Determination of 7 Phenolic Environmental Hormones in Citrus by QuEChERS/High Performance Liquid Chromatography£­Tandem Mass Spectrometry

KeyWord:high performance liquid chromatography£­tandem mass spectrometry  QuEChERS  environmental hormones  citrus

Abstract:

      A QuEChERS/high performance liquid chromatography£­tandem mass spectrometry£¨QuEChERS/HPLC£­MS/MS£© was established for the simultaneous detection of seven phenolic environmental hormones in citrus£®Effects of different extraction solvents£¬extraction time£¬extraction solvent volume and adsorbent types on the extraction efficiency for target compounds were compared£®The samples were ultrasonically extracted twice with acetonitrile containing 0.1% formic acid after homogenization£¬and then purified by modified QuEChERS method with 50 mg PSA + 50 mg C18£®The target compounds were separated on a Waters ACQUITY UPLC BEH C18 column£¨50 mm ¡Á 2.1 mm£¬1.7 ¦Ìm£© by gradient elution£¬with water containing 0.5 mmol/L ammonium acetate and methanol as the mobile phases at a flow rate of 0.2 mL/min and a column temperature of 40 ¡æ£®The mass spectra were recorded by negative electrospray ionization under the multiple reaction monitoring£¨MRM£© mode£®External standard method was used for the quantitative analysis£®Under the optimized conditions£¬bisphenol A£¨BPA£©£¬nonylphenol£¨NP£©£¬bisphenol F£¨BPF£© showed good linear relationships within the range of 0.5£­100 ¦Ìg/L£¬while bisphenol B£¨BPB£©£¬bisphenol S£¨BPS£©£¬n-nonylphenol£¨4-n-NP£©£¬n-octylphenol£¨4-n-OP£© exhibited good linear relationships within 0.2£­100 ¦Ìg/L£®The correlation coefficients£¨r2£© were not less than 0.994 1. The detection limits£¨LOD£©and the quantitation limits£¨LOQ£©of the method were in the ranges of 0.2£­0.5 ¦Ìg/L and 0.5£­1.5 ¦Ìg/L£¬respectively£®At the three spiked levels of 10£¬250 and 500 ¦Ìg/kg£¬the average recoveries for the target compounds ranged from 88.5% to 109%£¬with the relative standard deviations£¨RSD£©of 1.2%£­9.0%£®The method was applied to the detection of 8 commercially available citrus samples£®BPA was detected in 7 kinds of citrus£¬4-n-OP was detected in 5 kinds of citrus£¬NP and 4-n-NP were detected in 3 types of citrus£¬BPB was detected in 1 type of citrus£¬and BPF and BPS were not detected in all samples£®The above results indicate that bisphenol environmental hormones are commonly found in commercially available fruits and need to be paid attention to£®This method was simple to operate£¬rapid£¬sensitive£¬accurate and highly precise£®It was suitable for the determination of 7 bisphenol environmental hormones in citrus£®