食品接触硅橡胶制品中5种高关注物质的分析

Analysis of 5 Substances of Very High Concern(SVHC) in Food Contact Silicone Rubber Products

建立超声辅助溶剂萃取(ultrasound-assisted solvent extraction,UASE)-气相色谱-串联质谱(gas chromatography-tandem mass spectrometry,GC-MS/MS)法和固相微萃取(solid phase micro-extraction,SPME)-GC-MS/MS法对食品接触硅胶制品中N-甲基苯胺(N-methylaniline,NMA)、N,N-二甲基苯胺(N,N-dimethylphylamine,DMA)、壬醛、2,6-二叔丁基对甲苯酚(butylated hydroxytoluene,BHT)及苯并噻唑(benzothiazole,BTZ)5种高关注物质(substances of very high concern,SVHC)的检测方法。优化并评价2种方法,结果显示UASE-GC-MS/MS方法更加简单、高效,线性范围更宽,有良好的回收率和精密度,满足测定要求。利用UASE-GC-MS/MS法对29种奶嘴和27种模具中的5种SVHC进行定量分析,结果显示奶嘴中壬醛含量最高,为1 439.85 ng/g;模具中BHT含量最高,为4 828.78 ng/g;NMA和DMA均被检出。通过对5种物质在奶嘴和模具两类制品中的含量及差异性分析、毒性、来源、限量要求等对其在食品接触硅胶制品中的安全性进行评价。NMA和DMA在模具中的含量高于奶嘴,可能是由于模具中的有机染料等助剂所致,且根据法规要求,它们的检出对人体存在健康风险,应引起高度关注,有必要通过改进配方或工艺来控制苯胺类物质的生成。壬醛在奶嘴和模具中无显著性差异,尽管有较高的检出率,仍然可以认为食品接触硅胶制品中的壬醛含量在安全范围以内。BTZ和BHT有必要进行进一步的迁移实验研究和暴露评估。

The analytical methods of ultrasound-assisted solvent extraction （UASE） and solid phase micro-extraction method （SPME） coupled with gas chromatography-tandem mass spectrometry （GC-MS/MS）, respectively were developed for the determination of 5 substances of very high concern （SVHC）, including N-methylaniline （NMA）, N,N-dimethylphylamine （DMA）, nonanal, butylated hydroxytoluene （BHT） and benzothiazole （BTZ） in food contact silicone products. These two methods were optimized and evaluated. The results indicated that the USAE-GC-MS/MS method was simpler and more efficient and had wider linear range, higher recovery and precision, which met the requirements of determination. This method was then employed to determine the contents of 5 SVHCs in 29 silicone nipples and 27 molds. The results revealed that the highest content of aldehyde in the nipples was 1 439.85 ng/g and the highest content of BHT in the molds was 4 828.78 ng/g; both NMA and DMA were detected from all samples analyzed. The difference in the contents of these SVHCs in the food contact silicon products was analyzed and their safety was evaluated based on their toxicity, and source and limit requirements. The contents of NMA and DMA were higher in the molds than in the nipples, which may be derived from the organic dye or other additives in the molds. Considering NMA and DMA may pose a risk to human health, the generation of anilines must be controlled by improving the formulation or the process. There was no significant difference in the content of nonanal between the nipples and the molds product. Furthermore, despite the high detection rate, it was still considered that the content of nonanal in the food contact silicon products was within the safe range. Migration experiments and exposure assessments should be carried out for BTZ and BHT in the future.