On-line Gel Permeation Chromatography Coupled With Gas Chromatography Tandem Mass Spectrometry For Determination Of Organophosphorus Pesticide In Whole Blood Extracted By Different Pretreatment Methods

Nowadays,organophosphorus pesticides have been used widely.The acute organophosphorus poisoning accidents were making up a large proportion in practical cases,which had attracted much attention.Majority of the samples in the cases were whole blood samples,therefore quantitative analysis of organophosphorus pesticides in the whole blood became a very important research subject.It is well known that the whole blood samples containing various matrixes are complex and require pretreatment procedures.In this paper,three different pretreatment methods had been introduced and applied to extract organophosphorus pesticides from the whole blood samples,and the corresponding quantitative methods were established,respectively.This paper mainly consists of four chapters as below:In the first chapter,the categories,properties,and hazard of organophosphorus pesticides as well as the analysis methods of organophosphorus pesticides had been introduced.The pretreatment methods such as accelerated solvent extraction(ASE),QuEChERS and solid phase extraction(SPE)also had been introduced.Furthermore,on-line gel permeation chromatography coupled with gas chromatography tandem mass spectrometry method had been discussed deeply.In the second chapter,accelerated solvent extraction had been used for extracting organophosphorus pesticides from the whole blood.In this method,the solvent,temperature and static extraction time had been studied and optimized to realize a satisfactory result.PSA and GCB were used for cleansing the complex matrix in whole blood sample after concentration and redissolving.Using automatic accelerated solvent extraction apparatus,the whole blood sample was able to be injected to GC/MS after a batch processing,which showed a high degree of automation.An ASE-GPC-GC/MS method had been developed for the determination of 10 organophosphorus pesticides.The limits of detection(LODs)of the analyzed organophosphorus pesticides were 1.2-19.2 mg·L-1,and the recoveries were in the range of 80.0-107.2%at the three spiking levels with associated inter-day relative standard deviations(RSDs)below 5%except for acephate.In the third chapter,QuEChERS method were used for extracting organophosphorus pesticides from the whole blood.In this method,the usage amount of PSA and GCB,the kind and amount of the extract solvent had been studied and optimized to realize a satisfactory result.Under the optimal conditions,the QuEChERS method could reduce most of the matrix in the whole blood samples without much sacrifice of the recovery.The QuEChERS-GC/MS method had been developed for the determination of 10 organophosphorus pesticides.The limits of detection(LODs)of the analyzed organophosphorus pesticides were 2.2-48.7 mg·L-1,and the recoveries were in the range of 80.4-11.7%at the three spiking levels with associated inter-day relative standard deviations(RSDs)below 3%.The most time-consuming procedure was not needed in this method.Furthermore,validation results on linearity,specificity,trueness and precision,as well as application to the analysis of 10 organophosphorus pesticides in real samples demonstrated the applicability to acute organophosphorus poisoning accidents.In the fourth chapter,solid phase extraction was employed as the pretreatment method.Three cartridges i.e.,Waters Oasis HLB,Waters Sep-Pak C18 and CNWBOND GCB/PSA,had been used for extracting organophosphorus pesticides from the whole blood.The effect of extraction solvents were studied,and the results showed that the extract efficiency of Waters Oasis HLB was much better than the other two cartridges.The SPE-GC/MS method had been developed for the determination of 10 organophosphorus pesticides.The limits of detection(LODs)of the analyzed organophosphorus pesticides were 2.6-8.3 mg·L-1,and the recoveries were in the range of 80.3-109.1%at the three spiking levels with associated inter-dayrelative standard deviations(RSDs)below 10%except for acephate(15%).In short,the three analytical methods i.e.,ASE-GPC-GC/MS,QuEChERS-GPC-GC/MS and SPE-GPC-GC/MS method,had been developed and validated for the determination of 10 organophosphorus pesticides in the whole blood sample.Validation results and application to the analysis of 10 organophosphorus pesticides in real samples demonstrated the applicability to acute organophosphorus poisoning accidents.