SN/T 4441-2016 进出口化妆品中甲醇的测定 多维气相色谱-质谱联用法 SN/T4441-2016 标准压缩包解压密码：www.bzxz.net

中华人民共和国出入境检验检疫行业标准SN/T4441—2016
进出口化妆品中甲醇的测定
多维气相色谱-质谱联用法
Determination of methanol in cosmetics for import and export-MDGC-MSmethod
2016-03-09发布
中华人民共和国
国家质量监督检验检疫总局
2016-10-01实施
本标准按照GB/T1.1—2009给出的规则起草。SN/T4441—2016
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：中华人民共和国上海出入境检验检疫局、中华人民共和国厦门出人境检验检疫局。
本标准主要起草人：伊雄海、周瑶、柯志成、赵善贞、曲栗、时逸吟、邓晓军、徐敦明1范围
进出口化妆品中甲醇的测定
多维气相色谱-质谱联用法
本标准规定了化妆品中甲醇含量的多维气相色谱-质谱测定方法SN/T4441—2016
本标准适用于香水、指甲油、洗甲水、沐浴露、洗发水、洗面奶、卸妆露、润肤露、爽肤水、摩丝中甲醇的测定和确证。
2规范性引用文件
下列文件对于本文件的应用是必不可少的。凡是注日期的引用文件，仅注日期的版本适用于本文件。凡是不注H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方法提要
试样于密封的顶空进样瓶中，在一定的温度和时间平衡下，使试样中的甲醇在气液两相中达到动态平衡，以多维气相色谱-质谱联用法进行测定，外标法定量。4试剂材料
除非另有说明，所用试剂均为分析纯，水为GB/T6682一2008规定的一级水。4.1无甲醇乙醇：乙醇：纯度≥99.99%4.275%乙醇溶液：取无甲醇乙醇75ml.用水稀释至100ml4.3甲醇标准物质：甲醇（methonal,CAS：67-56-1，分子式：CH.0)纯度≥99.9%。4.4标准储备液的配制：准确量取适量的甲醇标准品，用75%乙醇配制成浓度为100g/L，10g/L的标准溶液。于一18℃避光密封保存，有效期6个月。4.5标准工作溶液的配置：根据需要，临用时吸取一定量的标准储备溶液，用75%乙醇配置成适当浓度的标准工作溶液。于4℃避光保存，现用现配。5仪器与设备
5.1电子天平：感量分别为0.01g,0.0001g。5.2顶空进样瓶：10mL。
5.3多维气相色谱-质谱仪：配有CTC自动顶空进样器。1D系统配有氢火焰离子化检测器（FID）和Deans switch切换阀。2D系统配有四级杆质谱仪（EI源）。1
SN/T4441—2016
6分析步骤
6.1取样
香水、指甲油、洗甲水、沐浴露、洗发水、洗面奶、卸妆露、润肤露和爽肤水直接取样。摩丝等含推进剂的样品，取一定量75%乙醇于顶空瓶中，在摩丝的喷嘴上装一注射器针头，连接聚四氟乙烯细管，将此管另一端插人到乙醇液面下，缓缓按压喷嘴，使发胶从针头流出经聚四氟乙烯细管流人到乙醇溶液中，用减差法计算取样量。如样品中甲醇浓度过高，应先将样品用75%乙醇稀释。6.2预处理
称取2.0g样品（准确至0.01g）于顶空进样瓶中，加人75%乙醇溶液2.0mL，密封后于自动顶空进样器中70℃恒温、500r/min振荡10min，取气液平衡后的液上气体供多维气相色谱-质谱联用仪测定。6.3测定
6.3.1第一维气相色谱测定条件
第一维气相色谱测定条件如下：色谱柱：DB-5ms，长30m，内径0.25mm，膜厚0.25μm，或相当者；a)
升温程序：45C保持4min，以30℃/min升至250℃（保持2.5min）；c)
载气：氮气，纯度≥99.999%，恒压模式：142.1kPa进样方式：分流进样，分流比：50：1；进样量：500μL；
进样口温度：240℃；
检测器：FID；
检测器温度：260℃；
切割压力（APC)：88.3kPa；
中心切割窗口：3.45min~3.65min此窗口只包含甲醇标准品所在位置，切勿包含乙醇或异丙醇）)。
第二维气相色谱-质谱测定条件
第二维气相色谱-质谱测定条件如下：a)
色谱柱：HP-INNOWAX，长30m，内径0.32mm，膜厚0.25μm，或相当者：升温程序：50℃保持6min，以30℃/min升至180℃（保持3min）；载气：氮气，纯度≥99.999%，流速：1.5mL/min；d)
电离方式：EI,70eV；
接口温度：250℃；
离子源温度：200℃：
溶剂延迟：3min；
测定方式：选择离子监测模式（SIM）)。h）
监测离子：31.0”，32.029.0，30.0，“*”为定量离子。2
7色谱测定
7.1定性测定
SN/T4441—2016
按照多维气相色谱-质谱条件测定样品和标准工作溶液，样品的质量色谱峰保留时间与标准品中对应的保留时间致；且样品中目标组分定性离子的相对丰度与接近浓度的标准工作溶液中相应的定性离子的相对丰度进行比较，偏差不超过表1规定的范围，则可判定样品中存在对应的被测物。表1定性确证时相对离子丰度的最大允许偏差相对离子丰度
允许的相对偏差
7.2定量测定
>20%~50%
>10%~20%
在仪器最佳工作条件下，对标准工作溶液进样。用标准工作曲线按外标法定量，样品溶液中被测物的响应值均应在仪器测定的线性范围内。根据试样中被测样液的含量情况，选取响应值相近的标准工作液进行色谱分析。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。在上述色谱条件下甲醇的参考保留时间约为5.56min，甲醇标准品的选择离子监测色谱图（SIM）和质谱图参见附录A。如样品中甲醇含量超过本方法线性范围，应将样品用75%乙醇稀释后再行分析。7.3空白试验
除不加试样外，均按上述操作步骤进行。8结果计算和表达
结果用色谱数据处理机或按式（1)计算试样中甲醇的含量，计算结果需扣除空白值：X
式中：
试样中甲醇含量，单位为毫克每千克（mg/kg）；样液中甲醇的峰面积；
-标准工作溶液中甲醇的浓度，单位为毫克每升（mg/L)；A
标准工作溶液中甲醇的峰面积；m
最终样液代表的试样量，单位为克（g）。注：计算结果应扣除空白值。
测定低限和回收率
测定低限
....(1)
本方法对进出口香水、指甲油、洗甲水、沐浴露、洗发水、洗面奶、卸妆露、润肤露、爽肤水、摩丝中甲醇含量的测定低限均为100rng/kg。SN/T4441—2016
9.2回收率
不同添加浓度范围内回收率的试验数据，见表2。表2
添加浓度
样品名称
指甲油
洗甲水
沐浴露
洗发水
标准添加浓度及回收率的试验数据（n=6）回收率范围此内容来自标准下载网
81.38~-96.79
82.35--103.54
9317--107.04
95.01103.14
85.59--99.5
81:41--96.42
80.72-86.69
84.29~97.83
67~102
35~~109.61
88.43-108.53
89.49-98.99
添加浓度
1：000.0
样品名称
洗面奶
卸妆露
润肤露
爽肤水
回收率范围
100.89~109.67
94.04~103.38
83.09~101.31
86.51~106.37
90.64-~104.09
93.47103.79
86.72~99.85
90.04105.98
86.53~107.25
90.74102.96
96.81-107.57
95.05108.33
81.19~94.76
93.81106.18
83.99-98.61
80.51~94.19
96.54~107.99
96.49--106.21
92.7798.29
99.09~109.85
附录A
（资料性附录）
甲醇标准品选择离子色谱图及质谱图甲醇标准品选择离子色谱图及质谱图见图A.1和图A.2。（X1.000,000)
2.03.04.050
10.011.012.0
图A1甲醇标准溶液的选择离子色谱图%
甲醇标准品的全扫描质谱图
SN/T4441—2016
SN/T4441—2016
Foreword
The standard is drafted in accordance with the rules given in the GB/T 1.1-2009 Directives forstandardization-Part1:Structureand draftingof standardsAttention is drawn to the possibility that some of the elements of this standard may be the subject ofpatent rights. The issuing body of this document shall not be held responsible for identifying any orall suchpatent rights.
This standard was proposed by and is under the charge of the Certification and Accreditation Admin-istrationof thePeople'sRepublicofChina.This standard was drafted by the Shanghai Entry-Exit Inspection and Quarantine Bureau of thePeople's Republic of China and Xiamen Entry-Exit Inspection and Quarantine Bureau of the People'sRepublicofChina
Themain drafters of this standard are Yi xionghai,Zhou yao,Ke zhicheng,Zhao shanzhen,Qu li,Shiyiyin,Deng xiaojun,Xu dunming.Note:This Englishversion,atranslation fromtheChinesetextis solelyforguidance1
SN/T4441—2016
Determination of methanol in cosmetics forimportandexportMDGC-MSmethodScope
This standard specifies the MGDC-MS method for determination ofmethanol in cosmetics for exportThis standard is applicable to the determination and confirmation of content of methanol in perfume.nail polish,nail polishremover,bathcream,shampoo.mildywash,make-up remover,body lotion,astringent lotion,mousseforexport.2Normativereference
The following normative documents contain provisions which,through reference in this text,constitute provisions of this standard.For dated references,subsequent amendments to, or revisionsofanyof these publicationsdonotapplied.Howeverpartiestoagreements based onthis standardare encouraged to investigate the possibility of applying the most recent editions of the normativedocuments indicated below.For undated references,the latest edition of the normative documentreferred to applies.
analysis laboratorywaterspecificationand testmethodGB/T6682
Principle
The test samples are weighed into sealed vials.Under certain temperature and time, the methanol insamples reaches dynamic balance in the gas-liquid two-phase,then determined by MultidimensionalGas Chromatography with Mass Spectrometric Detection.and quantified by external standard meth-od.
4 Reagents and materials
All the reagents used should be analytically pure unless otherwise specified.\Water\is first class wa-ter as GB/T 6682 specified.
Ethanol(containnomethonal):purity≥99.99%.SN/T4441—2016
4.275%ethanol:obtainedbydissolving75mLethanol inMilli-Qwater,withafinal volumeof100mL.
4.3Methonal standards：Methonal(CAS：67-56-1，分子式：CH.O)：Purity≥99.0%Standard stock solution: accurately weigh certain amount of methanol standard and dissolve4.4
with75% ethanol tomakethe standard stock solution of 100 g/L,10 g/L.The solution is stored in arefrigerator at -18 C ,assign a shelf life of 6 months.4.5Working standard solutio
ransferadeuqateintermediate solutionofstandards to 75% ethanol for preparation of working standard solutions when it will be used. storerefrigerated at 4.Prepare the solutions when use.5 Apparatus and equipment
Electronicbalance:accurateto0.01g.0.o005.1
5.2Headspacevials:10mL
5.3Multidimensional Gas Chromatography-Mass Spectrometric Detection,equippedwith CTCAna-lyticsCombiPALautomaticheadspacesampler.The 1D chromatograph,equipped with flame-ionization detection (FID)and Deans switching system.The 2D chromatograph,equipped with quadrupolemassspectrometerandelectronimpactionsource(El)6AnalysisSteps
Preparation of test sample
Perfume,nail polish,nail polish remover.bath cream,shampoo,mildywash,make-up remover,body lotion,astringent lotion are weighted directly.Samples which contain propellant,such asmousse, sample in the following way:Transfer certain 75% ethanol to the crimp top vial, install asyringe needle on the nozzle of the mousse to connect a teflon tube, then insert the other end of tef.lon tubeintothe ethanol liquid level,press thenozzle gently,make thehair spray outflow fromtef-lon tube into ethanol solution, and use the subtraction method to calculate the sample quantity.Ifconcentration of methanol in the sample is too high, samples shall be diluted.6.2Pretreatment
Weigh 2.0 g(accurate to 0.01 g)of the test sample into headspace vials, inject 2.0 mL 75% ethanol.Samples are sealed and incubated at 70 C in the heating block for 10 min with500 r/min vibration.Takethegason the liquid afterthebalance of gas-liquidand determinedbyMGDc-Ms8
Determination
6.3.11Dchromatographoperatingconditions1Dchromatographoperatingconditionsareasfollows：a)
SN/T4441—2016
Chromatographcolumn:DB-5mscolumn,30m×0.25mm（i.d),0.25μmfilmthickness（orother equivalentones);
Oven temperature program
(maintain for2.5min);
forAminthenincreaser
atarateof30℃/minto250℃
Carriergas:He,Purity≥99.999%.Constantvoltagemode.142.1kPa;c）
Injector mode:split mode;SplitInjectorvolume:500μL：
Injector port temperature:
Detector:FID;
Detector temperature:260
ratio:50:1
Cutting pressure (APC):88.3 kPa:Heart-Cuttingwindow:3.45min
mincThiswindowcontainsonlythelocationofmethanolstandard,be sure not to contain ethanol or isopropanol).6.3.22Dchromatographoperatingconitions
2D chromatographoperating conditions are as follows:a)
Chromatograph column:HP-INNOWAX column,30 m×0.32 mm (i.d),0.25μm filmthickness(orotherequivalentones);
Oven temperature program:50 C for 6 min,then increased at a rate of 30 ℃/min to 180 ℃b)
(maintainfor3min);
Carriergas:He，Purity≥99.999%.Flowrate:1.5mL/minlonizationmode:El,70eV;
SN/T4441—2016
Interface temperature:250℃:lonsourcetemperature：20oC
SolventDelay:3min;
Determination mode:select ion monitormode(SiM);Monitoringion:31.0\,32.0,29.0.30.0,\*\forthequantitativeion.7
ChromatographDetermination
Confirmation of the method
Under the MGDC-MS operating conditions,the standard working solution and sample solution is in-jected, If the retention times of sample chromatogram pecks are consistent with that of standard so-lution. calibration curve method is used for quantitative measurement.The relative intensities ofsample transitions shall correspond to those of standard solution transitions for confirmation.Theconcentration of standard solution should be same with those of sample solution.The permitted tol-erances listed inTable1,thecorrespondinganalytemustbepresent insample.Table 1-Maximum permitted tolerances relative ion intensities while confirmationrelativeintensity
permittedtolerances
Quantitationof themethod
20%~50%
>10%~20%
According to the approximate concentration of analyte in sample solution, select the standard work-ing solution with similar responses to that of sample solution.The responses of analyte in the stand.ard working solution and the sample solution should be within the linear range of the instrument de-tection.Under the above MGDC-MS operating conditions, the retention time of methanol is about5.56min.SiM chromatogram of methnol standard working solution is listed in Annex A.If the contentof methanol exceeds the method linearity, the sample should be diluted with 75% ethanol beforeanalysis.
7.3Blank test
Undergo according to the above procedures excluding the sample.10
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