Determination Of Organotin Compounds In Biomaterial With High Performance Liquid Chromatography Inductively Coupled Plasma Mass Spectrometry

Objective:Tin compounds have different properties,complex sample preparation,currently,reports about methyltin and ethyltin in biological samples are less at home and abroad,and organotin compounds have no occupational exposure limits and diagnostic basis.So it is important to select suitable methods for extracting,separating and detecting organotin compounds in biological materials.A rapid method was developed for the determination of dimethyltin chloride(DMT),trimethyltin chloride(TMT),diethyltin chloride(DET)and triethyltin chloride(TET)by high performance liquid chromatography-inductively coupled plasma mass spectrometry(HPLC-ICP-MS)in urine and whole blood and it provide scientific basis for formulation of occupational exposure restriction for organotins.Method:Four organotin compounds in urine were diluted five times with deionized water,which was filtered through 0.22μm membrane before detection.And all four species were separated by HPLC using C4 column of Ruby@C4(150 mm x 3 mm i.d,3μm)maintained at 30℃and a mobile phase(4%acetic acid-water containing of 0.25 mM tropolone,and methanol)at a flow rate of 0.3 mL/min,which was determined by ICP-MS.organotin compounds in whole blood were extracted with acetonitrile under acid condition which was filtered through 0.22μm membrane.All four species were separated by HPLC using C4 column of Ruby@C4(150mm x 3 mm i.d,3μm)maintained at 30℃and a mobile phase(4%acetic acid-water containing of 0.25 mM tropolone,and methanol)at a flow rate of 0.3 mL/min;which was determined by ICP-MS.Results:The results showed that the mass concentration of organotin compounds in urine has a liner range of 18.36~550.80μg/L、17.40~522.00μg/L、27.66~829.80μg/L and 20.43~612.90μg/L for DMT,TMT,DET and TET with good correlation coefficients(R~2≥0.998).Detection limits of 12.24,11.60,18.44 and 13.62μg/L for DMT,TMT,DET and TET,respectively.The recoveries of three different concentration of organotins were above 90%and the RSD were below 10%.Detection limits of 21.40,20.30,32.27 and 23.80μg/L for DMT,TMT,DET and TET in whole blood,respectively.The mass concentration of organotin compounds has a liner range of 30.60~550.80μg/L、29.00~522.00μg/L、46.10~829.80μg/L and 34.05~612.90μg/L for DMT,TMT,DET and TET with good correlation coefficients(R~2≥0.997).The recoveries of three different concentration of organotins were above 85%and the RSD were below 10%.This method was used to detect of organotin compounds in 9occupationally exposed volunteers who worked in a plastics factory.The experimental result indicated that organotins were found in some workes.GC-MS can not distinguish the form of ethyltin compounds,because the derivatives are all ethyl-alkyltin,while HPLC-ICP-MS can distinguish the form of methyltin and ethyltin simultaneously.The analytical results obtained by HPLC-ICP-MS and GC-MS were analyzed with paired design wilcoxon signed-rank test by spss 21.0.And due to P﹥0.05,two methods were not significance difference(α=0.05).This illustrated that the method was feasible and can be used for determine of organotin compounds in occupational exposure population.Conclusion:The method is simple,effective,reliable and highly sensitive,which can meet the requirements of the of biological material analysis methods,and can be used to determine organotin compounds in urine and whole blood.