浙江省黄酒中氨基甲酸乙酯的含量及变化趋势研究

Study on content of ethyl carbamate in yellow rice wine and its change in Zhejiang province

目的 了解浙江省黄酒中氨基甲酸乙酯（EC）含量现状及黄酒生产贮存期、流通货架期中EC的变化情况.方法 2008-2012年采用单纯随机法从浙江省超市、食品商场随机购买市售黄酒475份；同时采集生产企业不同酒龄贮酒49份进行EC含量调查,分别在4℃、室温、37℃下存放400 d进行贮存实验；2011年购买市售瓶、袋装黄酒各1份在室温放置400 d,定期测量EC含量,进行货架期贮存试验；样品采用D5-EC同位素稀释技术、碱性硅藻土固相萃取净化,气相色谱-质谱法测定EC.结果 2008-2012年浙江省黄酒中EC总检出 率为99％（472/475）,中位数为70～112 μg/kg,第90百分位数为190 ～333 μg/kg,第95百分位数为214 ～ 393 μg/kg,最大值为430 ～515 μg/kg;不同酒龄市售黄酒中EC含量随酒龄的增加而增加,贮酒EC含量的平均值与酒龄呈正相关（r=0.988）.黄酒在4℃、常温、37℃存放400 d,EC含量从原来的74 μg/kg分别上升至86、127、509 μg/kg,差异有统计学意义（F=14.73,P＜0.01）.同时,瓶、袋装黄酒EC含量随放置时间的延长而略有降低,分别从215和196 μg/kg降到184和158 μg/kg,放置250 d后随着存放时间的增加而增加,400 d后瓶、袋装黄酒中EC含量分别为252和210 μg/kg,EC含量差异有统计学意义（Z=2.37,P＜0.05）.结论 浙江省黄酒中普遍存在EC,其含量与贮存时间、贮存温度有关.

Objective To understand the content status of ethyl carbanate （EC） in yellow rice wine and the changes in storage period and shelf life in Zhejiang province.Methods A total of 475 samples of yellow rice wine purchased randomly from supermarkets and food stores in Zhejiang province during 2008-2012,and 49 samples collected from manufacturers were measured for EC content.The sample collected from manufacturers by filter sterilization was placed at 4 ℃,room temperature and 37 ℃ for 400 d,respectively;a bottled wine and a wine in bag were bought from market were placed for 400 d in room temperature to conduct shelf life storage test,and measure the content in every point in 2011.The EC of the samples was determinated by gas chromatography-mass spectrometry after the samples were diluted with D5-EC isotope dilution technique,and purified by alkaline diatomite solid phase extraction column.Results The overall detection rate of EC was 99％ （472/475） in yellow rice wine of Zhejiang province in 2008-2012,the median value was 70-112 μg/kg,the 90th percentile was 190-333 μg/kg,the 95th percentile was 214-393 μg/kg,and the maximum value was 430-515 μg/kg.The content of EC was increased gradually along with the increasing of storage age in commercially yellow rice wine,and the average content of EC were positively correlated with storage age （r =0.988）.The contents of EC in yellow rice wine after sterilization increased from 74 μg/kg to 86 μg/kg,127 μg/kg and 509 μg/kg at 4 ℃,room temperature and 37 ℃,respectively for 400 d storage,the differences had statistical significance（F =14.73,P ＜ 0.01）.The content of EC in yellow rice wines in shelf life,which stored in room temperature with bottle and bag package,was decreased slightly with increasing storage time in the beginning,from 215 to 184 μg/kg and 196 to 158 μg/kg,respectively,and increased again with increasing storage time after 250 d,with 252 μg/kg and 210 μg/kg in bottle and bag package after 400 d,respectively,the differences had statistical significance（Z =2.37,P ＜ 0.05）.Conclusion EC is widespread in rice wine,the content of EC was correlated with storage time and temperature.