Yu Zhen-Hua, Jing Miao, Wang Xiao-Ru, Chen Deng-Yun, Huang Yan-Liang
Institute of Oceanology, Chinese Academy of Sciences, Qingdao 266071, China.
Guang Pu Xue Yu Guang Pu Fen Xi. 2009 Oct;29(10):2855-9.
The hyphenated technique of high performance liquid chromatography coupled with inductively coupled plasma mass spectrometry (HPLC-ICP-MS) was applied to the simultaneous determination of five organotin compounds (trimethyltin, dibutyltin, tributyltin, diphenyltin and triphenyltin) in seawater samples. Agilent TC-C18 column was used for the separation, the mobile phase of HPLC was CH3CN : H2O : CH3COOH = 65 : 23 : 12 (phi3), 0.05% TEA, and pH value was adjusted to 3.0 by diluent ammonia. The flow rate was 0.6 mL x min(-1). Five mixed organotin compounds in a mix standard solution from 100 to 0.5 microg x L(-1) were applied for the method assessment. The experimental results indicate that the correlation coefficient of calibration curves (R2) for each organotin compound was over 0.998 and the detection limits of the five organotin compounds were lower than 3 ng x L(-1). Different mixed organic solvents including dichloromethane or toluene were used for extraction of organotin and the extraction condition of organotin from seawater was optimized. The 100 mL seawater acidized by hydrochloric acid was extracted by 10 mL carbon dichloride (CH2 Cl2) with 2% tropolone for 10 min twice. Extracted organic solvents were mixed and blown to one drop by nitrogen with the rate of 1.7 mL x min(-1), then 1 mL acetonitrile was added to the drop for redissolving the organotin compounds. Finally, the mixed redissolution was filtered by 0.22 microm organic filter membrane before analysis. It was found that the only organotin compound in seawater was triphenyltin (TPHT) and the content was 53.2 ng x L(-1). The recoveries test from the standard addition for diphenyltin (DPHT), dibutyltin (DBT), tributyltin (TBT) and triphenyltin (TPHT) were over 80%. However, the recovery for trimethyltin (TMT) was relatively low and the value was 50%. The reason might be attributed to the decomposition or adsorption of those compounds during the extraction procedure. Further study on this subject is in progress.
采用高效液相色谱-电感耦合等离子体质谱联用技术（HPLC-ICP-MS）同时测定海水样品中的5种有机锡化合物（三甲基锡、二丁基锡、三丁基锡、二苯基锡和三苯基锡）。使用安捷伦TC-C18柱进行分离，HPLC的流动相为CH3CN:H2O:CH3COOH = 65:23:12（φ），0.05%三乙胺，并用稀释氨水将pH值调至3.0。流速为0.6 mL·min-1。采用浓度范围为100至0.5 μg·L-1的混合标准溶液中的5种混合有机锡化合物进行方法评估。实验结果表明，各有机锡化合物校准曲线的相关系数（R2）均大于0.998，5种有机锡化合物的检出限均低于3 ng·L-1。采用二氯甲烷或甲苯等不同混合有机溶剂萃取有机锡，并对海水中有机锡的萃取条件进行了优化。用10 mL含2%托酚酮的二氯甲烷（CH2Cl2）对100 mL经盐酸酸化的海水萃取两次，每次10 min。将萃取后的有机溶剂混合，用氮气以1.7 mL·min-1的速率吹至一滴，然后向该液滴中加入1 mL乙腈以重新溶解有机锡化合物。最后，在分析前用0.22 μm有机滤膜对混合重溶液进行过滤。结果发现海水中唯一的有机锡化合物是三苯基锡（TPHT），含量为53.2 ng·L-1。二苯基锡（DPHT）、二丁基锡（DBT）、三丁基锡（TBT）和三苯基锡（TPHT）的加标回收率试验结果均超过80%。然而，三甲基锡（TMT）的回收率相对较低，为50%。原因可能是这些化合物在萃取过程中发生了分解或吸附。对此课题的进一步研究正在进行中。
