酱油中氯丙醇的研究进展

本文简要介绍了酱油中的毒性物质——氯丙醇的形成机理、主要种类及其毒性、国内外在解决氯丙醇问题上的研究进展,对氯丙醇控制、分析检测方法。     

二噁英、多氯联苯和氯丙醇的痕量与超痕量检测技术研究

为建立食品中二噁英、多氯联苯和氯丙醇的检测技术并达到国际水平，将稳定性同位素稀释质谱技术应用到中国食品安全和环境分析领域，针对不同目标化合物分别建立了高分辩磁质谱、四极杆低分辩质谱和离子阱串联质谱的标准化检测技术，特别是采用双同位素稀释同时测定4种氯丙醇的技术。通过对EPA1613A／1668A、FDA4084和EPSI／RM／31、AOAC2000．01等国际先进方法用食品（鱼、鱼油、鹿肉、奶粉和猪油）和环境样品（飞灰、土壤和底泥）开展对比筛选和一系列实验室闻协同性验证，确立了二噁英和多氯联苯的稳定性同位素稀释质谱检测方法，建立了用双稳定性同位素进行酱油中单氯取代和双氯取代氯丙醇同时测定的方法，提出了符合国际规范的技术方案，作为国家标准方法待颁布。利用该检测技术在中国首次开展鱼贝类和土壤中污染的二噁英和多氯联苯同系物类型特征指纹库研究和酱油中氯丙醇的大规模调查，获得了中国人群膳食二噁英毒性当量和氯丙醇摄入状况的暴露数据，不仅证明所建立的方法实用、可行，也为我国履行承诺摸清了家底，提供了依据。     

关于中国传统酿造酱油中是否含有氯丙醇的考证报告

通过对氯丙醇的生成机理进行分析,并对国内九个厂家的酱油产品进行抽样检测及模拟试验,得出以下结论：天然酿造酱油在发酵过程中没有发现有氯丙醇的存在。     

关于对酱油中氯丙醇的探讨

本文阐述由于酱油生产工艺技术上的差别，形成了3－氯丙醇这一人体有害物含量的增加，本文简述3－氯丙醇的产生机理，危害性及解决方法。     

小口径毛细管色谱柱测定酱油中三种氯丙醇含量的研究

目的：利用小口径毛细管色谱柱和GC-ECD检测器，建立了测定酱油中三种氯丙醇含量的检测方法。方法：采用弗罗里硅土（FLORISIL）和西雷脱（celite，硅藻土担体）作填料，用乙醚作洗脱剂对样品同时进行提取、净化，用三氟乙酸酐衍生，小口径毛细管柱分离，ECD检测器检测，对酱油中三种氯丙醇进行了测定。结果：1，3-DCP、2，3-DCP和3-MCPD分别在5～250、3.125～100、5～250pg范围内呈良好的线性关系，其最低检测限分别为1.0、1.0和0.02μg/kg；样品的回收率分别为100.64%±2.79%、114.78%±2.50%和103.61%±2.32%。结论：该方法对三种氯丙醇成分均具有较高的灵敏度，可用于样品中微量氯丙醇含量的测定。     

酿造酱油与配制酱油鉴别方法研究进展

以氯丙醇、铵盐、乙酰丙酸、氨基酸作为鉴别酿造酱油与配制酱油的指标,采用同位素稀释气相色谱-质谱联用法、顶空衍生化固相微萃取法等检测酸水解植物蛋白液(HVP)的氯丙醇,采用凯氏定氮法、近红外光谱法检测酱油中的铵盐与氨基酸,采用液相色谱-质谱法、气相色谱法等检测HVP中的乙酰丙酸,采用高效液相色谱法、氨基酸自动分析仪检测酱油中的氨基酸。     

酸水解植物蛋白液（HVP）生产中的化学变化

酸水解植物蛋白，简称HVP（Hydrolized Vegetable Protein)，主要作为鲜味剂添加到鲜味酱油，特鲜酱油，蚝油等调味品中，使产品具有特殊的鲜味，丰富的滋味而深受消费者的欢迎，但在1999年中国（包括香港特区）出口到欧洲的酱油，蚝油产品，被检测出大量含有致癌物质－氯丙醇而遭到封杀，随之而来在国内也引起了广大生产商和消费者的特别关注。     

酱油中的有害成分及其检测技术研究进展

酱油味道鲜美,富有营养价值,是我国主要的调味品之一,其安全问题备受关注。在酱油制造过程中,不可避免地会产生微量有害物质,如氯丙醇、氨基甲酸乙酯、真菌毒素等,对这些有害物质的产生来源、危害性和检测技术等方面进行了综述。     

食品中氯丙醇污染及其毒性

氯丙醇类化合物,尤其是3-MPCD对酱油污染成为国际上关注食品安全热点问题之一。为了对该类物质有一全面了解,该文对食品中氯丙醇类化合物的种类、特性、来源、毒性、检测方法和预防措施及各国限量标准进行综述。     

3‐Chloropropane‐1,2‐diol (3‐MCPD) in Soy Sauce: A Review on the Formation,Reduction, and Detection of This Potential Carcinogen

Soy sauce, a dark‐colored seasoning, is added to enhance the sensory properties of foods. Soy sauce can be consumed as a condiment or added during the preparation of food. There are 3 types of soy sauce: fermented, acid‐hydrolyzed vegetable protein (acid‐ HVP), and mixtures of these. 3‐Chloropropane‐1,2‐diol (3‐MCPD) is a heat‐produced contaminants formed during the preparation of soy sauce and was found to be a by‐product of acid‐HVP‐produced soy sauce in 1978. 3‐MCPD has been reported to be carcinogenic, nephrotoxic, and reproductively toxic in laboratory animal testing and has been registered as a chemosterilant for rodent control. 3‐MCPD is classified as a possible carcinogenic compound, and the maximum tolerated limit in food has been established at both national and international levels. The purpose of this review is to provide an overview on the detection of 3‐MCPD in soy sauce, its toxic effects, and the potential methods to reduce its concentration, especially during the production of acid‐HVP soy sauce. The methods of quantification are also critically reviewed with a focus on efficiency, suitability, and challenges encountered in analysis.     

我国高档酿造酱油生产工艺应创新

比较了日本的“低温动态稀发酵”和我国的“先中后低温静态先固后稀发酵”两种酱油生产工艺的特点、优点和缺点。提出采用适合我国国情的，近二十年来形成的创新工艺，产品质量可与日本高档酱油相媲美，生产成本每吨可降低100元以上。可以大力拓展优势酿造酱油的生产，增强产品在国际市场的竞争力。     

Mitigation Strategies for the Reduction of 2‐ and 3‐MCPD Esters and Glycidyl Esters in the Vegetable Oil Processing Industry

The refining of vegetable oils leads to the formation of 2‐ and 3‐monochloropropane‐1,2‐diol esters (2‐ and 3‐MCPD‐E), and glycidyl esters (Gly‐E). A literature review was performed aiming to provide up‐to‐date knowledge on mitigation strategies during oil refining that can reduce the formation of these three processing contaminants. The review used the database Scopus and covered the period from 2009 to 2017. Most of the 18 papers dealt with palm oil and two papers with vegetable oil. Most studies focused on 3‐MCPD‐E, some on Gly‐E, and none on 2‐MCPD‐E. Water degumming was able to reduce the concentrations of 3‐MCPD‐E by 84% and Gly‐E by 26%. Neutralization of the oil reduced concentrations of 3‐MCPD‐E by 81% and Gly‐E by 84%. Bleaching with synthetic magnesium silicate reduced the 3‐MCPD‐E concentration by 67%. For the deodorization step, several mitigation strategies, such as double‐deodorization, the addition of various antioxidants, or a longer deodorization time, can reduce the formations of 3‐MCPD‐E by 82% and Gly‐E by 78%. Postrefining mitigation, including the use of absorbents, enzymes, or rebleaching of the oil, has also been reported to produce desirable contaminant reduction. Postrefining treatment with calcinated zeolite was able to reduce the 3‐MCPD‐E concentration by 19% and the Gly‐E concentration by 77%. Applying combined mitigation strategies to multiple steps of oil refining is likely crucial in order to adequately reduce levels of 3‐MCPD‐E and Gly‐E.     

北方低温季节生产传统发酵酱油的探讨

回顾了传统酱油生产工艺近50年的发展概况，论述了我国传统风味酱油的工艺特点和风味特点。围绕冬季保温和阳光晒醪，提出了我国北方低温季节生产传统风味酱油需要解决的问题，同时概算了解决这些问题所需要的投资。     

科学利用微生物恢复和发展传统酱油工艺

针对《科学利用微生物推动中国酱油工艺大变革》一文的观点,论述了传统酱油生产工艺是实践经验的结晶,符合自然和思维的客观规律,产品质量好,开创了科学利用微生物酿造酱油的历史。指出日本酱油居世界领先水平,一是继承和发展了我国传统工艺,二是我国酱油质量下降为之创造了客观条件。认为要生产优质酱油,必须恢复和发展传统的生产工艺。     

现代酱油的感官检查

介绍了酱油感官检查的定义，基本要求，包括器具方面，环境方面及品评员的要求。同时介绍了日本酱油行业通用的感官检查的几种方法。     

Fatty acid esters of monochloropropanediol (MCPD) and glycidol in refined edible oils

Recently, fatty acid esters of monochloropropanediol (MCPD) and that of glycidol have been reported in refined edible oils. Since then a wealth of research has been published on the factors influencing the formation of these contaminants in foods. It can be noted that the predominant precursors in a given matrix will not necessarily be the same as in other matrices. Further, proven relationships in the past between precursors responsible for free MCPD or free glycidol formation will not necessarily be valid for their fatty acid-esterified counterparts. This review attempts to summarise the current status of the literature as it pertains to the reasons surrounding the manifestation of MCPD esters and glycidyl esters in oils and fats. Recent efforts to mitigate the levels of these contaminants were highlighted and put into the context of their respective reaction matrices. As more accurate occurrence data for MCPD esters and glycidyl esters in other foods are collected, more targeted mitigation experiments can be formulated with respect to the reaction matrices under investigation.     

关于提高酱油风味的方法和途径的探讨

对提高酱油风味的方法和途径进行了论述，将传统的酱油生产工艺与现代科学相结合，采用传统晒露发酵工工艺加酵母，多菌种混合制曲或晒露酱油多菌种发酵等工艺，可提高优质酱油的产量。     

Factors impacting the formation of Monochloropropanediol (MCPD) fatty acid diesters during palm (Elaeis guineensis) oil production

Recently, organic and inorganic chlorinated compounds were detected in crude and commercially refined palm oils. Further, the predominant formation mechanism of monochloropropanediol (MCPD) diesters at high temperatures (>170–180°C) was revealed. The present study involved the development and comparison of solutions to mitigate MCPD diester levels in oils from various stages of palm oil production. Partially refined palm oil samples and oil extracted from fresh palm fruits were submitted to bench-top deodorisation experiments. Application of glycerol and ethanol as refining aids during the deodorisation of refined-bleached palm oil proved to be moderately effective; about 25%–35% reduction of MCPD diester levels was achieved. Washing crude palm oil with ethanol–water (1:1) prior to deodorisation was also an effective strategy yielding an ～30% reduction of MCPD diester contents. Washing palm fruit pulp before oil extraction, however, was most impactful, resulting in a 95% reduction of MCPD diesters when compared to the deodorised control oil. This suggests that intervention upstream in the process chain is most efficient in reducing levels of these contaminants in refined oils. Following the study, a root-cause analysis was performed in order to map the parameters potentially responsible for the occurrence of MCPD diesters in refined palm oil and related fractions.     

Formation mechanisms of monochloropropanediol (MCPD) fatty acid diesters in refined palm (Elaeis guineensis) oil and related fractions

Monochloropropanediol (MCPD) fatty acid esters are process contaminants generated during the deodorisation of edible oils. In particular, MCPD diesters are found in higher abundance in refined palm oil than other edible oils. In the present study, a series of model reactions mimicking palm oil deodorisation has been conducted with pure acylglycerols in the presence or absence of either organic or inorganic chlorine-containing compounds. Results showed that the bulk of MCPD diesters are formed above 200°C through the reaction of organochlorines with triacylglycerols (TAG). Additional experiments confirmed that this reaction can be initiated during palm oil deodorisation by hydrogen chloride (HCl) gas evolved through the thermal degradation of organochlorines present in the oil. Therein, the majority of the ultimately produced MCPD diesters are the result of HCl reacting with TAG, via protonation, followed by the elimination of a fatty acid residue. Two possible MCPD diester formation mechanisms are highlighted, both of which involve acyloxonium ion reactive intermediates. Investigations with pure TAG regio-isomers showed that MCPD ester formation is regioselective and the sn-1(3) position of the glycerol backbone is favoured.