Study Of Sample Pretreatment Method For The Determination Of Polybrominated Diphenyl Ether And Organophosphate Flame Retardant In The Atmospheric Particulate Matter

With the increasing demand for PBDEs and OPEs,PBDEs and OPEs are ubiquitous in the environment.PBDEs and OPEs are easy to enter the air through volatilization or exudation,and accumulate on atmospheric particles,which have been widespread in the air environment.Some PBDEs and OPEs are persistent pollutants,which are easy to accumulate in living organisms and have gradually affected human health.Because there are many kinds of organic pollutants in atmospheric particulate matter and complex matrix,single extraction technology can not meet the requirements of instrument and equipment for sample analysis.Subsequently,impurities in the matrix should be removed in combination with purification technology.Therefore,it is very important to a establish green,simple and efficient pretreatment method for PBDEs and OPEs samples in atmospheric particulate matter.This paper in view of the flame retardant type of pollutants,respectively developed ultrasonic extraction-dispersive liquid-liquid microextraction determination of polybrominated diphenyl ethers and organophosphorus esters in atmospheric particulate matter,ultrasonic extraction-direct immersion solid-phase microextraction determination of organophosphorus esters in atmospheric particulate matter sample preparation method,and application development approach to the actual measurement of atmospheric samples.The content of the paper is as follows:（1）The experimental conditions for the extraction and purification of seven PBDEs from atmospheric particulate matter PM₁₀were optimized and determined by gas chromatography-mass spectrometry.After ultrasonic extraction,the samples were purified and enriched by dispersive liquid-liquid microextraction,and finally quantitatively analyzed by gas chromatography-mass spectrometry（GC-MS）.The detection limits and quantitation limits of 7 PBDEs ranged from 0.017 to 0.292 pg/m³and 0.057 to 0.972 pg/m³.The spiked recoveries were 72.77 to 125.02%and the relative standard deviation（RSD）were 0.42 to 12.40%.The method was used to determine PBDEs of PM₁₀in Suzhou area for a week,and it was found that PBDE homologues were detected in different degrees.The detected concentrations of seven kinds of∑PBDEs in PM₁₀ranged from 0.241 to 0.678 ng/m³.（2）A method was established for the determination of seven OPFRs in the atmosphere by ultrasonic extraction-dispersion liquid-liquid microextraction combined with gas chromatography tandem triple quadrupole mass spectrometry.In this experiment,single factor optimization method combined with Box-Benhnken experimental design method was used to optimize the process parameters of ultrasonic extraction and dispersed liquid-liquid microextraction to determine the optimal conditions of the experiment.The samples were extracted by ultrasonic extraction with mixed solution of ethyl acetate and acetone（3:2,V/V）as the extraction agent,and further purified and concentrated by dispersive liquid-liquid microextraction（pure water as the purified matrix,carbon tetrachloride as the extraction agent,anhydrous ethanol as the dispersant）.The limits of detection and quantitation were 0.005～0.331 pg/m³and 0.016～1.084 pg/m³.The recoveries were70.00～119.70%and the relative standard deviation（RSD）were 0.2～9.4%.This method was applied to the detection of PM₁₀in suzhou area,and the results showed that most OPFRs were present in PM₁₀.（3）A method was established for the determination of 10 OPEs in PM_2.5by ultrasonic-assisted extraction and direct immersion solid-phase microextraction combined with gas chromatography tandem triple quadrupole mass spectrometry.This method has been successfully applied to the analysis and determination of atmospheric samples.In this experiment,Plackett-Burman design was used to screen out the three factors with significant influence.Later,central combination design experimental design method was used to optimize the experimental parameters of direct immersion solid phase microextraction to determine the optimal conditions of the experiment.The sample was extracted by ultrasonic extraction with acetone and n-hexane（2:3,V/V）mixed solution.The concentrated extract was further purified and concentrated by direct immersion solid phase microextraction（pure water as the purified matrix）.Under the optimal conditions,the limits of detection were0.002～0.175μg/L,the limits of quantitation were 0.007～0.528μg/L,the maximum recoveries were 63.31～120.00%,and the relative standard deviations（RSD）were1.21%to 12.10%.This method was applied to the detection of PM_2.5in suzhou area,and the detection showed that there were most organophosphorus esters in PM_2.5.In the monitoring of outdoor OPEs concentration for one week in Suzhou area,the concentration of 10 OPEs ranged from 0.026 to 8.682 ng/m³.The OPEs respiratory exposure assessment of human body showed that the daily high exposure of children,adults and outdoor workers were 0.724 ng/kg,1.168 ng/kg and 2.920 ng/kg.