| [Objective]A monolithic spin columns-solid phase extraction-high performance liquid chromatography(MSC-SPE-HPLC)method was established to determine quinolone antibiotics in environmental water samples and biological samples.Salting-out assisted liquid liquid extraction-ultra-high performance liquid chromatography-mass spectrometry/mass spectrometry(SALLE-UPLC-MS/MS)method was established to determine sulfonamides in environmental water samples.The two methods provide a methodological basis for the sample pretreatment method and determination method for antibiotics.Based on the veterinary drug residue problems,data of the antibiotic drug residues monitoring published by Hainan Province from 2017 to 2021 were used for the dietary risk assessment.Moreover,drug residues of quinolone and sulfonamide antibiotics in some aquatic products sold in Haikou City were determined,and then the data were used for the dietary risk assessment.The results in this work provid data supports for food safety and a basis for the management department to formulate management measures.[Methods](1)In MSC-SPE-HPLC method,coffee grounds were used as the sorbent of MSC-SPE to extract three quinolone antibiotics:ciprofloxacin,enrofloxacin and norfloxacin from environmental samples,the MSC-SPE method was carried out using a SPE column equipped with two 1.5 m L centrifuge tubes.HPLC was used to determine three quinolones in environmental water samples and biological samples.(2)An analytical method was established for simultaneous determination of19 sulfonamides veterinary drug residues in sea water by SALLE-UPLC-MS/MS method.(3)Dietary risk assessement was analyzed by maximum residues limits(MRLs),allowable daily intake(ADI),estimated daily intake(EDI)and ADI contribution value(ADI%)methods and so on.[Results](1)The linear relationship between the methods of MSC-SPE-HPLC was good in the range of 0.1～10μg/m L(R~2>0.998).The limits of detection(LODs)were33.3 ng/m L,and the recoveries were 70.3%to 112.6%with relative standard deviations(RSD)in the range of 1.02%～9.78%at three spiked levels of 0.5,1,2μg/m L.(2)The linear relationship of the SALLE-UPLC-MS/MS method was good in the range of 0.05-20 ng/m L(R~2>0.994),the LODs were 0.05～0.2 ng/m L,and the recoveries were 62.6%～130.0%with RSD in the range of 1.10%～9.88%at 3spiked levels of 1,5 and 10 ng/m L.(3)In the past five years,the unqualified rate of veterinary drug residues in aquatic products is within 11%,the overall unqualified rate is less than 5%,and the percent of pass was gradually increasing from year to year.The most frequently detected veterinary drug residues in the aquatic product were enfloxacin,sulfonamide and ofloxacin.The most frequently detected aquatic products were tilapia,mango snail and raw fish.The residual detection values of veterinary drugs such as sulfonamide and enfloxacin exceeded the MRLs.In the dietary risk assessment of data published in Hainan Province,the ADI contribution value was much less than 1,so it was speculated that health risks can be ignored.36kinds of fishes including 142 samples were analyzed.The results showed that only sulfamidine was determined in two fishes.Health risk was assessed,and the detection value was not exceeded the MRL,the ADI contribution value was much less than 1.[Conclusion](1)MSC-SPE-HPLC method solved the problems of adsorption and purification for solid materials.The complicated experimental steps of SPE were optimized.The consumption of numerous organic solvents is avoided.The reuse of biomass solid waste in the SPE method.(2)SALLE-UPLC-MS/MS method with less solvent usage was suitable for the extraction of trace veterinary drug residues.There are no more cumbersome experimental steps.This method was simple,saved the preparation time,improved the efficiency of extraction.(3)The results of dietary risk assessment can provide some references for the monitoring and direction of future regulatory priorities of veterinary drug residues. |
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