乙基化衍生-气相色谱-串联质谱法测定葡萄酒中3种丁基锡:液液萃取和固相微萃取的比较

Determination of three butyltin compounds in wine by in-situ ethylation and gas chromatography coupled with tandem mass spectrometry-comparision with liquid-liquid extraction and solid-phase microextraction

建立了葡萄酒中一丁基锡、二丁基锡和三丁基锡检测的两种分析方法,分别采用液液萃取法（LLE）和固相微萃取法（SPME）,以四乙基硼化钠为衍生试剂,气相色谱-串联质谱（GC-MS/MS）检测,内标法定量。对两种方法的萃取条件（萃取时间、温度等）、衍生条件（pH、衍生试剂用量等）和GC-MS/MS条件进行了选择和优化。考察和对比了两种方法的灵敏度和准确度。结果表明,LLE和SPM E法的检出限分别为0.5μg/kg（以Sn计,下同）和0.01μg/kg,针对干红、干白和桃红3种葡萄酒基质,在4个添加水平下的回收率范围分别为70.7%~103.3%和61.7%~114.1%,RSD范围分别为2.2%~8.4%和6.6%~16.0%。LLE法稳定性好,方法准确可靠;SPM E法虽精密度稍差,但具有极高的灵敏度,而且操作简便,不需消耗有机溶剂。两种方法联合使用具有较宽的检测范围,适用于葡萄酒中丁基锡化合物的检测。

Two methods were developed for simultaneous determination of monobutyltin（ MBT）,dibutyltin（ DBT）,and tributyltin（ TBT） in wine. Three butyltin compounds（ BTs） were ethylated with sodium tetraethylborate（ NaBEt_4）,extracted using liquid-liquid extraction（ LLE） or solid-phase microextraction（ SPME） method,and finally determined by gas chromatography coupled with tandem mass spectrometry（ GCMS/MS）, using tripropyltin as internal standard. The extraction conditions（ time, temperature, etc.）,derivatization factors（ pH,amount of NaBEt_4,etc.）,and GC-MS/MS parameters were optimized for both LLE and SPME methods. The sensitivity and accuracy of the two methods were evaluated and compared. Results showed that,the limits of detection（ LODs） for three BTs were 0. 5 μg/kg（ as Sn,the same below） and 0. 01μg/kg,using LLE and SPME methods,respectively. The fortified recoveries,at four spiking levels,ranged70. 7% ~ 103. 3% by LLE,and 61. 7% ~ 114. 1% by SPME,with RSDs in the range of 2. 2% ~ 8. 4% and6. 6% ~ 16%,respectively. The LLE method shows good repeatability and reliability,while the SPME method is much more sensitive and has the advantages of quick,simple and solventless. The proposed two methods are practical with very wide detection range,which is suitable for the determination of butyltin compounds in wine.