超高效液相色谱－串联质谱法测定粮食中有机磷酸酯及其二酯代谢物

张博钠; 侯敏敏; 钱承敬; 史亚利; 蔡亚岐

Determination of Organophosphate Esters and Their Diester Metabolites in Cereals by Ultra?high Performance Liquid Chromatography－Tandem Mass Spectrometry

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KeyWord:organophosphate ester ultra-high performance liquid chromatography－tandem mass spectrometry cereal solid phase extraction

Author

Institution

ZHANG Bo?na,HOU Min?min,QIAN Cheng?jing,SHI Ya?li,CAI Ya?qi

1.School of Environment，Hangzhou Institute for Advanced Study，UCAS，Hangzhou ，China; 2. State Key Laboratory of Environmental Chemistry and Ecotoxicology，Research Center for Eco?Environmental Science，Chinese Academy of Sciences，Beijing ，China; 3. University of Chinese Academy of Sciences， Beijing ，China; 4. Beijing Key Laboratory of Nutrition & Health and Food Safety， Nutrition & Health Research Institute，COFCO Corporation，Beijing ，China

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Abstract:

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 diester metabolites（di-OPEs） in cereal samples in this paper，and the pre?treatment process of purification 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 methanol．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 acetate 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 0.1－20 μg/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 0.005 02－1.94 ng/g and 0.016 7－6.45 ng/g，respectively．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 cereal samples．Based on the measured OPEs and di-OPEs contents， the estimated daily intakes（EDIs） of Σ14OPEs 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，respectively．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.