCBintothecentrifugetube.Vibratevigorouslyfor1minandcentrifugeat8000r/minfor5min.Transfer0.5mLofthesupernatantandmakeuptothevolumeof1mLwithwater,vortexblendingfor1min.Filtertheanalysissolutionthrough0.22μmorganicmembrane,thefinalsolutionisreadyforanalysisbyLC-MS/MS.8.3Determination8.3.1Liquidchromatographyconditiona)Column:C184.6mm×150mm(i.d.),4.0μmparticlesizeorotherequivalent;b)Mobilephase:A:methanol,B:0.15%formicacid-water,theelutiongradientislistedinTable1;c)Flowrate:0.4mL/min;d)Columntemperature:40℃;;e)Injectionvolume:10μLTable1—MobilephaseandelutiongradientTime/minMobileA/%MobileB/%phasephase045.055.01.045.055.03.080.020.08.095.05.012.095.05.013.045.055.017.045.055.08.3.2Massspectrometrycondition(ESI);a)Ionsource:electrosprayionizationsourceb)Scanningmode:positiveionmode;19

23SN/T5440—2022(MRM);c)Monitoringmodel:multiplereactionmonitoringd)OtherreferencemassoperatingconditionsarelistedinappendixB.8.3.3QualitativeanalysisUnderthesameLC-MS/MSoperatingconditions,thematrixmatchedmixedstandardworkingsolu-tionandsamplesolutionisinjected.Iftheretentiontimeofsamplechromatogrampeaksareconsist-entwiththatofstandardsolutionwiththedifferencelessthan±2.5%.Therelativeintensityofsampletransitionsshallcorrespondtothoseofstandardsolutiontransitionsforconfirmation.Theconcentrationofstandardsolutionshouldbethesamewiththoseofsamplesolution.Thepermittedtoleranceslistedintable2,thenthecorrespondinganalytemustbepresentinsample.Table2—MaximumpermittedtolerancesrelativeionintensitieswhileconfirmationRelativeintensity/%>50>20~50>10~20≤10Permittedtolerances/%±20±25±30±508.3.4QuantitativeanalysisAccordingtotheamountofanalytesinthesampleliquid,selectedresponsevalueofsimilarmatrixmatchedmixedstandardworkingsolution.Theresponsesoftheanalyteinthestandardworkingso-lutionandthesamplesolutionshouldbewithinthelinearrangeoftheinstrumentdetection.UndertheaboveLC-MS/MSoperatingconditions,retentiontimeof5kindofamidefungicidesislis-(MRM)tedinTableB.1.Themultiplereactionmonitoringchromatogramsofstandardworkingsolu-tionarelistedinAnnexC.8.3.5BlanktestTheoperationoftheblanktestisthesameasthatdescribedinthemethodofdetermination,butwiththeomissionofsampleaddition.9CalculationandexpressionoftheresultCalculatethecontentofamidefungicideresiduesinthetestsamplebythechromatogramdatapro-(1).cessingsoftwareorbythefollowedformulaThebankvaluesshouldbedeductedfromthecal-culationresult.Ci×V…………………………()Xi=1m20

24SN/T5440—2022Where:/kg;Xi———thecontentofanalyteinthetestsample,μgci———theconcentrationofanalyteobtainedfromthematrixstandardworkingsolution,ng/mL;V———thefinalvolumeofthesamplesolution,mL;m———thecorrespondingmassofthetestsampleinthefinalsamplesolution,g.10Limitofquantificationandrecovery10.1LimitofquantificationThelimitofquantificationis10.0μg/kginthemethodformandipropamid,ethaboxam,amisulbrom,silthiopham,penthiopyrad.10.2RecoveryTherangesofrecoveryingrape,cabbage,celery,cucumber,tomato,strawberry,peanutandporkareshowedinappendixD.21

25SN/T5440—2022AnnexA(informative)Theinformationof5kindsofamidefungicideTableA.1—Theinformationof5kindsofamidefungicideNameCASNumberMolecularformulaMolecularweightethaboxam162650-77-3C14H16N4OS2320.43mandipropamid374726-62-2C23H22ClNO4411.88penthiopyrad183675-82-3C16H20F3N3OS359.41silthiopham175217-20-6C13H21NOSSi267.46amisulbrom348635-87-0C13H13BrFN5O4S2466.3122

26SN/T5440—2022AnnexB(Informative)1)ReferencemassconditionReferenceconditionsareasfollows:a)Ionsprayvoltage:3000V;(20b)Sheathgaspressure:3500kPaarb);c)Capillarytemperatures:275℃;(8d)Dryinggaspressure:1400kPaarb);e)Dryinggastemperatures:20℃;f)TheothermassparameterseetheTableB.1.TableB.1—Qualityions,quantityions,declusteringpotentialvoltageandcollisionenergyofanalyteRetentiontimeIonDeclusteringCollisionpairsCompound(min)(m/z)(v)energy(v)potential321.0/183.0*22ethaboxam6.6196321.0/200.026412.0/328.0*14mandipropamid7.3888412.0/124.935360.0/176.9*35penthiopyrad8.3882360.0/275.914268.0/138.9*19silthiopham8.4982268.0/73.032466.0/226.7*22amisulbrom9.5181466.0/148.146*markistheionquantificationpair.1)Non-commercialstatement:ParameterslistedinAppendixBareaccomplishedbyThermoFisherTSQVantageLC-MS/MS.Theequipmentanditstypeinvolvedinthestandardmethodisonlyforreferenceandnotrelatedtoanycommercialaim,andtheanalystsareencouragedtouseequipmentofdifferentcorporationordifferenttype.23

27SN/T5440—2022AnnexC(Informative)MRMchromatogramofstandard6.63mfe=182.50-183.50F:+cIESSFMrr^321.CC0100000[1S2.S09-183.OO1ethaboxam(321.0/183.0*)50000:_6.63N9.8^4nyz=1S9.9>200!.ESI^Mm2321.CC080000：[182.«9-183.001,60000!ethaboxam(321.0/200.0)40000：20oooi7,34MJ4.11E440000inVfe=327.5Q328.50F:-ESI3^lm£412CC0L809-124.SOI30000i′9&328.(001]MS20000;mandipropamid(412.0/328.0*)10000：7.34NJ2.85E4124.40-125.40R+c250001Ea3^lm£412C3C0i.ffie-124.'200001|jse932ac001)MS15000^mandipropamid(412.0/124.9)10OOOj500d84NJ1^rrizF17B.40-177.40R+C100000-ES)測也_360.00[176.勝17S.S01,penthiopyrad(360.0/176.9*)50OOO_1.168.34NE5275.40-276.40F:+c100000-ESJ測m£360.CC0[176.899-176.901,275.89&-275.901]MSpenthiopyrad(360.0/275.9)50000：0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0Time(min)8.451rr»5z=138.40-139.40F:60000，:+c田rrs2：268.00050000：[7299&-73.001,silthiopham(268.0/138.9*)138.899-138.901]IVB40000；30000；20000；10OOOj4.334.604.905.348530000：^725D-73.50R+cEaSR^/lrrB225000：[7299973.001，20OOOEsilthiopham(268.0/73)138.899-138.901].会g15oooj10oooj5000E-6.016.339^7350i+cKIS^MrrB24^.(X)030K[148.099-250227.09&-227.101]IVB200^iamisulbrom(466.0/226.7*)150j100!50j9.659.,47N-1.57E2147.60-■148.60F:40i+c田rrs220i紙.000amisulbrom(466.0/148.1)[148.099-1110022709&-227.101]IVBil10.0110.83'i'l0.00.'51：01.52：02：53：03：54：04：55：05：56：06：57：07：58：08：>59：69：5l(j.Old.5l.0Time(min)(1.0FigureC.1MRMChromatographyof5kindsofamidefungicideng/mL)24

28SN/T5440—2022AnnexD(Informative)ThefortifyingconcentrationandtherangeofrecoveryofanalyteTableD.1—RecoveryrangeofanalyteingrapeCompoundSpikelevel(μg/kg)Rangeofrecovery/%RSD/%10.098.0~102.01.720.086.0~97.04.6ethaboxam100.0102.7~107.01.65000.080.0~89.64.510.094.0~105.04.920.0104.0~115.53.7mandipropamid100.0114.4~121.82.65000.076.8~90.66.910.096.0~110.05.220.0102.0~107.51.8penthiopyrad100.0105.2~112.22.25000.080.1~92.05.310.092.0~105.04.420.098.0~108.53.6silthiopham100.0105.6~112.22.85000.080.5~97.67.710.072.0~100.014.320.086.0~94.53.7amisulbrom100.0105.9~108.91.05000.091.7~111.06.4TableD.2—RecoveryrangeofanalyteincabbageCompoundSpikelevel(μg/kg)Rangeofrecovery/%RSD/%10.084.0~95.04.620.088.5~92.51.9ethaboxam100.087.0~94.43.15000.083.5~94.54.825

29SN/T5440—2022(continued)TableD.2CompoundSpikelevel(μg/kg)Rangeofrecovery/%RSD/%10.078.0~83.02.420.076.5~79.51.3mandipropamid100.077.3~85.14.35000.085.6~95.34.12500080.8~91.25.010.087.0~91.01.620.084.5~88.52.1penthiopyrad100.083.9~94.54.95000.083.8~92.74.810.090.0~98.02.820.087.5~94.52.9silthiopham100.086.3~93.02.65000.081.2~88.33.410.084.0~95.04.420.071.0~82.56.6amisulbrom100.072.8~86.97.15000.092.1~99.32.9TableD.3—RecoveryrangeofanalyteinceleryCompoundSpikelevel(μg/kg)Rangeofrecovery/%RSD/%10.092.0~102.04.220.090.5~95.52.0ethaboxam100.087.3~94.63.15000.0108.3~111.11.010.084.0~101.06.320.080.0~98.06.8mandipropamid100.092.1~96.21.75000.085.6~92.13.010000.093.1~97.42.210.092.0~102.03.720.090.5~99.03.0penthiopyrad100.091.6~96.12.25000.084.7~92.33.220000.093.3~99.52.326

30SN/T5440—2022(continued)TableD.3CompoundSpikelevel(μg/kg)Rangeofrecovery/%RSD/%10.092.0~102.03.920.091.5~100.03.3silthiopham100.092.8~96.41.75000.093.9~97.31.210.075.0~97.010.920.081.0~99.07.2amisulbrom100.087.6~98.84.95000.095.3~102.02.7TableD.4—RecoveryrangeofanalyteincucumberCompoundSpikelevel(μg/kg)Rangeofrecovery/%RSD/%10.092.0~102.03.520.093.0~97.51.9ethaboxam100.0100.2~104.61.45000.083.8~92.13.510.0105.0~113.02.720.099.0~102.51.2mandipropamid100.099.4~125.38.15000.072.5~89.88.110.0102.0~112.03.320.0100.5~104.51.4penthiopyrad100.097.4~101.91.65000.0100.2~112.64.110.0103.0~115.04.320.0100.5~107.02.4silthiopham100.0103.4~106.71.55000.089.3~97.03.810.096.0~122.08.720.098.0~110.04.6amisulbrom100.0102.7~108.01.75000.099.5~117.65.927

31SN/T5440—2022TableD.5—RecoveryrangeofanalyteintomatoCompoundSpikelevel(μg/kg)Rangeofrecovery/%RSD/%10.098.0~106.03.020.097.0~99.00.9ethaboxam100.0100.4~103.41.15000.088.9~90.80.810.0100.0~114.05.520.0101.5~106.01.8mandipropamid100.097.6~99.70.85000.086.1~97.84.310.099.0~113.05.720.097.0~102.02.0penthiopyrad100.095.6~99.41.55000.086.0~90.92.210.098.0~107.03.220.095.0~103.03.0silthiopham100.096.7~99.51.25000.089.7~91.40.910.086.0~98.06.420.080.0~98.08.0amisulbrom100.091.2~100.03.25000.095.9~101.22.1TableD.6—RecoveryrangeofanalyteinstrawberryCompoundSpikelevel(μg/kg)Rangeofrecovery/%RSD/%10.0108.0~115.02.320.0101.0~110.03.5ethaboxam100.097.8~105.82.85000.080.3~88.13.510.0103.0~126.06.920.099.0~108.53.3mandipropamid100.0100.9~105.61.95000.085.3~100.05.828

32SN/T5440—2022(continued)TableD.6CompoundSpikelevel(μg/kg)Rangeofrecovery/%RSD/%10.0103.0~119.05.520.099.5~104.01.9penthiopyrad100.073.4~105.213.05000.076.0~86.65.610.0103.0~116.04.120.097.5~104.02.3silthiopham100.089.6~101.04.15000.086.3~89.71.810.0105.0~125.06.720.099.0~108.53.5amisulbrom100.077.3~102.09.55000.095.1~100.62.7TableD.7—RecoveryrangeofanalyteinporkCompoundSpikelevel(μg/kg)Rangeofrecovery/%RSD/%10.073.0~98.010.1ethaboxam20.087.0~99.55.4100.087.8~94.52.510.065.0~82.08.4mandipropamid20.080.0~98.49.3100.095.1~111.26.210.090.0~107.07.8penthiopyrad20.090.5~111.58.4100.0103.8~117.45.010.0100.0~115.05.0silthiopham20.098.5~110.04.6100.096.4~105.03.210.059.0~83.014.2amisulbrom20.064.5~82.19.3100.072.0~78.43.329

33SN/T5440—2022TableD.8—RecoveryrangeofanalyteinpeanutCompoundSpikelevel(μg/kg)Rangeofrecovery/%RSD/%10.071.0~77.05.8ethaboxam20.077.5~83.53.0100.080.7~84.32.310.072.0~86.05.9mandipropamid20.082.5~93.54.3100.082.5~93.14.410.079.0~88.05.7penthiopyrad20.090.5~94.02.0100.090.2~94.71.710.075.0~80.09.3silthiopham20.082.5~87.55.6100.089.2~91.82.810.066.0~82.09.1amisulbrom20.070.0~76.03.2100.072.2~76.23.530

34

35220—20445/TNS中华人民共和国出入境检验检疫行业标准出口食品中双炔酰菌胺、噻唑菌胺、吲唑磺菌胺等多种酰胺类杀菌剂残留量的测定液相色谱-质谱/质谱法SN/T5440—2022*中国海关出版社有限公司出版发行北京市朝阳区东四环南路甲1号(100023)编辑部:(010)65194242-7530网址www.customskb.com/book中国标准出版社秦皇岛印刷厂印刷*开本880×12301/16印张0.75字数17千字2022年9月第一版2022年9月第一次印刷印数1—500*SN/T5440-2022书号:155175·834定价36.00元