大蒜精油中塑化剂的两种检测方法比对.pdf

85欧金玉：大蒜精油中塑化剂的两种检测方法比对|检验检测大蒜精油中塑化剂的两种检测方法比对欧金玉（安徽中青检验检测有限公司，安徽合肥2 30 0 8 8）【摘要】本文主要研究了大蒜精油中16 种邻苯二甲酸酯类塑化剂的两种快速准确的检验方法，结果显示：采用GC-MS-MS能够很好地分离16 种化合物，且峰形好响应高，在0.0 5 1.5g/mL范围内线性良好，加标回收率为8 0%110%，相对标准偏差RSD为2%5%。该方法可作为大蒜精油中16 种邻苯二甲酸酯类塑化剂的最优检测方法。【关键词】气相色谱质谱联用仪；气相色谱-三重四级杆质谱仪；大蒜精油；塑化剂【D O I编码】10.39 6 9/j.issn.1674-4977.2023.05.027Comparison of Two Detection Methods for Plasticizer in Garlic Essential OilOUJinyu(Anhui Zhongqing Inspection and Testing Co.,Ltd.,Hefei 230088,China)Abstract:This paper mainly studied two rapid and accurate detection methods for 16 Phthalic acid ester Plasticizer in garlic essentialoil.The results showed that GC-MS-MS detection results showed that 16 compounds could be well separated,and the peak shape wasgood,and the linearity was good in the range of 0.051.5 g/mL,the recovery rate of standard addition was 80%110%,and therelative standard deviation was RSD2%5%.The best detection method for 16 Phthalic acid ester Plasticizer in garlic essential oil wasfound.Key words:gas chromatography-mass spectrometer;gas chromatography-triple quadrupole mass spectrometer;garlic essential oil;plasticizer塑化剂是邻苯二甲酸酯类化合物（phthalateacid esters，PAEs)的简称，,它是一种助剂。将塑化剂添加在塑料中可以增加塑料的柔韧性和可塑性，所以其被广泛地应用在食品包装材料、玩具、餐具等各种塑料制品中-2。塑化剂是可以迁移的。大蒜精油由大蒜辣素、大蒜新素及多种烯丙基和甲基组成的硫醚化合物组成，含有多种大蒜挥发油4,基质复杂，通过仪器比对,GC-MS-MS检测可以减弱基质影响。因此本文将同样处理的样品分别进GC-MS及GC-MS-MS检测，通过仪器比对结果，确立大蒜精油中塑化剂最优检测方法。11设备、材料与方法1.1设备与材料Agilent7820A/5977BMSD气相色谱质谱联用仪，ThermoTrace1300/TSQ8000Evo气相色谱-三重四级杆质谱，涡旋混合器，cence湘仪TGL-16M高速冷冻离心机。上海安谱实验科技股份有限公司色谱纯乙腈，甲醇，正已烷。16 种邻苯二甲酸酯类标准品（1mL，10 0 0 u g/mL）,均购买于北京坛墨质检科技有限公司。1.2方法1.2.1大蒜精油取1mL样品正已烷定容至5mL，涡旋混匀，10，30 0 0r/min，离心3min,取上清液待测。阳性大蒜精油样品：取一定量大蒜精油样品，加人邻苯二甲酸酯类混标，按照大蒜精油样品处理。混标标准品使用液：取1mL混标标准品，正已烷定容至10 mL,此为10 0 g/mL标准品中间液。取1mL中间液，正已烷定容至10 mL，此为10 g/mL标准品使用液。1.2.2仪器条件1.2.2.1单四级杆质谱（Agilent5977B）色谱柱：DB-5MS(30m0.25mm0.25um）进样口温度250,不分流进样，色谱柱流量1mL/min，氮气为载气。升温程序为初始温度6 0 保持1min，2 0/m i n 升至2 2 0 保持1min,5C/min升至2 8 0 C保持6 min。1.2.2.2三重四级杆质谱（ThermoTSQ8000Evo)86BRAND&STANDARDIZATION品牌与标准化2023年第5期1)色谱条件色谱柱：TG-5SILMS(30m0.25mm0.25um）进样口温度2 7 0，不分流进样，色谱柱流量1.2 mL/min，氨气为载气，氩气为碰撞气。升温程序为初始温度7 0 保持1min，2 0/min升至2 8 0,6 C/min升至310 保持1.5min。2)质谱条件传输线温度2 8 0，EI离子源温度30 0。溶剂延迟5min，采用SRM模式，进混标标样自动优化母离子、子离子以及碰撞能。2结果与分析2.1GC-MS检测结果2.1.1线性关系在0.0 5 0.8 g/mL浓度范围内，线性方程和相关系数R见表1，相关系数均大于0.9 9，线性良好，满足样品定量需求。表116种邻苯二甲酸酯类线性方程和相关系数名称方程R2DMPY=0.140052X-0.1427100.998DEPY=0.1505254X-0.2302740.998DIBPY=0.130030X-0.1012510.998DBPY=0.134758X-0.2283140.998DMEPY=0.041524X+0.2061310.998BMPPY=0.157071X-0.1425390.997DEEPY=0.202182X+0.211420.997DPPY=0.136023X-0.2048110.996DHXPY=0.130255X-0.3763410.996BBPY=0.123460X-0.1281340.997DBEPY=0.145589X-0.1312040.998DCHPY=0.155936X-0.3431480.998DEHPY=0.139831X-0.2033280.993DPhPY=0.126814X-0.0674280.994DNOPY=0.119980X-0.0998710.997DNPY=0.110359X-0.0200170.9952.1.2精密度及回收率试验精密度符合标准要求；大蒜精油中加人相当于0.5g/mL16种邻苯二甲酸酯类混标标液，检测得DMP、BMPP、D E E P、DEP回收率低于6 5%，BBP、D E BP、D BP、D C H P、D E H P、DHXP、D IBP、D NO P、D PH P、D PP回收率在7 6%10 2%，DMEP峰与基质融合，无法定量，实验结果见表2。表216种邻苯二甲酸酯类精密度名称123456平均值RSD/%DMP51.2452.0451.1151.2555.1450.8751.941.47DEP50.1251.4451.8556.65 55.2657.1453.742.72表216种邻苯二甲酸酯类精密度（续）名称123456平均值RSD/%DIBP50.2855.0453.1450.1952.3455.1452.692.00DBP50.2849.35 51.1553.3450.1152.6151.141.41DMEP50.1154.1257.1153.9452.1656.1553.932.34BMPP56.14 53.2550.8951.2554.0253.1253.111.75DEEP49.1951.6952.1155.1557.2652.1652.932.60DPP48.1849.2655.2553.2551.1546.2550.563.04DHXP55.18 49.1448.1556.8951.2049.2451.633.28BBP50.1652.3354.14 55.26 51.2850.1452.221.93DBEP48.7647.9952.1850.19 53.1450.8650.521.80DCHP55.2450.1448.2347.2151.3553.2150.902.76DEHP50.14 55.2650.48 53.1655.2450.1552.412.26DPhP49.4647.1452.14 55.86 57.1650.2452.003.53DNOP55.1456.5650.14 55.24 49.18 50.4652.792.92DNP49.2847.6955.1550.2853.4650.4451.052.522.2GC-MS-MS检测结果2.2.1线性关系在0.0 5 1.5g/mL范围内，16 种邻苯二甲酸酯类能够很好地被分离。各化合物线性方程和相关系数R值见表3。相关系数均大于0.9 9 5，线性良好，精确定量满足样品定量需求。表316种邻苯二甲酸酯类线性方程和相关系数名称方程R2DMPY=0.121152X-0.0568100.998DEPY-0.1305553X-0.1361730.997DIBPY=0.143330X-0.1447710.999DBPY=0.154868X-0.2397560.999DMEPY=0.040584X+0.2263910.995BMPPY=0.137172X-0.1863790.999DEEPY=0.207280X+0.200520.998DPPY=0.156023X-0.2844870.999DHXPY=0.160955X-0.3963460.997BBPY=0.123930X-0.1231540.997DBEPY=0.144579X-0.2341000.998DCHPY=0.165626X-0.3535900.998DEHPY=0.140824X-0.2143160.999DPhPY=0.130809X-0.0615850.998DNOPY=0.126980X-0.1071280.996DNPY=0.101769X-0.0131750.9992.2.2回收率及精密度试验大蒜精油中加相当于0.15g/mL，0.8 g/mL低浓度和高浓度水平标准品中间液，作为两个加标样品，每个样品6 个平行，计算加标回收率和精密度，16 种物质的回收率均在80%110%之间，符合要求，具体结果见表4。87（编辑：李加鹏）欧金玉：大蒜精油中塑化剂的两种检测方法比对|检验检测表416种邻苯二甲酸酯类加标试验结果加标水平/回收率/%名称RSD/%(g/mL)123456平均0.1585.5587.2895.1482.1789.2290.0588.244.02DMP0.8099.1896.24105.24109.2198.25110.92103.175.610.1585.9180.9782.3680.3980.1181.9681.951.94DEP0.8080.3682.2681.2486.2380.2883.2682.272.050.1582.6596.2583.1189.2487.1593.2688.614.97DIBP0.8096.2590.1595.1197.188.1480.1591.155.890.1580.2881.3586.1582.3480.1188.6183.143.17DBP0.8087.2588.1280.0089.2588.5481.1185.713.710.1580.1186.1287.1187.9487.1688.1586.102.76DMEP0.8088.1280.1182.1483.6587.9269.9981.996.100.15109.14100.2599.89118.25120.02106.12108.957.90BMPP0.80108.79115.24101.22120.04119.2599.99110.768.050.1586.1984.6980.1187.1587.2687.1685.432.54DEEP0.8086.1883.1580.1685.8787.2279.1183.623.090.1599.18105.26112.25107.25100.15110.25105.724.82DPP0.80103.1599.87106.11114.89109.25100.11105.565.300.15106.18102.14108.15105.89101.20105.24104.802.40DHXP0.80102.11107.89101.24105.98101.35109.12104.623.190.1599.25102.1199.17110.25105.14101.24102.863.87BBP0.80100.2899.19110.27110.26108.11101.02104.864.780.15109.35105.24110.35102.07108.91110.25107.703.04DBEP0.80101.58109.14102.98107.04109.04108.9106.453.060.1599.28110.24107.11101.18100.2499.35102.904.23DCHP0.80101.2499.13101.24106.22110.2499.25102.894.040.15103.25109.22110.24108.35101.11100.88105.513.88DEHP0.80105.41101.24101.07100.87109.58100.91103.183.280.1599.14105.14100.11105.58102.34104.59102.822.49DPhP0.80105.04101.09103.2499.25108.24101.00102.982.980.15110.34106.22109.24103.22105.77105.98106.802.36DNOP0.80106.24104.85110.29109.25107.25104.66107.092.100.15109.24109.25108.24107106.11102.78107.102.24DNP0.80109.25105.46105.86105.94105.24108.15106.651.503丝结论通过优化条件以及仪器GC-MS、G C-MS-MS比对，16 种邻苯二甲酸酯类标准品在GC-MS上均有良好的响应，且各邻苯二甲酸酯类可以很好地分开，峰形好。但是对于大蒜精油阳性样品，多种邻苯二甲酸酯类回收率较低，且DMEP未检出，无法准确定量样品中目标物含量。三重四级杆质谱因其多一重四级杆，多一层质量筛选，具有更高的特异性，受基质影响更小，大蒜精油中16 种邻苯二甲酸酯类均可检测出，加标回收率和精密度满足样品检测需求。因此GC-MS-MS检测大蒜精油中邻苯二甲酸酯类，具有更快速、更准确的特点，前处理简单，适用于大蒜精油中塑化剂的检测分析。品【参考文献】1张微.邻苯二甲酸酯在食品检测中的研究进展 1.现代食品,2 0 19(7):19 4-19 6.2邹燕娣，包李林，周青燕，等.食用植物油中邻苯二甲酸酯类塑化剂来源和风险控制措施研究 J.中国油脂，2 0 19，44(5):123-127.【作者简介】欧金玉，女，19 9 4年出生，助理工程师，学士，研究方向为检验检测。