GC-MS/MS法测定食品接触用硅橡胶制品中6种环硅氧烷迁移量

Determination of Migration of Six Cyclosiloxanes in Silicone Rubber Products for Food Contact by GC-MS/MS

基于气相色谱-串联质谱(GC-MS/MS)建立了食品接触用硅橡胶制品中6种环硅氧烷(D4~D9)向50%乙醇、95%乙醇、异辛烷迁移量的检测方法,并应用于38批次实际样品的检测。取10 mL迁移实验得到的50%乙醇浸泡液,使用2 mL正己烷萃取,经过滤后测定,95%乙醇和异辛烷浸泡液直接经过滤后测定。采用HP-5 MS色谱柱分离,多反应监测模式进行分析。结果表明,D4~D9在0.05~1.00 mg/L或0.20~5.00 mg/L范围内具有良好的线性关系,相关系数(r^(2))不低于0.9960。各目标物的检出限为0.02~0.07 mg/L,定量下限为0.05~0.20 mg/L,回收率为90.1%~106%,相对标准偏差不大于13%。使用该方法对市面上的食品接触用硅橡胶制品进行迁移实验,发现D4~D9向50%乙醇存在迁移风险;向95%乙醇和异辛烷迁移的检出率为80%,迁移风险最大。D4~D9在95%乙醇和异辛烷第3次的迁移检出率显著大于第1次,而在50%乙醇中第1次迁移和第3次迁移的检出率无明显差异。

A method for the determination of the migration of six cyclosiloxanes(D4-D9)to 50%ethanol,95%ethanol and isooctane in food contact silicone rubber products was developed based on gas chromatography-tandem mass spectrometry(GC-MS/MS),which was applied to the determination of 38 actual samples.2 mL of n-hexane was used to extract D4-D9 from 10 mL of 50% ethanol obtained from the migration test followed by filtration and detection.Meanwhile,the 95% ethanol and isooctane were simply determined after filtration.The analysis was carried out in multiple reaction monitoring mode using an HP-5 MS column for separation.The results showed that there were good linear relationships for D4-D9 in the range of 0.05-1.00 mg/L or 0.20-5.00 mg/L,with correlation coefficients(r^(2))not less than 0.9960.The limits of detection and limits of quantitation for each target were in the range of 0.02-0.07 mg/L and 0.05-0.20 mg/L,respectively.The recoveries ranged from90.1% to 106%,with relative standard deviations not more than 13%.The method was used to determine the migration of D4-D9 in commercially available food contact silicone rubber products,and it was found that there was a migration risk of D4-D9 to 50% ethanol,while the migration risk of D4-D9 to 95% ethanol and isooctane was the highest as the detection rate for D4-D9 was 80%.The detection rate for the third migration of D4-D9 to 95% ethanol and isooctane was significantly greater than that for the first migration,while the detection rates for the first migration and the third migration to 50% ethanol were not significantly different.