| In this paper, the nature, the source of the pollution situation and enrichment, purification and analysis method of HBCD (Hexabromocylcododecane, HBCDs) were reviewed comprehensively. So far there is no universal method of analysis in domestic and foreign. This study develops the sample determination techniques systematically and the factors influencing recovery and sensitivity were investigated and optimized with single factor experiment and orthogonal experiment. Ultrasound-assisted ionic liquid dispersive liquid liquid microextraction (USA-IL-DLLME) coupled with liquid chromatography and tandem quadrupole mass spectrometry(LC-MS/MS) was developed for determination of HBCDs in environmental water samples; QuEChERs approach followed by liquid chromatography coupled with tandem mass spectrometry (LC-ESI-MS/MS) method has been developed for the determination of hexabromocyclododecane enantiomers (±α±β, and ±γ-HBCD) in chicken blood; MSPD procedure has been developed for the determination of hexabromocyclododecane enantiomers (±α, ±β and ±γ-HBCD) in chicken muscle. This dissertation included the following conclusions:(1) Based on ultrasound-assisted ionic liquid dispersive liquid phase microextraction coupled with liquid chromatography tandem quadrupole mass spectrometry (USA-IL-DLLME-LC-MS-MS), a simple, rapid, environmental, methods were established for the determination of HBCDs. The advantages of USA-IL-DLLME-LC-MS-MS using dozens microliters of room temperature ionic liquids (RTIL) instead of the traditional several hundred milliliters of toxic organic reagent, avoiding environmental pollution, reducing the cost, improving work efficiency. The results from analysis of the real water samples demonstrated that the proposed methods are good accuracy, high precision and lower level of detection, and can be used widely in environmental research.The factors influencing extraction efficiencies, including kinds and volume of ionic liquid, ultrasonic time, the sample pH and salt concentration, were investigated and optimized. The final optimum conditions are 70μL [C6MIM][PF6], extraction time 3min, solution pH 7 and 0% salt content. Under the optimum conditions, the calibration graph of the proposed method was line in the range of 0.5～100ng/mL and the correlation coefficient is greater than 0.998. The limit of detection was 156.4ng/L、84.6ng/L、85.5ng/L and the precisions were 5.3-9.7%. The method was applied to analyze the environmental water samples, the recoveries at the spike levels of 1 μg/L and 20μg/L were at about 71%to 102%.(2) A novel analytical method has been developed for the determination of hexabromocyclododecane enantiomers (±α, ±β and±γ-HBCD) in chicken blood. The method is based on the quick, easy, cheap, effective, rugged, and safe (QuEChERS) approach followed by liquid chromatography coupled with tandem mass spectrometry (LC-ESI-MS/MS). Isotope dilution method was used to eliminate the influence of the mechanism of the matrix effect. The final optimum conditions are 7mg GCB,120mg neutral alumina, 100mg anhydrous MgSO4,2.5mL ACN and 1mLblood sample.. The type of extraction solvent and dispersive adsorbent, were investigated by single factor experiment. The volume of extraction solvent, amount of decoloring adsorbent and purifying dispersive adsorbents were optimized by the Box-Behnken design through response surface methodology. Under optimized conditions, lml samples were blended with 1 g of Forisil and 1.2g C18 in the follow for liposuction. Under the optimized conditions, the proposed method showed good linearity within the range of 1-500 ng/mL and good repeatability (RSD less than 9.5%, n= 5).The limits of detection was 0.04-0.19 ng/mL (S/N=3:1). The proposed method had been applied for the determination of HBCD enantiomers in two real chicken blood samples, and satisfactory recoveries range of 83.6%-115.0% was obtained at three spiked levels (5,20 and 100 ng/mL). All the above results demonstrated that the proposed method would be an application value method for the determination of HBCDs in chicken blood. Experimental results indicated that QuEChERS combined LC-ESI-MS/MS method would be a rapid, simple and application value method for the determination of lipophilic organic pollutants in blood.(3) MSPD procedure has been developed for the determination of hexabromocyclododecane enantiomers ((±α, ±β and ±γ-HBCD) in chicken muscle. To obtain excellent method efficiency, the factors including the type of elution solvent and dispersive adsorbent, were investigated by single factor experiment. The volume of elution solvent, amount of dispersive adsorbent and C18 were optimized by the Box-Behnken design through response surface methodology. Under optimized conditions,0.5g samples were blended with 1 g of Forisil and 1.2g C18 in the follow for liposuction. Then the dispersed samples were eluted with 5 mL acetonitrile (ACN). Finally the extract was concentrated to dryness, re-constituted with 100μL acetonitrile and injected into the LC/MS-MS system. Under the optimized conditions, satisfactory recoveries range of 84.0%-117.3% and good repeatability (RSD less than 12.5%, n= 8) was obtained at three spiked levels (5,20 and 100 μg·L-1), the proposed method showed good linearity within the range of 0.5-100 ugL-1. The limits of detection was 0.05-0.18ugL-1 (S/N=3:1). All the above results demonstrated that the proposed method would be an application value method for the determination of HBCDs in chicken muscles.Experimental results indicated that MSPD combined LC-ESI-MS/MS method would be a efficient, rapid and application value method for the determination of lipophilic organic pollutants in muscle. |
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