白酒中邻苯二甲酸酯类物质的典型污染特征及源解析研究

Chinese Liquor industry occupied an important role in the national economy. The safety issues of Chinese Liquor affected not only the majority of people's health, but also could cause panic and doubt in whole society. Currently, the enterprises of Chinese Liquor implemented the reform that the plastic was replaced by steel in production process and the packaging materials also tried to avoid the use of plastics. However, the phthalate esters (PAEs) were still detected. The typical pollution characteristic and the real sources of PAEs were not clear in Chinese Liquor. This study under the overall assessment and whole production chain control, was used to elucidate the typical pollution characteristics of PAEs in different flavor type, alcohol content and producing area. A modified QuEChERS sample preparation method combined with GC-MS was established to determine the PAEs in raw materials including sorghum, rice, glutinous rice, corn, barley and wheat. A dispersive liquid-liquid micro-extraction method combined with GC-MS was established to determine the PAEs of water in Chinese Liquor production. The predictive mathematical model of the PAEs content was built on the basis of chemical analysis coupled with principal component and multiple regression analysis. The critical control points were clarified. The migration regularity that migrated from raw material, water to Chinese Liquor was revealed. The funding of this project would be helpful to improve the daily quality control standards and risk warning level of Chinese Liquor enterprises.

白酒产业在国民经济中占据重要地位，白酒安全问题不仅影响广大人民身体健康，更极易造成全社会的恐慌和质疑。目前，酒企大范围施行“以钢代塑”改革，商品酒包装也尽力规避塑料制品，但邻苯二甲酸酯类物质（PAEs）仍被检出，其典型污染特征尚不明确，真正来源尚不清楚。本课题以白酒中PAEs类物质为研究对象，从全产业链控制角度出发，在总体评估的基础上，阐明不同香型、酒精度、产地酒的PAEs典型污染特征；建立QuEChERS-GC/MS法检测酿酒原料（高粱、大米、糯米、玉米、大麦和小麦）PAEs类物质的方法；建立分散液液微萃取-GC/MS法检测酿酒用水PAEs类物质的方法；在上述化学分析的基础上，应用主成分分析和多元回归分析手段，构建白酒PAEs含量的预测模型，阐明其来源的关键控制点，揭示PAEs类物质从谷物、水体到酒样的迁移规律。本课题的资助为提高酒企的日常质控标准和风险预警水平提供科学数据。

白酒产业在国民经济中占据重要地位，2018年我国规模以上白酒企业白酒产量达到871.2万吨。自2012年塑化剂风波后，白酒安全问题受到了全社会的普遍关注，引起了消费者一定的恐慌和质疑。本课题聚焦于白酒中邻苯二甲酸酯（PAEs）类物质，主要进行了如下4方面的工作：.1. 建立了非离子型表面活性剂/涡旋-液液微萃取结合GC/MS对白酒中14种PAEs的检测方法。应用该方法对59种市售商品酒样的检测结果显示：所有酒样中均检出DMP、DEP、DIBP、DBP、DEHP等5种PAEs；41个酒样中检出DPP、DMP、DEP、DIBP、DBP、DPP和DEHP等6种PAEs，其中，DEHP和DBP含量均远低于GB9685-2016的限量规定；应用PCA方法分析了不同香型、酒精度白酒PAEs的分布特征，发现未呈现因PAEs含量差异导致的聚类现象。.2. 建立了QuEChERS结合GC/MS对高粱中14种PAEs的检测方法，高粱样品经乙腈萃取、N-丙基乙二胺（PSA）和十八烷基硅胶（C18）净化后，取上层清液直接进GC/MS检测，应用基质匹配法建立标准曲线，外标法定量分析。对采自全国不同地区32个高粱样品PAEs的检测结果显示：所有样品中均只检出DMP、DEP、DIBP、DBP和DEHP等5种PAEs，其中，DEHP和DBP含量均低于GB9685-2016的限量规定；应用PCA分析发现32个高粱样品并未呈现明显的区域聚类现象。.3. 建立了QuEChERS结合GC/MS对酿酒小麦、大麦和玉米中PAEs多残留的检测方法。对采自全国不同地区的7个小麦样品、6个玉米样品和5个大麦样品的PAEs检测结果显示：均仅检出DMP、DEP、DIBP、DBP和DEHP等5种PAEs，其中小麦和玉米的个别样品中DEHP和DBP含量接近或超过GB9685-2016的限量规定；大麦样品则均低于GB9685-2016规定的限量标准。.4. 研究了蒸馏过程原酒PAEs的变化趋势，对采自1家浓香型白酒企业100年窖池酒醅蒸馏过程实时取样的20个原酒进行分析，结果表明：不同时间段采集的馏分原酒中均仅检出DMP、DEP、DIBP、DBP和DEHP等5种PAEs；随蒸馏时间的延长，其PAEs含量均呈现下降趋势，DMP、DEP等小分子量PAEs下降速率相对较快。.上述研究对白酒企业的质量控制具有一定的实践指导意义。