气相色谱-质谱法检测益智药材中16种多环芳烃

Determination of 16 Polycyclic Aromatic Hydrocarbons in Alpinia Oxyphylla Miq by Gas Chromatography-Mass Spectrometry

建立了气相色谱-质谱联用技术同时测定益智药材中16种多环芳烃(PAHs)的分析方法。最佳萃取条件为:取样品2.0 g,加入同位素内标后用无水乙醇、水混合溶解,以10 mL正己烷提取;提取液先过Florisil柱固相萃取,经氢氧化钾-乙醇溶液皂化,多环芳烃分子印迹柱固相萃取后,以5 mL二氯甲烷-正己烷(1∶1,体积比)进行洗脱;采用DB-EUPAH毛细管色谱柱进行分离,内标标准曲线法定量测定。在此条件下,16种多环芳烃的线性范围为1.0~200.0μg/L(r^(2)≥0.9925);检出限(S/N=3)为0.3~1.0μg/kg;在不同浓度(1、3、10μg/kg)基质加标条件下,苯并[c]芴(BcFL)的加标回收率为65.4%~72.8%,日内相对标准偏差(RSD,n=6)为6.0%~7.4%,日间RSD(n=6)为8.5%;其他15种多环芳烃的加标回收率为89.3%~116%,日内RSD(n=6)为0.10%~6.1%,日间RSD(n=6)为1.2%~7.5%。该方法的前处理净化效果好、灵敏度高、准确度高,适用于益智药材中16种多环芳烃的定量检测。

An effective method was developed for the determination of 16 polycyclic aromatic hydrocarbons(PAHs)in Alpinia oxyphylla Miq based on gas chromatography-mass spectrometry(GC-MS).The samples were separated on a DB-EUPAH capillary chromatography column,detected by GC-MS with electron ionization source in selective ion mode,and quantified by stable isotope internal standard method.The optimal extraction conditions were as follows:2.0 g of sample was added with isotope standard solution,then mixed with absolute ethanol and water to dissolve,followed by addition of 10 mL n-hexane for extraction.The extract was firstly subjected to solid-phase extraction with a Florisil column,then saponified with KOH-ethanol solution,and extracted again by solid-phase extraction with a polycyclic aromatic hydrocarbon molecularly imprinted column,finally,eluted with 5 mL dichloromethane-n-hexane(1∶1,by volume).Results showed that the 16 PAHs presented good linear relationships in the concentration range of 1.0-200.0μg/L with correlation coefficients(r^(2))not less than 0.9925.The limits of detection were in the range of 0.3-1.0μg/kg,and the limits of quantitation were 1.0-3.0μg/kg.The average recoveries(n=6)for benzo[c]fluorene(BcFL)ranged from 65.4%to 72.8%,with intra-day relative standard deviations(RSD,n=6)of 6.0%-7.4%and inter-day relative standard deviations(RSD,n=6)of 8.5%,respectively,while the average recoveries for the other 15 PAHs were in the range of 89.3%-116%,with intra-day RSDs(n=6)of 0.10%-6.1%and inter-day RSDs(n=6)of 1.2%-7.5%,respectively.The developed method showed excellent purification effect,sensitivity and high accuracy,and was suitable for the simultaneous determination of 16 PAHs in Alpinia oxyphylla Miq.