手性高效液相色谱-同位素稀释串联质谱法测定土壤及蚯蚓中的六溴环十二烷对映体  

Determination of Hexabromocyclododecanes Enantiomers in Earthworm and Soil by Chiral High Performance Liquid ChromatographyIsotopic Dilution-Tandem Mass Spectrometry

作　　者：田芹[1] 佟玲[1] 宋淑玲[1] 王晓春[1,2] 焦杏春[1] 姜润飞 

机构地区：[1]国家地质实验测试中心,北京100037 [2]国土资源部生态地球化学重点实验室,北京100037 [3]首都师范大学化学系,北京100048

出　　处：《分析化学》2015年第9期1383-1388,共6页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金(Nos.21307018;41473008)资助项目~~

摘　　要：采用高效液相色谱-同位素稀释串联质谱法（LC-ID-MS/MS）建立了土壤和蚯蚓中手性α-,β-,γ-六溴环十二烷（HBCD）的分离分析方法。样品添加d18-HBCDs作为同位素内标后提取,土壤样品采用正己烷-二氯甲烷（1∶1,V/V）作萃取剂,加速溶剂萃取（ASE）,硅胶固相萃取小柱净化;蚯蚓样品采用乙酸乙酯涡旋超声提取,浓硫酸磺化后过硅胶小柱净化。α-,β-,γ-HBCD各对映体的线性范围为0.25~50 ng/m L;土壤中检出限为0.00544~0.00766 ng/g,定量限为0.0173~0.0244 ng/g,在0.05和2.5 ng/g添加浓度的回收率为80.0%~95.9%,相对标准偏差RSD为5.7%~11.9%;在蚯蚓中,检出限为0.0103~0.0148 ng/g,定量限为0.0328~0.0471 ng/g,在0.1和5.0 ng/g添加浓度的回收率为78.0%~94.4%,相对标准偏差RSD为6.1%~12.2%。可满足实际样品的测定要求。An enantioseleetive method was developed for the separation and determination of three chiral hexabromocyelododecanes （HBCDs） including α-HBCD, β-HBCD, γ-HBCD in soil and earthworm by HPLC-ID-MS/MS. d18-HBCDs used as internal standards were added to the samples before extraction. HBCDs enantiomers were extracted from soil by accelerated solvent extraction （ASE） with n-hexane/DCM （ 1 ： 1, V/V） at 100℃ and 10 MPa for 5 min, and further cleaned up using silica column. HBCDs enantiomers were extracted from earthworm by vortex turbulence with ethyl acetate. The extracts were orderly sulphonated by sulfuric acid, and purified by silica column. For all HBCDs enantiomers, good linearities were obtained in the concentration range of 0.25-50 ng/mL. Limits of detection （LOD） and limits of quantification （LOQ） were 0. 00544-0. 00766 ng,/g and 0. 0173 -0. 0244 ng/g, respectively in soil. The recoveries of spiked samples at 0.05 and 2.5 ng/g levels were 80.0% -95.9% with relative standard deviations （RSD, % ） of 5.7% -11.9% in soil. Limits of detection （LOD） and limits of quantification （LOQ） were 0. 0103-0.0148 ng/g and 0. 0328-0. 0471 ng/g, respectively in earthworm. The recoveries of spiked samples at 0. 1 and 5 ng/g levels were 78.0% -94.4% with relative standard deviations （RSD, %） of 6. 1% -12.2% in earthworm. This method can meet the requirements of determination of trace HBCDs in soil and earthworm.

关 键 词：同位素稀释 高效液相色谱-串联质谱 六溴环十二烷 对映体 土壤 蚯蚓 

分 类 号：S151.9[农业科学—土壤学] S154.5[农业科学—农业基础科学]