Simultaneous Determination of 85 Acid Synthetic Pigments in Sauce by Liquid Chromatography Tandem Mass Spectrometry
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摘要: 建立了测定调味酱中85种酸性合成色素的液相色谱串联质谱高通量筛查方法。样品经甲醇提取，C18净化后，用水进行稀释，液相色谱串联质谱多反应监测模式测定，外标法定量。结果表明，85种酸性合成色素在10~1000 ng/mL的浓度范围内均呈良好的线性关系，相关系数均大于0.99，方法检出限为8.08~885.2 μg/kg，定量限为26.94~2950.7 μg/kg。在3个不同加标水平下，平均回收率在70.2%~116.5%，RSD为0.1%~15.0%。测定了市售的番茄酱、辣椒酱等50批次样品，在2批次样品中筛查出酸性红13、酸性橙II等禁止使用的色素。该方法通用性强、检测对象范围较广、分析时间短、灵敏度高，适合用于调味酱中85种酸性合成色素的分析测定。Abstract: A high-throughput liquid chromatography tandem mass spectrometry method was developed for the determination of 85 acid synthetic pigments in sauce. The acid synthetic pigments were extracted with methanol, purified with C18 and diluted with water. Subsequently, the sample was analyzed by liquid chromatography-tandem mass spectrometry under multiple reaction monitoring (MRM) mode, and quantified by external standard method. The results showed that the method had a good linearity in the range of 10~1000 ng/mL which correlation coefficients were greater than 0.99. The detection limit of the method was 8.08~885.2 μg/kg, and the quantitative limit was 26.94~2950.7 μg/kg. The average recoveries of synthetic pigments from spiked samples ranged from 70.2% to 116.5%, and the relative standard deviations were between 0.1% and 15.0%. This method was applied to analyze 50 batches of sauce such as tomato sauce and chili sauce, acid red 13 and acid orange II were screened out. The method has strong universality, wide range of detection objects, short analysis time and high sensitivity. It is suitable for the determination of 85 acid synthetic pigments in sauce.
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合成色素着色力强、价格便宜、稳定性好[1]，常用于食品中色泽的增强。但合成色素主要以苯、甲苯等工业原料，经磺化、偶氮化等一系列有机反应制得，进入人体吸收后会在体内分解成潜在的致癌物质，对人体造成不同程度的伤害[2]。合成色素按结构可以分为偶氮类、芳甲烷类、蒽醌类、杂环类、菁类、靛类等[3]。自2008年以来，我国陆续发布了1~5批《食品中可能违法添加的非食用物质和易滥用的食品添加剂名单》，公布了部分非食用色素名单。根据GB 2760-2014《食品安全国家标准 食品添加剂使用标准》[4]，我国仅允许使用日落黄等11种酸性合成色素，并规定了使用限量。国际《食品添加剂通用法典标准》规定了食品中仅允许使用胭脂红、赤藓红、日落黄、苋菜红、坚牢绿、亮蓝、靛蓝、诱惑红等8种酸性合成色素[5]。但合成色素种类繁多，不法商人在非食用色素的使用上层出不穷，给食品安全带来隐患[6-7]。
目前，合成色素的监督检测主要关注苏丹红[8]、罗丹明[9]等碱性非食用色素以及胭脂红、日落黄等酸性可食用色素[10-11]，酸性非食用色素的监测存在盲区。酸性色素检测方法的现有报道主要有液相色谱法[12-16]和液相色谱串联质谱法[17-23]。液相色谱法在面对调味酱等复杂基质样品时容易受到天然色素的干扰，液相色谱串联质谱法特异性强、灵敏度高，适用于复杂基质样品中酸性合成色素的高通量检测。本研究以调味酱为研究对象，优化色谱、质谱条件和前处理方法，建立85种酸性合成色素的液相色谱串联质谱筛查方法，为合成色素的监管提供技术支撑保障。
1. 材料与方法
1.1 材料与仪器
甲醇、乙腈、甲酸铵、乙酸铵 色谱纯，美国Thermo Fisher Scientific公司；0.22 μm聚四氟乙烯滤膜 上海安谱科学仪器有限公司；喹啉黄（纯度99.50%）、偶氮玉红（纯度92%）、酸性红60、酸性橙10、日落黄（纯度90%）、铬变素2R、铬变素2B、酸性黄17、滂酰洋红2B（纯度93.0%）、酸性红13、酸性红17、荧光素钠、滂酰紫6R、酸性红265（纯度95.0%）、酸性红87（纯度90.0%）、酸性红52、酸性紫49、酸性紫34、酸性红9、酸性红 88、酸性红92（纯度85.0%）、酸性红94、酸性红151、直接黄8、酸性橙 6、酸性绿50、酸性蓝92、酸性绿16、酸性橙20、二甲苯青FF、藏花橙 G、酸性绿9、酸性橙 17、酸性蓝83、酸性蓝90、酸性绿27（纯度75.0%）、酸性黑1（纯度97.0%）、酸性黄36（纯度98.0%） 日本TCI公司；酸性红44、酸性红66（纯度60%）、刚果红（纯度98.0%）、酸性红71、丽春红3R、酸性黄9（纯度95%）、酸性紫7（纯度40%）、酸性红50（纯度60%）、酸性橙8（纯度65%）、酸性蓝113（纯度50%） 美国Sigma公司；酸性紫3、甲基橙（纯度98.0%）、酸性绿A（纯度97.0%）、酸性红289、酸性兰27（纯度98%）、酸性蓝3 德国CNW公司；柠檬黄（纯度90.0%）、新红（纯度92.0%）、靛蓝（纯度89%）、坚牢绿（纯度94.9%）、胭脂红SX（纯度90.5%）、酸性蓝1（纯度100.0%）、酸性黄11（纯度74.6%）、酸性紫9（纯度72.0%）、酸性蓝62（纯度91.6%）、酸性橙II（纯度94%） 德国Dr.Ehrenstorfe GmbH公司；酸性红33、酸性绿41、食品红105 美国IL公司；酸性棕14（纯度98%）、颜料红49（纯度98%） 上海damas-beta公司；酸性蓝7、乙基曙红 美国Chemservice公司；溶剂蓝37 美国Santa Cruz公司；酸性黑210 上海麦克林生化科技有限公司；苋菜红（浓度0.5 mg/mL）、胭脂红（浓度0.5 mg/mL）、亮蓝（浓度0.5 mg/mL） 中国计量科学研究院；诱惑红（浓度1.0 mg/mL）、赤藓红（浓度1.0 mg/mL） 北京海岸鸿蒙标准物质技术有限责任公司；酸性红26（纯度96.0%）、色酚黄S、食品黑1（纯度96.0%）、酸性红1（纯度98.0%）、橙黄IV（批号：BCBJ7871V）、酸性红73（纯度97.0%） 美国FLUKA公司；酸性蓝41（纯度98%） 上海金锦乐实业有限公司；番茄酱、辣椒酱等50批次样品 购自广州市某几十个大型超市和生产企业。
Waters Xevo TQ-S超高效液相色谱-串联质谱仪 美国Waters公司；M37610-33CN旋涡振荡混合器 美国Thermo Fisher Scientific公司；BSA2202S电子天平 德国Sartorius公司；Allegra X-30R冷冻离心机 美国贝克曼库尔特公司。
1.2 实验方法
1.2.1 标准溶液的配制
柠檬黄、酸性红33、食品黑1、溶剂蓝37、酸性黑210、酸性绿9、酸性红289、酸性绿41、酸性紫34、颜料红49、酸性红92、酸性红94、食品红105、酸性蓝83、酸性蓝90等15种化合物：准确称取0.05 g标准品，用甲醇溶解并定容至10 mL，得到5.0 mg/mL的标准储备液；移取适量各标准品溶液，用甲醇稀释，得到浓度为100.0 mg/L的混合标准中间液1。
其余化合物：准确称取0.05 g标准品，用甲醇溶解并定容至50 mL，得到1.0 mg/mL的标准储备液；移取适量各标准品溶液，用甲醇稀释，得到浓度为10.0 mg/L的混合标准中间液2。
1.2.2 样品前处理
准确称取2.00 g样品（精确至0.01 g）放置于50 mL离心管中，加入10 mL甲醇，于旋涡振荡混合器上涡旋5 min，以10000 r/min离心5 min，转移上清液；残渣用10 mL甲醇重复提取一次，合并上清液。取2 mL上清液置于5 mL离心管中，加入200 mg C18净化剂，旋涡1 min后，10000 r/min离心5 min，得到提取液1（以1 g为基准，样品稀释10倍）。吸取1 mL提取液1，用水稀释至10 mL，得到提取液2（以1 g为基准，样品稀释100倍），过膜后待测[24]。
1.2.3 实验条件
1.2.3.1 色谱条件
色谱柱：ACQUITY UPLC HSS T3 （100 mm×2.1 mm, 1.8 μm）；柱温：40 ℃；进样体积：2 μL；流速：0.4 mL/min；流动相A为5 mmol/L乙酸铵水溶液，流动相B为甲醇；梯度：0~1 min，2%B；1~15 min，2%~95%B；15~18 min，95%B；18~21 min，95%~2%B[25]。
1.2.3.2 质谱条件
离子化模式：ESI-；电喷雾离子源温度为150 ℃；多反应监测模式；毛细管电压为2.5 kV；脱溶剂气温度为500 ℃；脱溶剂气流量为1000 L/h；锥孔气流量为150 L/h；碰撞气（氩气）压力为0.05 MPa[26]。
1.3 数据处理
方法重复性及回收率试验均做6次重复试验，采用Excel 2016 进行数据整理、分析，仪器数据采集软件为MassLynx 4.1，数据分析软件为TargetLynx 3.12。
2. 结果与分析
2.1 质谱条件的优化
分别配制浓度为1.0 μg/mL的各化合物标准溶液，仪器进样自动优化各化合物母离子、子离子、碰撞能量、锥孔电压等参数，各优化参数见表1。由于酸性色素为多钠钾盐化合物，在负离子模式下响应较好，离子峰类型均表现为[M-mNa/K+nH]（m-n）-，电荷数从1~4不等。对于一钠和二钠盐化合物，除杂环类的二钠盐外，离子峰类型表现为失去所有的钠；对于三钠或以上盐化合物，离子峰类型表现为失去所有的钠后加上一个氢离子。
表 1 85种酸性色素的质谱参数Table 1. MS/MS parameters of 85 acid pigments序号 化合物 结构类别 离子峰类型 母离子
（m/z）子离子
（m/z）去簇电压
（V）碰撞能量
（V）保留时间
（min）1 柠檬黄 偶氮类 [M-3Na+H]2- 197.9 106.0*/79.9 50 20/25 2.99 2 酸性黄9 偶氮类 [M-2Na]2- 177.6 171.0*/156.0 30 15/15 3.00 3 新红 偶氮类 [M-3Na+H]2- 271.5 172.0*/182.3 20 15/30 3.20 4 苋菜红 偶氮类 [M-3Na+H]2- 268.0 142.2*/228.3 10 35/15 3.51 5 靛蓝 靛类 [M-2Na]2- 209.9 155.8*/177.7 40 20/15 3.95 6 色酚黄S 偶氮类 [M-2Na]2- 313.0 233.0*/296.0 50 20/20 4.01 7 酸性紫 3 偶氮类 [M-Na]- 438.1 318.0*/254.0 20 25/35 4.32 8 胭脂红 偶氮类 [M-3Na+H]2- 268.0 206.2*/79.8 20 10/40 4.43 9 酸性红 60 偶氮类 [M-2Na]2- 276.0 165.7*/151.2 20 20/20 4.52 10 喹啉黄 菁类 [M-2Na]2- 215.2 183.4*/161.7 40 15/20 5.02 11 酸性橙10 偶氮类 [M-2Na]2- 203.0 150.3*/145.1 10 10/30 5.09 12 酸性红33 偶氮类 [M-2Na]2- 210.5 157.9*/79.9 10 10/20 5.11 13 日落黄 偶氮类 [M-2Na]2- 202.9 171.1*/206.1 30 15/25 5.27 14 酸性橙 6 偶氮类 [M-Na]- 293.1 171.2*/156.2 50 20/30 5.58 15 食品黑1 偶氮类 [M-4Na+H]3- 388.6 185.2*/291.1 20 35/25 5.59 16 酸性紫7 偶氮类 [M-2H]2- 260.0 158.2*/171.5 30 15/20 5.72 17 铬变素2R 偶氮类 [M-2Na]2- 211.2 158.7*/80.0 10 15/25 5.91 18 铬变素2B 偶氮类 [M-2Na]2- 233.6 158.4*/126.7 20 15/20 6.08 19 酸性红1 偶氮类 [M-2Na]2- 231.4 179.2*/158.1 30 10/15 6.14 20 酸性黄17 偶氮类 [M-2Na]2- 252.0 170.8*/107.1 40 15/30 6.29 21 诱惑红 偶氮类 [M-2Na]2- 225.2 217.8*/136.2 30 10/30 6.38 22 酸性绿50 芳甲烷类 [M-Na]- 553.3 510.9*/495.8 50 25/40 6.82 23 滂酰洋红2B 偶氮类 [M-2Na]2- 246.8 179.1*/158.1 10 15/20 6.85 24 酸性蓝 92 偶氮类 [M-3Na+H]2- 313.5 273.5*/297.0 40 10/20 7.20 25 溶剂蓝37 偶氮类 [M-3Na+H]2- 313.4 273.5*/297.2 40 15/10 7.20 26 酸性红13 偶氮类 [M-2Na]2- 227.9 207.2*/207.0 30 15/25 7.41 27 酸性红44 偶氮类 [M-2Na]2- 227.9 150.3*/145.3 10 10/30 7.49 28 酸性红26 偶氮类 [M-2Na]2- 216.8 143.1*/150.5 20 15/15 7.60 29 偶氮玉红 偶氮类 [M-2Na]2- 227.9 170.2*/221.2 30 20/15 7.86 30 坚牢绿 芳甲烷类 [M-2Na]2- 381.1 170.1*/340.9 10 40/15 7.94 31 酸性红17 偶氮类 [M-2Na]2- 228.1 150.6*/136.6 10 15/25 8.05 32 亮蓝 芳甲烷类 [M-2Na]2- 373.2 170.2*/333.2 50 35/15 8.09 33 胭脂红SX 偶氮类 [M-2Na]2- 217.2 170.2*/80.0 30 15/20 8.15 34 荧光素钠 杂环类 [M-2Na+H]- 330.9 286.9*/285.2 40 20/35 8.22 35 酸性绿16 芳甲烷类 [M-Na]- 593.2 469.3*/513.1 50 45/30 8.24 36 酸性橙 20 偶氮类 [M-Na]- 326.8 170.7*/247.2 40 25/20 8.27 37 滂酰紫 6R 偶氮类 [M-2Na]2- 236.0 158.5*/126.7 40 10/20 8.28 38 丽春红3R 偶氮类 [M-2Na]2- 223.9 136.6*/150.2 30 20/15 8.30 39 二甲苯青FF 芳甲烷类 [M-Na]- 515.2 435.3*/406.1 50 30/35 8.39 40 甲基橙 偶氮类 [M-Na]- 304.0 156.2*/288.2 30 30/30 8.74 41 酸性红265 偶氮类 [M-2Na]2- 294.2 235.1*/157.2 10 10/15 8.97 42 酸性红73 偶氮类 [M-2Na]2- 255.2 150.3*/241.3 10 10/10 9.02 43 酸性蓝1 芳甲烷类 [M-Na]- 543.1 419.2*/463.3 40 45/35 9.03 44 酸性红50 杂环类 [M-Na]- 529.2 405.0*/449.0 20 40/35 9.13 45 酸性绿A 芳甲烷类 [M-K]- 571.4 491.4*/79.8 30 15/40 9.26 46 酸性红87 杂环类 [M-2Na+H]- 642.7 518.8*/440.9 10 25/30 9.33 47 酸性棕 14 偶氮类 [M-2Na]2- 287.9 221.0*/247.9 40 15/15 9.44 48 酸性红66 偶氮类 [M-2Na]2- 511.1 156.2*/276.1 10 45/25 9.45 49 酸性黑1 偶氮类 [M-2Na]2- 285.0 163.9*/239.2 30 15/10 9.52 50 刚果红 偶氮类 [M-2Na]2- 325.1 152.3*/81.0 20 20/30 9.53 51 酸性蓝3 芳甲烷类 [M-Na]- 559.3 479.0*/435.0 20 30/45 9.53 52 酸性红52 杂环类 [M-Na]- 557.3 433.0*/80.0 20 45/40 9.56 53 酸性橙II 偶氮类 [M-Na]- 326.9 170.7*/156.2 30 30/30 9.57 54 藏花橙 G 偶氮类 [M-Na]- 326.9 206.8*/235.2 20 25/20 9.61 55 酸性黑210 偶氮类 [M-2K]2- 429.4 284.2*/317.0 50 20/15 9.81 56 橙黄IV 偶氮类 [M-Na]- 352.0 155.9*/79.9 20 30/45 9.96 57 酸性绿 9 芳甲烷类 [M-Na]- 701.3 170.2*/260.2 20 45/40 9.99 58 赤藓红 杂环类 [M-2Na+H]- 834.9 662.8*/536.9 50 35/30 10.11 59 酸性橙8 偶氮类 [M-Na]- 340.8 184.6*/169.8 40 20/35 10.17 60 酸性黄11 偶氮类 [M-Na]- 357.2 236.8*/207.8 20 20/35 10.18 61 酸性蓝7 芳甲烷类 [M-Na]- 667.6 561.0*/481.0 10 40/40 10.24 62 酸性黄36 偶氮类 [M-Na]- 351.7 155.6*/79.7 40 25/45 10.25 63 酸性红71 偶氮类 [M-2Na]2- 269.0 136.7*/209.8 20 25/15 10.49 64 酸性红289 杂环类 [M-Na]- 653.2 572.1*/79.8 30 40/45 10.62 65 酸性紫49 芳甲烷类 [M-Na]- 710.4 169.6*/260.1 10 45/45 10.76 66 酸性绿41 蒽醌类 [M-2Na]2- 304.1 79.9*/264.1 10 25/15 10.78 67 酸性紫9 杂环类 [M-Na]- 589.3 185.2*/544.1 50 40/40 10.79 68 酸性蓝41 蒽醌类 [M-Na]- 464.1 369.9*/400.0 50 45/35 10.85 69 酸性紫 34 蒽醌类 [M-Na]- 577.3 497.2*/417.1 40 25/40 10.97 70 酸性红 9 偶氮类 [M-Na]- 377.2 220.8*/205.8 40 25/35 10.98 71 酸性兰27 蒽醌类 [M-Na]- 421.2 80.0*/341.1 30 35/25 11.03 72 酸性红 88 偶氮类 [M-Na]- 377.1 221.1*/142.7 30 30/25 11.09 73 酸性橙 17 偶氮类 [M-Na]- 355.0 207.1*/206.5 20 30/40 11.16 74 颜料红49 偶氮类 [M-Na]- 377.1 269.2*/206.1 50 25/20 11.22 75 酸性红92 杂环类 [M-2Na+H]- 784.7 658.7*/660.3 30 30/30 11.31 76 酸性蓝62 蒽醌类 [M-H]- 399.1 315.7*/225.1 50 35/45 11.47 77 乙基曙红 杂环类 [M-K]- 674.7 520.6*/646.5 20 35/30 11.47 78 酸性红94 杂环类 [M-2Na+H]- 972.7 674.7*/737.4 30 35/40 11.73 79 食品红105 杂环类 [M-2Na+H]- 972.7 674.8*/892.6 40 40/30 11.73 80 酸性蓝 83 芳甲烷类 [M-2Na]2- 802.5 170.0*/602.3 30 65/45 11.91 81 酸性蓝 90 芳甲烷类 [M-2Na]2- 830.3 170.0*/644.3 50 70/45 12.08 82 酸性蓝113 偶氮类 [M-2Na]2- 317.4 155.9*/80.0 40 35/35 12.27 83 酸性红151 偶氮类 [M-Na]- 430.8 274.6*/155.7 10 25/40 12.35 84 直接黄8 偶氮类 [M-Na]- 506.9 344.8*/318.1 40 25/35 12.43 85 酸性绿27 蒽醌类 [M-2Na]2- 330.2 79.7*/308.2 10 30/25 12.63 注：*代表定量离子。 2.2 色谱条件的优化
由于酸性色素多为极性较强的离子型化合物，因此在流动相中添加适量的缓冲盐能有效增强化合物的保留效果并改善峰型[27]。考察了100 ng/mL的标准溶液在甲醇-5 mmol/L乙酸铵和甲醇-5 mmol/L甲酸铵两种流动相体系下各化合物的响应情况，结果表明，大部分化合物在甲醇-5 mmol/L乙酸铵的流动相体系下色谱峰响应较高（见图1），因此，本研究采用甲醇-5 mmol/L乙酸铵作为流动相。85种酸性色素的总离子流图如图2所示。
以保留时间最小的柠檬黄为对象，考察了1、2、4、6、8、10 μL等不同进样量对色谱峰峰型的影响，结果如图3所示。当进样量在4 μL以上时，色谱峰开始出现明显的分叉，表现出较强的溶剂效应。因此，本研究选择2 μL作为进样量。
2.3 前处理方法的优化
由于调味酱基质复杂，样品提取后，提取液中含有大量的共提取物，在质谱测定时共流出，使待测物的信号发生增强或减弱，因此需要对基质效应进行消除。当基质效应控制在−20%~20%的范围内时[28]，可以认为基质效应较弱，基本不影响样品定量。消除基质效应常见的方法有配制基质标准、采用内标法定量等。但由于食品种类繁多，配制基质标准需要耗费大量的时间；色素品种较多内标物较少，难以对所有色素进行覆盖。因此，本研究在保证灵敏度的前提下，采用增大提取液稀释倍数的方式降低基质效应。分别以提取液1和提取液2作溶剂配制标准曲线，采用计算公式（B/A−1）×100计算基质效应，其中B为基质曲线斜率，A为相应的溶剂曲线斜率。结果发现，当稀释倍数为100倍时，基质效应有了明显的下降（图4），同时100倍稀释也减少了溶剂效应的干扰。
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图 4 稀释10倍与稀释100倍基质效应比较Figure 4. Comparison of matrix effect between diluted 10 times and 100 times2.4 方法学评估
将85种色素混合标准溶液配制成系列浓度（柠檬黄、酸性红33、食品黑1、溶剂蓝37、酸性黑210、酸性绿9、酸性红289、酸性绿41、酸性紫34、颜料红49、酸性红92、酸性红94、食品红105、酸性蓝83、酸性蓝90线性范围为100~1000 ng/mL，其余为10~100 ng/mL，以质量浓度为横坐标，峰面积为纵坐标作校正曲线，结果如表2所示。以信噪比（S/N=3）计算85种色素的检出限，检出限在8.08~885.2 μg/kg之间，定量限在26.94~2950.7 μg/kg之间。按照实验测定步骤，选取空白基质，以高（25/2.5 mg/kg）、中（10/1.0 mg/kg）、低（5/0.5 mg/kg）3个浓度水平进行加标回收试验。结果表明，85种酸性色素的回收率为70.2%~116.5%，相对标准偏差为0.1%~15.0%。该方法回收率和重复性良好，满足日常检测需求。
表 2 85种酸性色素的线性范围、相关系数、检出限、定量限和回收率Table 2. Linear range, correlation coefficients (r), limits of detections (LODs), limits of quantification (LOQs) and recoveries of 85 acid pigments化合物 线性范围
（ng/mL）线性方程 相关系数
（r）检出限
（µg/kg）定量限
（µg/kg）低浓度 中浓度 高浓度 回收率
（%）相对标准
偏差（%）回收率
（%）相对标准
偏差（%）回收率
（%）相对标准
偏差（%）柠檬黄 100~1000 y=419.75342x+13293.96176 0.9904 152.49 508.31 115.8 4.9 107.3 2.4 106.4 3.1 酸性黄9 10~100 y=1165.76324x+849.26566 0.9967 38.15 127.16 101.6 1.1 113.1 0.8 92.7 3.3 新红 10~100 y=586.84034x−560.03503 0.9936 30.80 102.65 88.0 3.6 90.9 2.9 72.9 12.2 苋菜红 10~100 y=562.21137x−924.83450 0.9906 14.08 46.93 93.3 1.6 93.8 1.1 83.3 4.9 靛蓝 10~100 y=134.05458x−255.30849 0.9924 65.82 219.38 77.8 5.9 76.1 3.3 79.0 8.5 色酚黄S 10~100 y=21827.42298x−4475.72304 0.9947 10.46 34.88 90.6 4.2 106.6 0.4 94.7 2.4 酸性紫 3 10~100 y=3271.87798x+904.34590 0.9988 14.90 49.67 101.7 2.9 103.8 11.6 82.2 13.6 胭脂红 10~100 y=558.85611x−494.82490 0.9980 29.42 98.06 104.1 1.5 97.3 4.7 87.0 11.1 酸性红60 10~100 y=1199.9715x−213.73797 0.9993 22.53 75.09 94.2 1.7 89.6 5.4 83.3 7.7 喹啉黄 10~100 y=6247.77427x−3947.52115 0.9996 26.97 89.90 107.6 0.1 101.5 0.2 93.3 6.5 酸性橙10 10~100 y=160.59832x−184.67970 0.9973 45.78 152.59 91.4 10.5 98.4 8.6 104.8 11.6 酸性红33 100~1000 y=169.90660x−1126.83787 0.9982 622.48 2075.0 94.8 0.3 93.2 0.1 93.3 5.9 日落黄 10~100 y=4253.86766x−5537.11732 0.9961 27.76 92.54 98.8 5.9 99.1 0.1 98.4 1.8 酸性橙 6 10~100 y=2865.52589x−961.02528 0.9996 11.05 36.82 92.4 2.9 106.5 10.2 100.6 2.4 食品黑1 100~1000 y=174.87205x−901.71077 0.9989 793.66 2645.5 71.4 9.7 80.7 0.9 73.4 7.2 酸性紫7 10~100 y=67.41726x+73.80884 0.9973 140.76 469.22 112.3 10.0 98.8 10.8 107.7 7.6 铬变素2R 10~100 y=240.13601x+200.63802 0.9987 114.39 381.29 98.8 11.0 100.6 9.8 110.5 10.5 铬变素2B 10~100 y=801.04175x+76.55551 0.9997 45.49 151.65 78.9 4.6 114.5 0.1 108.2 4.4 酸性红1 10~100 y=481.16256x−116.68974 0.9975 47.48 158.27 93.0 4.3 96.2 5.4 93.8 6.1 酸性黄17 10~100 y=10635.01818x−11012.86251 0.9964 12.16 40.52 89.9 0.2 94.8 0.5 95.8 9.2 诱惑红 10~100 y=1766.55337x−2259.23950 0.9914 36.94 123.13 90.4 1.4 91.5 1.6 78.7 11.3 酸性绿50 10~100 y=55.32164x+27.40617 0.9975 98.82 329.42 110.1 12 106 11.6 94.4 13.2 滂酰洋红2B 10~100 y=99.85972x+13.80873 0.9935 143.85 479.50 95.3 1.3 98.3 9.5 103.7 8.4 酸性蓝92 10~100 y=1620.34499x−3042.96129 0.9939 49.02 163.39 89.1 9.1 85.6 2.5 72.1 11.8 溶剂蓝37 100~1000 y=878.57610x−21684.12771 0.9942 338.98 1130.0 88.3 8.3 82.8 2.3 79.7 12.3 酸性红13 10~100 y=11401.29157x+1275.58866 0.9999 16.18 53.95 89.5 3.8 97.9 8.5 88.0 1.5 酸性红44 10~100 y=340.45100x−211.24931 0.9982 43.77 145.91 91.4 4.9 90.7 0.1 99.2 12.6 酸性红26 10~100 y=105.08363x−180.38596 0.9960 121.10 404.01 111.8 1.1 91.3 2.3 100.7 13.3 偶氮玉红 10~100 y=1088.82710x−1714.86761 0.9925 31.27 104.25 89.1 11.8 93.5 2.1 86.8 5.8 坚牢绿 10~100 y=762.02013x−477.29113 0.9933 55.39 184.62 104.5 4.4 103.3 9.1 82.6 3.4 酸性红17 10~100 y=122.89447x−125.66492 0.9988 131.33 437.78 103.3 13.0 79.8 5.2 109.2 7.6 亮蓝 10~100 y=4002.75902x−4809.19018 0.9964 40.21 134.04 94.0 3.4 111.0 13.3 93.4 2.4 胭脂红SX 10~100 y=390.43358x+172.95286 0.9967 63.56 211.88 95.5 10.4 109.7 2.5 105.3 7.5 荧光素钠 10~100 y=2029.02871x+573.12887 0.9984 41.02 136.73 98.3 0.7 101.1 6.1 104.5 0.6 酸性绿16 10~100 y=332.49546x−98.50748 0.9997 68.37 227.91 89.3 15.0 84 7.1 93.3 2.4 酸性橙 20 10~100 y=5475.73159x+16148.51213 0.9906 33.92 113.05 99.5 8.5 106.3 7.1 88.2 14.5 滂酰紫 6R 10~100 y=352.22884x−209.59916 0.9928 100.07 333.55 94.9 14.9 95.3 2.5 94.0 6.3 丽春红3R 10~100 y=649.50980x+125.24164 0.9996 103.50 344.99 90.9 1.9 108.6 3.2 104.3 8.0 二甲苯青FF 10~100 y=532.92910x−228.74751 0.9976 48.22 160.74 94.8 12.3 100 9.1 90.6 3.4 甲基橙 10~100 y=27680.55735x−38547.59789 0.9969 24.59 81.98 101.6 2.5 101.8 2.2 88.7 12.2 酸性红265 10~100 y=655.27716x−349.59825 0.9985 97.97 326.55 99.1 1.7 94.7 0.2 87.1 7.6 酸性红73 10~100 y=540.57088x−507.99513 0.9938 130.44 434.80 88.5 6.7 99.1 1.4 97.5 10.1 酸性蓝1 10~100 y=1134.63730x−1.25066 0.9976 53.50 178.33 100.4 2.9 96 4.9 99.7 4.2 酸性红50 10~100 y=272.27449x−252.93147 0.9987 92.68 308.94 92.6 11.1 91 4.9 97.8 2.4 酸性绿A 10~100 y=475.80571x+269.22426 0.9943 94.65 315.48 102.9 7.3 108.3 7 99.9 4.7 酸性红87 10~100 y=595.30367x+99.95480 0.9970 73.26 244.21 91.8 1.5 96.1 1.8 95.7 3.7 酸性棕 14 10~100 y=13524.13274x−5800.62123 0.9973 31.36 104.54 85.3 2.2 90.5 10.1 82.5 14.6 酸性红66 10~100 y=2623.84379x−2924.91568 0.9969 40.01 133.37 93.4 6.1 91.1 0.6 93.1 3.6 酸性黑1 10~100 y=553.63382x−348.03812 0.9984 92.64 308.81 75.7 3.7 89.4 6.3 99.6 7.4 刚果红 10~100 y=886.19997x−653.86795 0.9943 59.73 199.11 95.5 8.4 92.4 9.1 95.9 8.3 酸性蓝3 10~100 y=4209.58253x−702.33371 0.9984 24.19 80.62 94.2 3.3 104.1 3.7 99.1 5.3 酸性红52 10~100 y=332.13625x+284.76560 0.9968 133.15 443.83 110.5 14.3 104 0.2 96.5 4.1 酸性橙II 10~100 y=15472.87341x−563.41077 0.9998 19.57 65.24 101.0 0.3 90.8 2.7 92.4 4.8 藏花橙 G 10~100 y=28399.43170x−8085.22028 0.9993 14.53 48.43 100.3 3.6 91.8 2.1 92.5 8.6 酸性黑210 100~1000 y=80.90117x+1616.49951 0.9940 885.20 2950.7 75.9 7.6 97.5 12.2 101.0 7.6 橙黄IV 10~100 y=39978.93219x−67914.83647 0.9956 8.35 27.85 106.1 7.1 101.2 8.7 92.5 9.4 酸性绿 9 100~1000 y=146.35189x+1097.94132 0.9991 375.80 1252.6 111.0 1.1 107.9 12.7 100.1 10.1 赤藓红 10~100 y=1531.56882x−1493.63090 0.9983 57.14 190.47 88.3 1.1 93.1 7.8 93.5 0.9 酸性橙8 10~100 y=14245.34852x−10143.37898 0.9995 25.33 84.43 92.7 3.1 94.0 9.1 84.6 5.3 酸性黄11 10~100 y=7268.14346x+11675.66549 0.9970 42.53 141.77 115 12.6 106.5 0.7 94.4 2.8 酸性蓝7 10~100 y=1054.13872x−1135.91525 0.9977 52.37 174.55 88.5 2.6 92.4 6.9 88.6 1.1 酸性黄36 10~100 y=29665.55767x−57181.71917 0.9969 12.42 41.40 99.5 7.8 96.2 6.5 89.6 11.5 酸性红71 10~100 y=366.12316x−104.30076 0.9981 113.57 378.57 90.0） 8.3 93.1 0.2 91.1 3.2 酸性红289 100~1000 y=13.41741x+169.59362 0.9975 815.37 2717.9 72.7 9.6 110.7 13 98.9 6.8 酸性紫49 10~100 y=400.58787x−98.38858 0.9994 55.09 183.62 70.2 5 72.5 13.1 76.7 1.8 酸性绿41 100~1000 y=31.05411x−1080.29451 0.9910 685.35 2284.5 116.5 1.4 100.6 2.7 84.7 5.2 酸性紫9 10~100 y=1055.91180x−351.69408 0.9976 37.24 124.14 102.3 2.4 97.2 1.5 85.5 3.4 酸性蓝41 10~100 y=16662.06544x−19926.57491 0.9987 15.42 51.39 97.4 2.1 96.7 6.1 81.5 8.1 酸性紫 34 100~1000 y=1813.20031x−8926.37811 0.9994 105.25 350.84 95.9 0.7 99.2 7.6 94.4 1.1 酸性红 9 10~100 y=22862.36142x−66680.38419 0.9914 11.53 38.44 96.8 4.1 87.3 1.9 80.5 5.4 酸性兰27 10~100 y=288.12016x−288.95028 0.9982 82.08 273.61 95.5 14.2 88.5 1.4 84.1 0.4 酸性红 88 10~100 y=20945.35351x−15778.83872 0.9968 16.14 53.81 97.2 2.1 101.9 14.9 87.2 5.2 酸性橙 17 10~100 y=16014.50483x−15196.82310 0.9969 21.33 71.10 99.0 3.2 100.9 12.9 93.5 10.6 颜料红49 100~1000 y=1777.76946x−30821.06732 0.9948 172.49 574.98 94.2 0.1 92.4 6.8 87.4 6.3 酸性红92 100~1000 y=501.20203x+2656.97264 0.9997 146.80 489.34 98.9 4.9 108.1 1.2 95.0 3.7 酸性蓝62 10~100 y=14656.86894x+2177.11205 0.9982 17.18 57.28 88.5 7.4 97.2 1.8 80.9 5.7 乙基曙红 10~100 y=335.87537x−709.10966 0.9908 140.95 469.82 87.0 7.3 84.4 0.3 73.9 3.7 酸性红94 100~1000 y=2125.56345x+29066.92700 0.9984 118.53 395.12 99.6 0.9 109.1 0.8 99.8 1.6 食品红105 100~1000 y=1719.19175x+25320.78291 0.9985 86.47 288.22 98.3 1.1 108.7 1.1 101.4 0.6 酸性蓝 83 100~1000 y=401.35032x+2870.96522 0.9974 153.22 510.75 73.3 9.7 74.5 10.3 79.3 5.9 酸性蓝 90 100~1000 y=361.75519x−5443.64145 0.9942 58.25 194.18 87.4 7.2 92.2 2.2 93.0 2.1 酸性蓝113 10~100 y=3235.11512x−4630.72122 0.9944 139.41 464.71 92.2 9.9 90.9 3.1 80.7 5.3 酸性红151 10~100 y=15980.74614x−8516.41801 0.9975 10.97 36.57 100.4 2.5 98.3 2.9 87.7 6.9 直接黄8 10~100 y=15608.60549x−17626.54950 0.9983 8.08 26.94 98.0 0.1 93.5 1.7 88.4 11.4 酸性绿27 10~100 y=200.28220x−312.59313 0.9917 63.13 210.42 96.4 5.2 90.1 7.7 99.5 13.1 2.5 实际样品检测
按照实验方法，对市售的番茄酱、辣椒酱等样品共计50批次进行检测，在2批次样品中筛查出酸性红13、酸性橙II等禁止使用的色素（见表3），但含量较低，推测是使用了工艺较差的可食用色素作为原料。
表 3 调味酱筛查结果Table 3. Screening result of sauce样品名称 禁用色素 含量（µg/kg） 可食用色素 含量（µg/kg） 草莓果酱 酸性红13 21.5 胭脂红 3982 柠檬黄 539 巧克力调味酱 酸性橙II 30.7 胭脂红 5650 日落黄 5650 3. 结论与讨论
本实验采用液相色谱结合质谱法对调味酱中85种酸性合成色素进行检测，优化了流动相、进样量等色谱条件以及质谱条件，采用增大稀释倍数的方式降低基质效应，建立了一个快速简便的通用型分析方法。与现有固相萃取方法相比[10-11]，本方法采用QuEChERS净化技术，操作较简便；与其他高通量分析方法相比[20-23]，本方法通过优化前处理方法，减少配制基质曲线的步骤，在日常监督检测时可提高检测效率。本方法通用性强，检测对象范围较广，分析时间短，灵敏度高，为食品中合成色素的监管提供强有力的技术保障。
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图 4 稀释10倍与稀释100倍基质效应比较
Figure 4. Comparison of matrix effect between diluted 10 times and 100 times
表 1 85种酸性色素的质谱参数
Table 1 MS/MS parameters of 85 acid pigments
序号 化合物 结构类别 离子峰类型 母离子
（m/z）子离子
（m/z）去簇电压
（V）碰撞能量
（V）保留时间
（min）1 柠檬黄 偶氮类 [M-3Na+H]2- 197.9 106.0*/79.9 50 20/25 2.99 2 酸性黄9 偶氮类 [M-2Na]2- 177.6 171.0*/156.0 30 15/15 3.00 3 新红 偶氮类 [M-3Na+H]2- 271.5 172.0*/182.3 20 15/30 3.20 4 苋菜红 偶氮类 [M-3Na+H]2- 268.0 142.2*/228.3 10 35/15 3.51 5 靛蓝 靛类 [M-2Na]2- 209.9 155.8*/177.7 40 20/15 3.95 6 色酚黄S 偶氮类 [M-2Na]2- 313.0 233.0*/296.0 50 20/20 4.01 7 酸性紫 3 偶氮类 [M-Na]- 438.1 318.0*/254.0 20 25/35 4.32 8 胭脂红 偶氮类 [M-3Na+H]2- 268.0 206.2*/79.8 20 10/40 4.43 9 酸性红 60 偶氮类 [M-2Na]2- 276.0 165.7*/151.2 20 20/20 4.52 10 喹啉黄 菁类 [M-2Na]2- 215.2 183.4*/161.7 40 15/20 5.02 11 酸性橙10 偶氮类 [M-2Na]2- 203.0 150.3*/145.1 10 10/30 5.09 12 酸性红33 偶氮类 [M-2Na]2- 210.5 157.9*/79.9 10 10/20 5.11 13 日落黄 偶氮类 [M-2Na]2- 202.9 171.1*/206.1 30 15/25 5.27 14 酸性橙 6 偶氮类 [M-Na]- 293.1 171.2*/156.2 50 20/30 5.58 15 食品黑1 偶氮类 [M-4Na+H]3- 388.6 185.2*/291.1 20 35/25 5.59 16 酸性紫7 偶氮类 [M-2H]2- 260.0 158.2*/171.5 30 15/20 5.72 17 铬变素2R 偶氮类 [M-2Na]2- 211.2 158.7*/80.0 10 15/25 5.91 18 铬变素2B 偶氮类 [M-2Na]2- 233.6 158.4*/126.7 20 15/20 6.08 19 酸性红1 偶氮类 [M-2Na]2- 231.4 179.2*/158.1 30 10/15 6.14 20 酸性黄17 偶氮类 [M-2Na]2- 252.0 170.8*/107.1 40 15/30 6.29 21 诱惑红 偶氮类 [M-2Na]2- 225.2 217.8*/136.2 30 10/30 6.38 22 酸性绿50 芳甲烷类 [M-Na]- 553.3 510.9*/495.8 50 25/40 6.82 23 滂酰洋红2B 偶氮类 [M-2Na]2- 246.8 179.1*/158.1 10 15/20 6.85 24 酸性蓝 92 偶氮类 [M-3Na+H]2- 313.5 273.5*/297.0 40 10/20 7.20 25 溶剂蓝37 偶氮类 [M-3Na+H]2- 313.4 273.5*/297.2 40 15/10 7.20 26 酸性红13 偶氮类 [M-2Na]2- 227.9 207.2*/207.0 30 15/25 7.41 27 酸性红44 偶氮类 [M-2Na]2- 227.9 150.3*/145.3 10 10/30 7.49 28 酸性红26 偶氮类 [M-2Na]2- 216.8 143.1*/150.5 20 15/15 7.60 29 偶氮玉红 偶氮类 [M-2Na]2- 227.9 170.2*/221.2 30 20/15 7.86 30 坚牢绿 芳甲烷类 [M-2Na]2- 381.1 170.1*/340.9 10 40/15 7.94 31 酸性红17 偶氮类 [M-2Na]2- 228.1 150.6*/136.6 10 15/25 8.05 32 亮蓝 芳甲烷类 [M-2Na]2- 373.2 170.2*/333.2 50 35/15 8.09 33 胭脂红SX 偶氮类 [M-2Na]2- 217.2 170.2*/80.0 30 15/20 8.15 34 荧光素钠 杂环类 [M-2Na+H]- 330.9 286.9*/285.2 40 20/35 8.22 35 酸性绿16 芳甲烷类 [M-Na]- 593.2 469.3*/513.1 50 45/30 8.24 36 酸性橙 20 偶氮类 [M-Na]- 326.8 170.7*/247.2 40 25/20 8.27 37 滂酰紫 6R 偶氮类 [M-2Na]2- 236.0 158.5*/126.7 40 10/20 8.28 38 丽春红3R 偶氮类 [M-2Na]2- 223.9 136.6*/150.2 30 20/15 8.30 39 二甲苯青FF 芳甲烷类 [M-Na]- 515.2 435.3*/406.1 50 30/35 8.39 40 甲基橙 偶氮类 [M-Na]- 304.0 156.2*/288.2 30 30/30 8.74 41 酸性红265 偶氮类 [M-2Na]2- 294.2 235.1*/157.2 10 10/15 8.97 42 酸性红73 偶氮类 [M-2Na]2- 255.2 150.3*/241.3 10 10/10 9.02 43 酸性蓝1 芳甲烷类 [M-Na]- 543.1 419.2*/463.3 40 45/35 9.03 44 酸性红50 杂环类 [M-Na]- 529.2 405.0*/449.0 20 40/35 9.13 45 酸性绿A 芳甲烷类 [M-K]- 571.4 491.4*/79.8 30 15/40 9.26 46 酸性红87 杂环类 [M-2Na+H]- 642.7 518.8*/440.9 10 25/30 9.33 47 酸性棕 14 偶氮类 [M-2Na]2- 287.9 221.0*/247.9 40 15/15 9.44 48 酸性红66 偶氮类 [M-2Na]2- 511.1 156.2*/276.1 10 45/25 9.45 49 酸性黑1 偶氮类 [M-2Na]2- 285.0 163.9*/239.2 30 15/10 9.52 50 刚果红 偶氮类 [M-2Na]2- 325.1 152.3*/81.0 20 20/30 9.53 51 酸性蓝3 芳甲烷类 [M-Na]- 559.3 479.0*/435.0 20 30/45 9.53 52 酸性红52 杂环类 [M-Na]- 557.3 433.0*/80.0 20 45/40 9.56 53 酸性橙II 偶氮类 [M-Na]- 326.9 170.7*/156.2 30 30/30 9.57 54 藏花橙 G 偶氮类 [M-Na]- 326.9 206.8*/235.2 20 25/20 9.61 55 酸性黑210 偶氮类 [M-2K]2- 429.4 284.2*/317.0 50 20/15 9.81 56 橙黄IV 偶氮类 [M-Na]- 352.0 155.9*/79.9 20 30/45 9.96 57 酸性绿 9 芳甲烷类 [M-Na]- 701.3 170.2*/260.2 20 45/40 9.99 58 赤藓红 杂环类 [M-2Na+H]- 834.9 662.8*/536.9 50 35/30 10.11 59 酸性橙8 偶氮类 [M-Na]- 340.8 184.6*/169.8 40 20/35 10.17 60 酸性黄11 偶氮类 [M-Na]- 357.2 236.8*/207.8 20 20/35 10.18 61 酸性蓝7 芳甲烷类 [M-Na]- 667.6 561.0*/481.0 10 40/40 10.24 62 酸性黄36 偶氮类 [M-Na]- 351.7 155.6*/79.7 40 25/45 10.25 63 酸性红71 偶氮类 [M-2Na]2- 269.0 136.7*/209.8 20 25/15 10.49 64 酸性红289 杂环类 [M-Na]- 653.2 572.1*/79.8 30 40/45 10.62 65 酸性紫49 芳甲烷类 [M-Na]- 710.4 169.6*/260.1 10 45/45 10.76 66 酸性绿41 蒽醌类 [M-2Na]2- 304.1 79.9*/264.1 10 25/15 10.78 67 酸性紫9 杂环类 [M-Na]- 589.3 185.2*/544.1 50 40/40 10.79 68 酸性蓝41 蒽醌类 [M-Na]- 464.1 369.9*/400.0 50 45/35 10.85 69 酸性紫 34 蒽醌类 [M-Na]- 577.3 497.2*/417.1 40 25/40 10.97 70 酸性红 9 偶氮类 [M-Na]- 377.2 220.8*/205.8 40 25/35 10.98 71 酸性兰27 蒽醌类 [M-Na]- 421.2 80.0*/341.1 30 35/25 11.03 72 酸性红 88 偶氮类 [M-Na]- 377.1 221.1*/142.7 30 30/25 11.09 73 酸性橙 17 偶氮类 [M-Na]- 355.0 207.1*/206.5 20 30/40 11.16 74 颜料红49 偶氮类 [M-Na]- 377.1 269.2*/206.1 50 25/20 11.22 75 酸性红92 杂环类 [M-2Na+H]- 784.7 658.7*/660.3 30 30/30 11.31 76 酸性蓝62 蒽醌类 [M-H]- 399.1 315.7*/225.1 50 35/45 11.47 77 乙基曙红 杂环类 [M-K]- 674.7 520.6*/646.5 20 35/30 11.47 78 酸性红94 杂环类 [M-2Na+H]- 972.7 674.7*/737.4 30 35/40 11.73 79 食品红105 杂环类 [M-2Na+H]- 972.7 674.8*/892.6 40 40/30 11.73 80 酸性蓝 83 芳甲烷类 [M-2Na]2- 802.5 170.0*/602.3 30 65/45 11.91 81 酸性蓝 90 芳甲烷类 [M-2Na]2- 830.3 170.0*/644.3 50 70/45 12.08 82 酸性蓝113 偶氮类 [M-2Na]2- 317.4 155.9*/80.0 40 35/35 12.27 83 酸性红151 偶氮类 [M-Na]- 430.8 274.6*/155.7 10 25/40 12.35 84 直接黄8 偶氮类 [M-Na]- 506.9 344.8*/318.1 40 25/35 12.43 85 酸性绿27 蒽醌类 [M-2Na]2- 330.2 79.7*/308.2 10 30/25 12.63 注：*代表定量离子。 
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表 2 85种酸性色素的线性范围、相关系数、检出限、定量限和回收率
Table 2 Linear range, correlation coefficients (r), limits of detections (LODs), limits of quantification (LOQs) and recoveries of 85 acid pigments
化合物 线性范围
（ng/mL）线性方程 相关系数
（r）检出限
（µg/kg）定量限
（µg/kg）低浓度 中浓度 高浓度 回收率
（%）相对标准
偏差（%）回收率
（%）相对标准
偏差（%）回收率
（%）相对标准
偏差（%）柠檬黄 100~1000 y=419.75342x+13293.96176 0.9904 152.49 508.31 115.8 4.9 107.3 2.4 106.4 3.1 酸性黄9 10~100 y=1165.76324x+849.26566 0.9967 38.15 127.16 101.6 1.1 113.1 0.8 92.7 3.3 新红 10~100 y=586.84034x−560.03503 0.9936 30.80 102.65 88.0 3.6 90.9 2.9 72.9 12.2 苋菜红 10~100 y=562.21137x−924.83450 0.9906 14.08 46.93 93.3 1.6 93.8 1.1 83.3 4.9 靛蓝 10~100 y=134.05458x−255.30849 0.9924 65.82 219.38 77.8 5.9 76.1 3.3 79.0 8.5 色酚黄S 10~100 y=21827.42298x−4475.72304 0.9947 10.46 34.88 90.6 4.2 106.6 0.4 94.7 2.4 酸性紫 3 10~100 y=3271.87798x+904.34590 0.9988 14.90 49.67 101.7 2.9 103.8 11.6 82.2 13.6 胭脂红 10~100 y=558.85611x−494.82490 0.9980 29.42 98.06 104.1 1.5 97.3 4.7 87.0 11.1 酸性红60 10~100 y=1199.9715x−213.73797 0.9993 22.53 75.09 94.2 1.7 89.6 5.4 83.3 7.7 喹啉黄 10~100 y=6247.77427x−3947.52115 0.9996 26.97 89.90 107.6 0.1 101.5 0.2 93.3 6.5 酸性橙10 10~100 y=160.59832x−184.67970 0.9973 45.78 152.59 91.4 10.5 98.4 8.6 104.8 11.6 酸性红33 100~1000 y=169.90660x−1126.83787 0.9982 622.48 2075.0 94.8 0.3 93.2 0.1 93.3 5.9 日落黄 10~100 y=4253.86766x−5537.11732 0.9961 27.76 92.54 98.8 5.9 99.1 0.1 98.4 1.8 酸性橙 6 10~100 y=2865.52589x−961.02528 0.9996 11.05 36.82 92.4 2.9 106.5 10.2 100.6 2.4 食品黑1 100~1000 y=174.87205x−901.71077 0.9989 793.66 2645.5 71.4 9.7 80.7 0.9 73.4 7.2 酸性紫7 10~100 y=67.41726x+73.80884 0.9973 140.76 469.22 112.3 10.0 98.8 10.8 107.7 7.6 铬变素2R 10~100 y=240.13601x+200.63802 0.9987 114.39 381.29 98.8 11.0 100.6 9.8 110.5 10.5 铬变素2B 10~100 y=801.04175x+76.55551 0.9997 45.49 151.65 78.9 4.6 114.5 0.1 108.2 4.4 酸性红1 10~100 y=481.16256x−116.68974 0.9975 47.48 158.27 93.0 4.3 96.2 5.4 93.8 6.1 酸性黄17 10~100 y=10635.01818x−11012.86251 0.9964 12.16 40.52 89.9 0.2 94.8 0.5 95.8 9.2 诱惑红 10~100 y=1766.55337x−2259.23950 0.9914 36.94 123.13 90.4 1.4 91.5 1.6 78.7 11.3 酸性绿50 10~100 y=55.32164x+27.40617 0.9975 98.82 329.42 110.1 12 106 11.6 94.4 13.2 滂酰洋红2B 10~100 y=99.85972x+13.80873 0.9935 143.85 479.50 95.3 1.3 98.3 9.5 103.7 8.4 酸性蓝92 10~100 y=1620.34499x−3042.96129 0.9939 49.02 163.39 89.1 9.1 85.6 2.5 72.1 11.8 溶剂蓝37 100~1000 y=878.57610x−21684.12771 0.9942 338.98 1130.0 88.3 8.3 82.8 2.3 79.7 12.3 酸性红13 10~100 y=11401.29157x+1275.58866 0.9999 16.18 53.95 89.5 3.8 97.9 8.5 88.0 1.5 酸性红44 10~100 y=340.45100x−211.24931 0.9982 43.77 145.91 91.4 4.9 90.7 0.1 99.2 12.6 酸性红26 10~100 y=105.08363x−180.38596 0.9960 121.10 404.01 111.8 1.1 91.3 2.3 100.7 13.3 偶氮玉红 10~100 y=1088.82710x−1714.86761 0.9925 31.27 104.25 89.1 11.8 93.5 2.1 86.8 5.8 坚牢绿 10~100 y=762.02013x−477.29113 0.9933 55.39 184.62 104.5 4.4 103.3 9.1 82.6 3.4 酸性红17 10~100 y=122.89447x−125.66492 0.9988 131.33 437.78 103.3 13.0 79.8 5.2 109.2 7.6 亮蓝 10~100 y=4002.75902x−4809.19018 0.9964 40.21 134.04 94.0 3.4 111.0 13.3 93.4 2.4 胭脂红SX 10~100 y=390.43358x+172.95286 0.9967 63.56 211.88 95.5 10.4 109.7 2.5 105.3 7.5 荧光素钠 10~100 y=2029.02871x+573.12887 0.9984 41.02 136.73 98.3 0.7 101.1 6.1 104.5 0.6 酸性绿16 10~100 y=332.49546x−98.50748 0.9997 68.37 227.91 89.3 15.0 84 7.1 93.3 2.4 酸性橙 20 10~100 y=5475.73159x+16148.51213 0.9906 33.92 113.05 99.5 8.5 106.3 7.1 88.2 14.5 滂酰紫 6R 10~100 y=352.22884x−209.59916 0.9928 100.07 333.55 94.9 14.9 95.3 2.5 94.0 6.3 丽春红3R 10~100 y=649.50980x+125.24164 0.9996 103.50 344.99 90.9 1.9 108.6 3.2 104.3 8.0 二甲苯青FF 10~100 y=532.92910x−228.74751 0.9976 48.22 160.74 94.8 12.3 100 9.1 90.6 3.4 甲基橙 10~100 y=27680.55735x−38547.59789 0.9969 24.59 81.98 101.6 2.5 101.8 2.2 88.7 12.2 酸性红265 10~100 y=655.27716x−349.59825 0.9985 97.97 326.55 99.1 1.7 94.7 0.2 87.1 7.6 酸性红73 10~100 y=540.57088x−507.99513 0.9938 130.44 434.80 88.5 6.7 99.1 1.4 97.5 10.1 酸性蓝1 10~100 y=1134.63730x−1.25066 0.9976 53.50 178.33 100.4 2.9 96 4.9 99.7 4.2 酸性红50 10~100 y=272.27449x−252.93147 0.9987 92.68 308.94 92.6 11.1 91 4.9 97.8 2.4 酸性绿A 10~100 y=475.80571x+269.22426 0.9943 94.65 315.48 102.9 7.3 108.3 7 99.9 4.7 酸性红87 10~100 y=595.30367x+99.95480 0.9970 73.26 244.21 91.8 1.5 96.1 1.8 95.7 3.7 酸性棕 14 10~100 y=13524.13274x−5800.62123 0.9973 31.36 104.54 85.3 2.2 90.5 10.1 82.5 14.6 酸性红66 10~100 y=2623.84379x−2924.91568 0.9969 40.01 133.37 93.4 6.1 91.1 0.6 93.1 3.6 酸性黑1 10~100 y=553.63382x−348.03812 0.9984 92.64 308.81 75.7 3.7 89.4 6.3 99.6 7.4 刚果红 10~100 y=886.19997x−653.86795 0.9943 59.73 199.11 95.5 8.4 92.4 9.1 95.9 8.3 酸性蓝3 10~100 y=4209.58253x−702.33371 0.9984 24.19 80.62 94.2 3.3 104.1 3.7 99.1 5.3 酸性红52 10~100 y=332.13625x+284.76560 0.9968 133.15 443.83 110.5 14.3 104 0.2 96.5 4.1 酸性橙II 10~100 y=15472.87341x−563.41077 0.9998 19.57 65.24 101.0 0.3 90.8 2.7 92.4 4.8 藏花橙 G 10~100 y=28399.43170x−8085.22028 0.9993 14.53 48.43 100.3 3.6 91.8 2.1 92.5 8.6 酸性黑210 100~1000 y=80.90117x+1616.49951 0.9940 885.20 2950.7 75.9 7.6 97.5 12.2 101.0 7.6 橙黄IV 10~100 y=39978.93219x−67914.83647 0.9956 8.35 27.85 106.1 7.1 101.2 8.7 92.5 9.4 酸性绿 9 100~1000 y=146.35189x+1097.94132 0.9991 375.80 1252.6 111.0 1.1 107.9 12.7 100.1 10.1 赤藓红 10~100 y=1531.56882x−1493.63090 0.9983 57.14 190.47 88.3 1.1 93.1 7.8 93.5 0.9 酸性橙8 10~100 y=14245.34852x−10143.37898 0.9995 25.33 84.43 92.7 3.1 94.0 9.1 84.6 5.3 酸性黄11 10~100 y=7268.14346x+11675.66549 0.9970 42.53 141.77 115 12.6 106.5 0.7 94.4 2.8 酸性蓝7 10~100 y=1054.13872x−1135.91525 0.9977 52.37 174.55 88.5 2.6 92.4 6.9 88.6 1.1 酸性黄36 10~100 y=29665.55767x−57181.71917 0.9969 12.42 41.40 99.5 7.8 96.2 6.5 89.6 11.5 酸性红71 10~100 y=366.12316x−104.30076 0.9981 113.57 378.57 90.0） 8.3 93.1 0.2 91.1 3.2 酸性红289 100~1000 y=13.41741x+169.59362 0.9975 815.37 2717.9 72.7 9.6 110.7 13 98.9 6.8 酸性紫49 10~100 y=400.58787x−98.38858 0.9994 55.09 183.62 70.2 5 72.5 13.1 76.7 1.8 酸性绿41 100~1000 y=31.05411x−1080.29451 0.9910 685.35 2284.5 116.5 1.4 100.6 2.7 84.7 5.2 酸性紫9 10~100 y=1055.91180x−351.69408 0.9976 37.24 124.14 102.3 2.4 97.2 1.5 85.5 3.4 酸性蓝41 10~100 y=16662.06544x−19926.57491 0.9987 15.42 51.39 97.4 2.1 96.7 6.1 81.5 8.1 酸性紫 34 100~1000 y=1813.20031x−8926.37811 0.9994 105.25 350.84 95.9 0.7 99.2 7.6 94.4 1.1 酸性红 9 10~100 y=22862.36142x−66680.38419 0.9914 11.53 38.44 96.8 4.1 87.3 1.9 80.5 5.4 酸性兰27 10~100 y=288.12016x−288.95028 0.9982 82.08 273.61 95.5 14.2 88.5 1.4 84.1 0.4 酸性红 88 10~100 y=20945.35351x−15778.83872 0.9968 16.14 53.81 97.2 2.1 101.9 14.9 87.2 5.2 酸性橙 17 10~100 y=16014.50483x−15196.82310 0.9969 21.33 71.10 99.0 3.2 100.9 12.9 93.5 10.6 颜料红49 100~1000 y=1777.76946x−30821.06732 0.9948 172.49 574.98 94.2 0.1 92.4 6.8 87.4 6.3 酸性红92 100~1000 y=501.20203x+2656.97264 0.9997 146.80 489.34 98.9 4.9 108.1 1.2 95.0 3.7 酸性蓝62 10~100 y=14656.86894x+2177.11205 0.9982 17.18 57.28 88.5 7.4 97.2 1.8 80.9 5.7 乙基曙红 10~100 y=335.87537x−709.10966 0.9908 140.95 469.82 87.0 7.3 84.4 0.3 73.9 3.7 酸性红94 100~1000 y=2125.56345x+29066.92700 0.9984 118.53 395.12 99.6 0.9 109.1 0.8 99.8 1.6 食品红105 100~1000 y=1719.19175x+25320.78291 0.9985 86.47 288.22 98.3 1.1 108.7 1.1 101.4 0.6 酸性蓝 83 100~1000 y=401.35032x+2870.96522 0.9974 153.22 510.75 73.3 9.7 74.5 10.3 79.3 5.9 酸性蓝 90 100~1000 y=361.75519x−5443.64145 0.9942 58.25 194.18 87.4 7.2 92.2 2.2 93.0 2.1 酸性蓝113 10~100 y=3235.11512x−4630.72122 0.9944 139.41 464.71 92.2 9.9 90.9 3.1 80.7 5.3 酸性红151 10~100 y=15980.74614x−8516.41801 0.9975 10.97 36.57 100.4 2.5 98.3 2.9 87.7 6.9 直接黄8 10~100 y=15608.60549x−17626.54950 0.9983 8.08 26.94 98.0 0.1 93.5 1.7 88.4 11.4 酸性绿27 10~100 y=200.28220x−312.59313 0.9917 63.13 210.42 96.4 5.2 90.1 7.7 99.5 13.1
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表 3 调味酱筛查结果
Table 3 Screening result of sauce
样品名称 禁用色素 含量（µg/kg） 可食用色素 含量（µg/kg） 草莓果酱 酸性红13 21.5 胭脂红 3982 柠檬黄 539 巧克力调味酱 酸性橙II 30.7 胭脂红 5650 日落黄 5650
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