摘要
建立了粮食样品中14种有机磷酸酯(OPEs)及其8种二酯代谢物(di-OPEs)的超高效液相色谱-串联质谱分析方法(UPLC-MS/MS)。样品以甲醇为溶剂超声萃取后,直接加载到活化后的ENVI-18固相萃取柱中,萃取液用5 mL甲醇洗脱,合并洗脱液氮吹定容后进样分析,采用内标法定量。22种目标物在0.1~20µg/L范围内线性关系良好(r>0.99),方法检出限(S/N=3)为0.00502~1.94 ng/g,定量下限(S/N=10)为0.0167~6.45 ng/g;除磷酸二丁氧酯(BBOEP)的加标回收率为141%外,其它目标物的回收率为60.0%~131%,相对标准偏差为0.57%~22%。采用该方法对25个小麦样品进行测定,14种OPEs的总含量为0.843~23.5 ng/g,其中4种OPEs在全部样品中均检出,磷酸三(1-氯-2-丙基)酯(TCIPP)是主要物质;8种di-OPEs的总含量为0.126~4.81 ng/g,其中4种di⁃OPEs的检出率高于50%,磷酸二(2-乙基己基)酯(BEHP)是主要物质。结果表明,有机磷酸酯及其二酯代谢物在粮食样品中普遍存在。暴露估算结果显示,我国成年人和儿童通过食用小麦对OPEs的暴露量分别为4.23~118 ng/kg bw/day和5.56~155 ng/kg bw/day;对di-OPEs的暴露量分别为0.633~24.2 ng/kg bw/day和0.832~31.7 ng/kg bw/day。整体上,通过小麦摄入的暴露量远低于各OPEs的人体口服参考剂量,但考虑到小麦的加工运输过程可能引入更多OPEs及其代谢物,同时还存在其他种类饮食的暴露,人体通过饮食对OPEs及di-OPEs的暴露应引起重视。
An ultra⁃high performance liquid chromatography-tandem mass spectrometric(UPLC-MS/MS)method was developed for the detection of 14 organophosphate esters(OPEs)and their 8 di⁃ester metabolites(di-OPEs)in cereal samples in this paper,and the pre⁃treatment process of purifica⁃tion was optimized.The cereal samples were ultrasonically extracted with methanol three times,and then purified directly with ENVI-18 cartridges without solvent conversion and eluted with 5 mL meth⁃anol.The combined eluent was concentrated under nitrogen.Finally,the analytes were analyzed by UPLC-MS/MS and quantified by the internal standard method.The analytes were separated on an Acquity UPLC BEH C18 column by gradient elution using methanol and 5 mmol/L ammonium ace⁃tate aqueous solution as mobile phases,and ionized in electrospray ionization positive mode for OPEs and negative mode for di-OPEs under the multiple reaction monitoring(MRM)mode.Results showed that there were good linear relationships for all compounds in the range of 0.1-20µg/L,with their correlation coefficients(r)greater than 0.99.The detection limits(LOD)and quantitation limits(LOQ)for OPEs and di⁃OPEs were in the range of 0.00502-1.94 ng/g and 0.0167-6.45 ng/g,respective⁃ly.The average recoveries(n=3)for 22 compounds in cereal samples at three spiked levels of 5,10 and 20 ng/g ranged from 60.0%to 131%except BBOEP(141%),with relative standard deviations(RSD)of 0.57%-22%.The optimized method was applied to the quantitation of OPEs and di-OPEs in 25 wheat samples.The total contents of 14 OPEs were in the range of 0.843-23.5 ng/g.Four OPEs(TEP,TCEP,TCIPP and EHDPP)were detected in all samples,while TCIPP was the main OPEs.The total contents of 8 di-OPEs were in the range of 0.126-4.81 ng/g,and the detection frequencies for 4 di⁃OPEs(DBP,DPHP,BEHP and BDCPP)were higher than 50%,while BEHP was the main di⁃OPEs.These results indicated that these OPEs and di⁃OPEs were widespread in ce⁃real samples.Based on the measured OPEs and di-OPEs contents,the estimated daily intakes(EDIs)ofΣ14OPEs via cereal intake were in the range of 4.23-118 ng/kg bw/day and 5.56-155 ng/kg bw/day for Chinese adults and children,respectively.The daily intake of 8 di-OPEs were in the range of 0.633-24.2 ng/kg bw/day and 0.832-31.7 ng/kg bw/day for adults and children,respec⁃tively.Overall,the EDIs through wheat intake were much lower than the Reference Dose(RfD)of OPEs.However,considering that the processing and transportation may introduce more OPEs and their metabolites into the wheat and there exists the possibility of other food contaminated by OPEs or di-OPEs,the human exposure to OPEs and di-OPEs through diet should be concerned.
作者
张博钠
侯敏敏
钱承敬
史亚利
蔡亚岐
ZHANG Bo-na;HOU Min-min;QIAN Cheng-jing;SHI Ya-li;CAI Ya-qi(School of Environment,Hangzhou Institute for Advanced Study,UCAS,Hangzhou 310024,China;State Key Laboratory of Environmental Chemistry and Ecotoxicology,Research Center for Eco-Environmental Science,Chinese Academy of Sciences,Beijing 100083,China;University of Chinese Academy of Sciences,Beijing 100049,China;Beijing Key Laboratory of Nutrition&Health and Food Safety,Nutrition&Health Research Institute,COFCO Corporation,Beijing 102209,China)
出处
《分析测试学报》
CAS
CSCD
北大核心
2022年第1期91-99,共9页
Journal of Instrumental Analysis
基金
国家自然科学基金项目(22036007,21777182,22176198)。
关键词
有机磷酸酯
超高效液相色谱-串联质谱
粮食
固相萃取
organophosphate ester
ultra-high performance liquid chromatography-tandem mass spectrometry
cereal
solid phase extraction
