The Applications Of Solid Phase Microextraction-internal Extractive Electrospray Ionization Mass Spectrometry In The Detection Of Residual Pharmaceuticals In Environmental Water

The use of chemically synthesized pharmaceuticals in human production and life is increasing,and plays a huge role in the prevention and control of human and animal diseases and crop production.However,these pharmaceuticals are often not fully and effectively used.Most of them were discharged into the environment,which posing a serious threat to human health and ecosystem.At present,the main methods for detection of residual pharmaceuticals in environmental water are chromatography,chromatography-mass spectrometry,electrochemical sensor and so on.However,these detection methods usually required complex sample pretreatments,which is cumbersome,time consuming and laborious,and are difficult to meet the needs of rapid analysis of real samples.In this paper,solid phase microextraction coupled with internal extractive electrospray ionization mass spectrometry?SPME-iEESI-MS?was established to analyze the fluoroquinolone antibiotics?FQs?and organophosphorus pesticides?OPPs?in environmental water based on the the high enrichment ability of SPME and the characteristics of on-line extraction and direct mass spectrometry analysis of iEESI-MS.The main contents of this paper are as follows:1.A brief overview of the residual status of FQs and OPPs and their harm to human health and ecological environment.The mainly used methods and their shortcomings of residual pharmaceuticals analysis in environmental water samples.2.The principle,characteristics,device structure,and analysis performance of SPME-iEESI-MS technology were investigated.3.SPME-iEESI-MS was applied to the analysis of FQs in environmental water samples.Molecularly imprinted polymers?MIPs?was used as SPME materials for selective enrichment of three FQs?fleroxacin,norfloxacin and enoxacin?in environmental water samples.Then,the MIPs adsorbed FQs was retained on the syringe filter and the excess water samples were removed through a 0.22?m syringe filter.Finally,FQs adsorbed on MIPs were eluted with 2%ammonia/methanol?v/v?,getting an eluate of FQs for mass spectrometric interrogation.Under the optimized experimental conditions,low limits of detections?LODs?of 0.015-0.026?g L^-1 were obtained.The present method also provides good recoveries?91.14-103.60%?with acceptable precision?RSDs less than 6.18%?and have no serious matrix effects for environmental water samples.The experimental results demonstrated that SPME-iEESI-MS contains the advantages of easy-to-use,high speed and high sensitivity,and showing potential application in environmental science and environmental pollution protection.4.The SPME-iEESI-MS was applied to the analysis of OPPs in environmental water samples.Magnetic Fe₃O₄-ZrO₂ nanocomposites prepared by co-precipitation method was applied to enrichment of OPPs in environmental water samples and then combined with iEESI-MS to achieve rapid quantification detection of 15 kinds of OPPs.The parameters such as the amounts of Fe₃O₄-ZrO₂ nanocomposites,pH value,adsorption time,type and volume of desorption solvent,shaking time of desorption were systematically optimized.Under the optimized experimental conditions,the limits of detections?LODs?of 0.14-16.39 ng L^-1 were obtained.The present method also provides good recoveries?85.4-105.9%?with the relative standard deviations?RSDs?less than 6.7%.Furthermore,multiple analytes were simultaneously detected in a single sample run,resulting in significantly improved analytical throughput for quantitative analysis of bulk amounts of samples.The experimental results proved that SPME-iEESI-MS contains the advantages of high sensitivity,high speed and reasonable selectivity,which provides a powerful analytical method for the detection of residual pharmaceuticals in complex environmental water samples.