标准编号:	GB 31604.50-2020
中文名称:	食品安全国家标准 食品接触材料及制品 壬基酚迁移量的测定
英文名称:	National food safety standard - Food contact materials and articles - Determination of nonylphenol migration
中标分类:	X09    卫生、安全、劳动保护
行业分类:	GB    国家标准
发布机构:	国家卫生健康委员会 国家市场监督管理总局
发布日期:	2020-09-11
实施日期:	2021-3-11
标准状态:	valid
翻译语言:	英文
文件格式:	PDF
中文字符数:	7000 字
翻译价格(元):	420.0
交付时间:	付款后 1 个工作日

Codeofchina.com is in charge of this English translation. In case of any doubt about the English translation, the Chinese original shall be considered authoritative. National food safety standard Food contact materials and articles Determination of nonylphenol migration 1 Scope This standard specifies the determination of nonylphenol migration in food contact materials and articles by liquid chromatography-mass spectrometry/mass spectrometry method. This standard is applicable to the determination of nonylphenol in soaking solution obtained by migration test on food contact materials and articles which use water, 4% (volume fraction) acetic acid solution, 10% (volume fraction) ethanol solution, 20% (volume fraction) ethanol solution, 50% (volume fraction) ethanol solution, olive oil and 95% (volume fraction) ethanol solution as food simulants respectively or use 95% (volume fraction) ethanol solution and isooctane chemical alternative solvent. 2 Principle For 4% (volume fraction) acetic acid solution as food simulant, determination is carried out on the sample from the soaking solution obtained by migration test on 4% (volume fraction) acetic acid and neutralized with ammonia water; for olive oil as food simulant, determination is carried out on the sample from the soaking solution obtained by migration test on olive oil and extracted with acetonitrile and purified with n-hexane; for isooctane as chemical alternative solvent, determination is carried out on the sample from the soaking solution obtained by migration test on isooctane and evaporated to dryness, then redissolved with methanol; for other solutions or chemical alternative solvent, determination is directly carried out on the soaking solutions obtained by migration test. The nonylphenol in soaking solution is determined by liquid chromatography-mass spectrometry/mass spectrometry method and quantified by external standard method. 3 Reagents and materials Unless otherwise specified, analytically-pure reagents and Class-I water specified in GB/T 6682 are adopted for the purpose of this method. 3.1 Reagents 3.1.1 Glacial acetic acid (C2H4O2). 3.1.2 Anhydrous ethanol (C2H6O). 3.1.3 95% ethanol. 3.1.4 Isooctane (C8H18). 3.1.5 Olive oil: chemically pure, complying with GB 5009.156. 3.1.6 Methanol (CH4O): chromatographically pure. 3.1.7 Acetonitrile (C2H3N): chromatographically pure. 3.1.8 N-hexane (C6H14). 3.1.9 Ammonia water: chromatographic purity, with a volume fraction ≥25%. 3.2 Preparation of reagents 4% (volume fraction) acetic acid solution, 10% (volume fraction) ethanol solution, 20% (volume fraction) ethanol solution and 50% (volume fraction) ethanol solution are prepared according to GB 5009.156. 3.3 Standards Nonylphenol (mixture of branched isomers, C15H24O, CAS No.: 84852-15-3) standard solution: 1,000mg/L 3.4 Preparation of standard solutions 3.4.1 Standard intermediate solution (100mg/L) Accurately transfer 1.00mL nonylphenol standard solution (1,000mg/L) into a 10mL volumetric flask, dilute to the scale with methanol, and then mix well. The solution is valid for 6 months in the refrigerator at 0℃~4℃. 3.4.2 Standard intermediate solution (5mg/L) Accurately transfer 0.50mL nonylphenol standard intermediate solution (100mg/L) into a 10mL volumetric flask, dilute to the scale with methanol, and then mix well. 3.4.3 Standard working solutions 3.4.3.1 4% (volume fraction) acetic acid standard working solution Accurately transfer 0.02mL, 0.04mL, 0.06mL, 0.10mL, 0.20mL and 0.40mL standard intermediate solutions (5mg/L) into six 10mL volumetric flasks respectively, and dilute to the scale with 4% (volume fraction) acetic acid solution. The standard working solutions with mass concentrations of 0.01mg/L, 0.02mg/L, 0.03mg/L, 0.05mg/L, 0.10mg/L and 0.20mg/L are obtained. Prior to practice, the solutions shall be treated synchronously with food simulant soaking solution according to 5.1.2.1. 3.4.3.2 Oil-based food simulant standard working solution Accurately weigh 5.00g (accurate to 0.1mg) olive oil into six glass centrifuge tubes with stoppers respectively, add 0.01mL, 0.02mL, 0.03mL, 0.05mL, 0.10mL and 0.20mL standard intermediate solutions (5mg/L) respectively, vortex for mixing well to obtain 0.01mg/kg, 0.02mg/kg, 0.03mg/kg, 0.05mg/kg, 0.10mg/kg and 0.20mg/kg standard working solutions. Prior to practice, the solutions shall be treated synchronously with food simulant soaking solution according to 5.1.2.2. 3.4.3.3 Isooctane standard working solution Accurately transfer 0.02mL, 0.04mL, 0.06mL, 0.10mL, 0.20mL and 0.40mL standard intermediate solutions (5mg/L) into six 10mL volumetric flasks respectively, dilute to the scale with isooctane, and mix well to obtain the standard working solutions with mass concentrations of 0.01mg/L, 0.02mg/L, 0.03mg/L, 0.05mg/L, 0.10mg/L and 0.20mg/L respectively. Prior to practice, the solutions shall be treated synchronously with food simulant soaking solution according to 5.1.2.3. 3.4.3.4 Other food simulant and chemical alternative solvent standard working solutions Accurately pipet 0.02mL, 0.04mL, 0.06mL, 0.10mL, 0.20mL and 0.40mL standard intermediate solutions (5mg/L) into six 10mL volumetric flasks respectively, dilute to the scale with corresponding food simulant or chemical alternative solvent to obtain other water-based food simulant or chemical alternative solvent standard working solutions with mass concentrations of 0.01mg/L, 0.02mg/L, 0.03mg/L, 0.05mg/L, 0.10mg/L and 0.20mg/L respectively. 4 Apparatus 4.1 Liquid chromatography-tandem triple quadrupole mass spectrometer: equipped with electrospray ionization (ESI). 4.2 Vortex oscillator. 4.3 Analytical balances: with sensibility of 0.0001g and 0.01g respectively. 4.4 High-speed centrifuge: with a maximum rotation speed ≥10,000r/min. 5 Analysis steps 5.1 Preparation of test solution 5.1.1 Migration test Food contact materials and articles are subjected to migration test according to the requirements of GB 31604.1 and GB 5009.156. The soaking solution obtained by migration test shall be stored in a refrigerator at 4℃ free from light if cannot be tested immediately. The soaking solution shall be restored to room temperature before the next test. 5.1.2 Treatment of soaking solution 5.1.2.1 Treatment of 4% (volume fraction) acetic acid soaking solution Transfer 5.0mL 4% (volume fraction) acetic acid soaking solution obtained by migration test, add 0.5mL ammonia water, mix well, centrifuge for 5min at 10,000r/min, and the supernatant is to be determined. 5.1.2.2 Treatment of oil-based food simulants Weigh 5.00g (accurate to 0.01g) olive oil soaking solution obtained by migration test into a glass centrifuge tube with stopper, add 2mL n-hexane, mix well, then add 5.0mL acetonitrile, vortex for oscillating for 0.5min, centrifuge for 5min at 4,000r/min, take the upper acetonitrile solution for centrifuging at 10,000r/min for 5min, and the supernatant is to be determined. 5.1.2.3 Treatment of isooctane soaking solution Transfer 10.0mL isooctane soaking solution obtained by migration test, evaporate to nearly dry at 40℃ in a rotary way, accurately transfer 10.0mL dissolved methanol residue, centrifuge for 5min at 10,000r/min , and the supernatant is to be determined. 5.1.2.4 Treatment of other food simulant soaking solutions and chemical alternative solvent soaking solutions Transfer a proper amount of soaking solution obtained by migration test, centrifuge for 5min at 10,000r/min, and the supernatant is to be determined. 5.1.3 Preparation of blank test solution Treat the food simulants and chemical alternative solvents that are not in contact with food contact materials and articles according to 5.1.1 and 5.1.2. 5.2 Instrument reference conditions 5.2.1 Liquid chromatography conditions The liquid chromatography reference conditions are as follows: a) Chromatographic column: C18 column, 2.6μm, 2.1mm×150mm (or equivalent). b) Mobile phase: methanol-water (90+10, volume ratio). c) Flow rate: 0.3mL/min. d) Column temperature: 40℃. e) Injection volume: 2μL. 5.2.2 Mass spectrometry conditions The mass spectrometry reference conditions are as follows: a) Ionization mode: electrospray ionization in negative ion mode (ESI-). b) Scanning mode of mass spectrometry: multi-reaction monitoring (MRM). c) See Table A.1 for other mass spectrometry parameters. 5.3 Plotting of standard curve Determine the standard working solution according to the instrument reference conditions listed in 5.2, plot the standard curve with the concentration of nonylphenol in the standard working solution as X-coordinate and the corresponding quantitative ion peak area as Y-coordinate, and obtain the linear equation. See Annex B for the chromatogram of nonylphenol standard working solution.

1 Scope 2 Principle 3 Reagents and materials 4 Apparatus 5 Analysis steps 6 Expression of analysis results 7 Precision 8 Others Annex A Reference mass spectrometry conditions Annex B MRM chromatogram of nonylphenol standard working solution

中华人民共和国国家标准 GB 31604.50—2020 食品安全国家标准 食品接触材料及制品 壬基酚迁移量的测定 2020-09-11发布 2021-03-11实施 中华人民共和国国家卫生健康委员会 国家市场监督管理总局 发布 食品安全国家标准 食品接触材料及制品 壬基酚迁移量的测定 1 范围 本标准规定了食品接触材料及制品壬基酚迁移量的液相色谱质谱/质谱测定方法。 本标准适用于食品接触材料及制品以水、4％(体积分数)乙酸溶液、10％(体积分数)乙醇溶液、20％(体积分数)乙醇溶液、50％(体积分数)乙醇溶液、橄榄油、95％(体积分数)乙醇溶液为食品模拟物或采用95％(体积分数)乙醇溶液、异辛烷化学替代溶剂经迁移试验所得浸泡液中壬基酚的测定。 2 原理 以4％(体积分数)乙酸溶液为食品模拟物经迁移试验所得浸泡液加氨水中和后进样测定；以橄榄油为食品模拟物经迁移试验所得浸泡液经乙腈萃取和正己烷净化后进样测定；以异辛烷为化学替代溶剂经迁移试验所得浸泡液蒸干后用甲醇复溶，进样测定；其他迁移试验所得浸泡液、化学替代溶剂浸泡液直接进样测定。浸泡液中的壬基酚采用液相色谱质谱/质谱法测定，外标法定量。 3试剂和材料 除非另有说明，本方法所用试剂均为分析纯，水为GB/T 6682规定的一级水。 3.1 试剂 3.1.1 冰乙酸(C2H4O2)。 3.1.2无水乙醇(C2H6O)。 3.1.3 95%乙醇。 3.1.4异辛烷(C8H18)。 3.1.5橄榄油：化学纯，符合GB 5009.156的要求。 3.1.6 甲醇(CH4O)：色谱纯。 3.1.7 乙腈(C2H3N)：色谱纯。 3.1.8正己烷(C6H14)。 3.1.9氨水：色谱纯，体积分数≥25％。 3.2 试剂配制 4％(体积分数)乙酸溶液、10％(体积分数)乙醇溶液、20％(体积分数)乙醇溶液、50％(体积分数)乙醇溶液的配制按GB 5009.156操作。 3.3 标准品 壬基酚(支链异构体的混合物，C15H24O，CAS号：84852-15-3)标准溶液：1 000 mg/L。 3.4标准溶液配制 3.4.1标准中间液(100 mg/L) 准确移取壬基酚标准溶液(1 000 mg/L)1.00 mL于10 mL容量瓶中，用甲醇稀释并定容至刻度，混匀。此溶液在0℃～4℃冰箱中保存，有效期为6个月。 3.4.2标准中间液(5 mg/L) 准确移取壬基酚标准中间液(100 mg/L)0.50 mL于10 mL容量瓶中，用甲醇稀释并定容至刻度，混匀。 3.4.3标准工作溶液 3.4.3.1 4％(体积分数)乙酸标准工作溶液 分别准确移取标准中间液(5 mg/L)0.02 mL、0.04 mL、0.06 mL、0.10 mL、0.20 mL、0.40 mL于6个10 mL容量瓶中，用4％(体积分数)乙酸溶液定容至刻度。得到质量浓度分别为0.01 mg/L、0.02 mg/L、0.03 mg/L、0.05 mg/L、0.10 mg/L、0.20 mg/L标准工作溶液。上机前需按照5.1.2.1与食品模拟物浸泡液同步处理。 3.4.3.2 油基食品模拟物标准工作溶液 分别准确称取5.00 g(精确到0.1 mg)橄榄油于6个具塞玻璃离心管中，分别加入标准中间液(5 mg/L)0.01 mL、0.02 mL、0.03 mL、0.05 mL、0.10 mL、0.20 mL，涡旋混匀，得到分别为0.01 mg/kg、0.02 mg/kg、0.03 mg/kg、0.05 mg/kg、0.10 mg/kg、0.20 mg/kg标准工作溶液。上机前需按照5.1.2.2与食品模拟物浸泡液同步处理。 3.4.3.3异辛烷标准工作溶液 分别准确移取标准中间液(5 mg/L)0.02 mL、0.04 mL、0.06 mL、0.10 mL、0.20 mL、0.40 mL于6个10 mL容量瓶中，用异辛烷定容至刻度，混匀，得到质量浓度分别为0.01 mg/L、0.02 mg/L、0.03 mg/L、0.05 mg/L、0.10 mg/L、0.20 mg/L标准工作溶液。上机前需按照5.1.2.3与食品模拟物浸泡液同步处理。 3.4.3.4 其他食品模拟物、化学替代溶剂标准工作溶液 分别吸取标准中间液(5 mg/L)0.02 mL、0.04 mL、0.06 mL、0.10 mL、0.20 mL、0.40 mL于6个10 mL容量瓶中，用相应的食品模拟物或化学替代溶剂定容至刻度，得到质量浓度分别为0.01 mg/L、0.02 mg/L、0.03 mg/L、0.05 mg/L、0.10 mg/L、0.20 mg/L的其他水基食品模拟物或化学替代溶剂标准工作溶液。 4仪器和设备 4.1 液相色谱串联三重四极杆质谱仪：配电喷雾离子源(ESI)。 4.2涡旋振荡器。 4.3分析天平：感量0.000 1 g、0.01 g。 4.4高速离心机：最高转速>10 000 r/min。 5分析步骤 5.1试液的制备 5.1.1 迁移试验 食品接触材料及制品按照GB 31604.1和GB 5009.156的要求进行迁移试验。迁移试验所得浸泡液如不能立即测试，应置于4℃冰箱中避光保存。若进行下一步试验，应将浸泡液恢复至室温后使用。 5.1.2浸泡液的处理 5.1.2.1 4％(体积分数)乙酸浸泡液的处理 移取迁移试验所得4％(体积分数)乙酸浸泡液5.0 mL，加入0.5 mL氨水混匀后，经10 000 r/min离心5 min后，上清液待测。 5.1.2.2 油基食品模拟物的处理 称取5.00 g(精确至0.01 g)迁移试验所得橄榄油浸泡液至具塞玻璃离心管中，加入2 mL正己烷混匀，再加入5.0 mL乙腈，涡旋振荡0.5 min，4 000 r/min离心5 min，取上层乙腈溶液经10 000 r/min离心5 min，上清液待测。 5.1.2.3异辛烷浸泡液的处理 移取迁移试验所得异辛烷浸泡液10.0 mL，于40℃旋蒸至近干，准确移取10.0 mL甲醇溶解残渣，经10 000 r/min离心5 min，上清液待测。 5.1.2.4 其他食品模拟物浸泡液、化学替代溶剂浸泡液的处理 移取适量迁移试验所得浸泡液，经10 000 r/min离心5 min，上清液待测。 5.1.3 空白试液的制备 按5.1.1和5.1.2处理未与食品接触材料及制品接触的食品模拟物、化学替代溶剂。 5.2仪器参考条件 5.2.1 液相色谱条件 液相色谱参考条件如下： a)色谱柱：C18柱，2.6 μm，2.1 mm×150 mm(或等效色谱柱)。 b)流动相：甲醇-水(90+10，体积比)。 c)流速：0.3 mL/min。 d)柱温：40℃。 e)进样量：2μL。 5.2.2 质谱条件 质谱参考条件如下： a)离子化模式：电喷雾电离负离子模式(ESI)。 b)质谱扫描模式：多反应监测(MRM)。 c)其他质谱参数参见附录A中表A.1。 5.3标准曲线的绘制 按照5.2所列的仪器参考条件，对标准工作溶液进行测定，以标准工作溶液中壬基酚的浓度为横坐标，以对应的定量离子峰面积为纵坐标，绘制标准曲线，得到线性方程。壬基酚标准工作溶液的色谱图参见附录B。 5.4试液的测定 5.4.1 定性测定 按照5.2所列的仪器参考条件，测定食品模拟物试液和标准工作溶液，若试液与标准溶液中待测物的质量色谱峰保留时间的偏差在±2.5％范围内；所有定性离子的信噪比均超过3：1，且定性离子对的相对丰度与浓度相当的标准溶液的相对丰度一致，相对丰度偏差不超过表1的规定，则可判断样品中存在相应的待测物。 表1 定性测定时相对离子丰度的最大允许偏差 相对离子丰度，k/％ k≥50 20