食品接触材料中非有意添加物的检测方法

近年来,随着生活水平与健康安全意识的不断提升,人们越来越重视食品安全问题。食品接触材料是现代食品的重要组成部分,其所迁移出的非有意添加物是影响食品安全的主要风险来源。本文就食品接触材料中非有意添加物的检测方法做了相关的阐述与分析。     

食品接触塑料材料及制品中高关注化合物的高分辨质谱分析技术研究进展

食品接触塑料材料及制品向食品可能发生的高关注化合物迁移一直是食品接触材料安全研究和合规管理的重点。这些高关注化合物分为有意添加物和非有意添加物。由于塑料食品接触材料高关注化合物来源复杂,迁移水平低且相当数量是未知的物质,在缺乏完整的化学物结构数据库、质谱谱图数据库以及标准品等情况下,对这些物质的鉴定和定量测定一直是食品接触材料安全分析所面临的重大技术挑战。近年来,基于气相色谱、液相色谱与各种高分辨率质谱联用的分析技术被视为一种有效手段,逐渐应用于对食品接触材料中高关注化合物的鉴定和定量分析。本文重点介绍近年来针对食品接触塑料高关注化合物分析的高分辨精确质谱(high resolution mass spectrometry, HRMS)分析技术进展,包括迁移试验条件、前处理技术、数据采集以及数据处理技术等。并总结应用HRMS技术所分析的不同食品接触塑料中的高关注化合物,以期为食品接触塑料的风险评估和管理工作提供参考。     

食品接触材料中非有意添加物的安全评估

食品接触材料所迁移出的非有意添加物(non intentionally added substance,NIAS)作为影响食品安全的重要因素而日益受到关注。由于这些NIAS来源复杂且相当数量是未知,给食品接触材料的安全评估和监管带来很大的挑战。基于毒理学关注阈值(threshold of toxicological concern,TTC)方法,结合Cramer决策树方法、化学和生物分析技术的使用,可建立一个针对食品接触材料中NIAS的快速筛查和安全评价模型,对缺乏完整毒理学数据且暴露量较低的化学物质进行风险评估。选择Cramer III所对应的1.5μg/kg BW作为NIAS通用安全暴露阈值,通过分步评估手段,可以得出所迁移未知物质是否需要予以安全关注,重点对食品接触材料迁移高于该TTC的物质进行进一步的确证和风险评估,实现对食品接触材料中高关注物的安全评价从基于检测限模式向TTC安全阈值模式的转变,从而避免不必要的动物试验,节约大量人力、物力和时间,有利于加快食品接触材料中低暴露量化学物质的风险评估和提升产品安全管理效能。     

食品接触材料中非有意添加物的检测方法

食品接触材料中的非有意添加物(non-intentionally added substance, NIAS)作为影响食品安全的重要因素而日益受到关注。对NIAS的化合物种类鉴定和含量测定是对食品接触材料进行安全评估和监管的前提条件。目前, 主流的分析策略是依据待测NIAS的挥发特性, 分别选择气相色谱(gas chromatography, GC)或高效液相色谱(high performance liquid chromatography, HPLC)进行分离和定量, 利用质谱(mass spectrometry, MS)谱图特征和色谱出峰时间(retention time, RT), 借助质谱数据库对NIAS进行定性。与欧洲国家相比, 我国在NIAS分析检测领域起步较晚, 亟需补强食品接触材料NIAS物质数据库和物质鉴定领域的研究基础。下一步建议加强化学结构分析的基础研究, 培养食品接触材料中NIAS鉴定人才团队, 构建食品接触材料中IAS和NIAS物质的信息数据库, 最终提高食品接触材料NIAS检测技术水平。     

草莓干燥过程中酯类香气化合物及相关酶活性的变化

为研究草莓片干燥过程中酯类香气化合物的变化,采用顶空-固相微萃取结合气相色谱-质谱联用技术,对干燥过程中草莓酯类化合物进行分析,并且考察干燥过程中与酯类化合物有关酶活性。结果表明,草莓在干燥过程中,新生成了己酸乙酯、乙酸辛酯、辛酸乙酯、癸酸乙酯等酯类化合物,己酸甲酯、乙酸己酯、乙酸辛酯等含量增加,同时也有部分酯类化合物损失;主成分分析显示,干燥15 h的草莓片酯类香气化合物综合得分最高;相关性分析显示,乙醇脱氢酶与某酸乙酯以及乙酸辛酯、(S)-3-羟基丁酸甲酯等酯类香气化合物呈显著正相关;醇酰基转移酶与乙酸某酯、己酸甲酯和辛酸乙酯等呈显著正相关;脂氧合酶与乙酸辛酯、乙酸己酯、己酸甲酯、丁酸乙酯、癸酸乙酯、丁位辛内酯呈显著正相关。     

12种婴幼儿食品接触热塑性弹性体制品中潜在迁移物的分析

利用固相微萃取-气相色谱-质谱联用技术对12种婴幼儿食品接触热塑性弹性体制品中挥发性及半挥发性的潜在迁移物进行定性及半定量分析。样品通过DVB/CAR/PDMS、CAR/PDMS、Polyacrylate三个固相微萃取纤维头进行非目标物的提取,气相色谱-质谱联用进行分离鉴定,检出的68种化合物结合标准品和保留指数进行确证,单点内标法进行半定量分析。根据检出率、保留指数及含量进行步分3级筛选,最后提出32种需要重点关注的化合物,包括硅氧烷类、芳香烃类、烷烃类、醛类、酯类及酚类等。该研究为后续的特定物质的迁移实验、暴露评估等研究提供了研究思路和科学依据。     

菠萝蜜果实挥发物的热脱附-气相色谱/质谱(TCT-GC/MS)联用分析

采用热脱附-气相色谱/质谱(TCT-GC/MS)联用技术,对动态顶空密闭循环吸附捕集的菠萝蜜果肉及果皮挥发物分别进行检测。结果表明,菠萝蜜果皮与果肉挥发物中富含酯类化合物,果皮挥发物中的乙酸正丙酯和乙酸正己酯相对含量高于果肉中的,果肉挥发物中的异戊酸甲酯、戊酸丁酯、丁酸乙酯相对含量高于果皮挥发物中的,二者中的戊酸乙酯相对含量接近;二者中的其他酯和醇、羧酸(酐)、含氮及含硫类化合物均无共同成分;果皮挥发物中未检出而果肉挥发物中检出的化合物类型还有醛、醚、萜烯类。     

我国食品接触材料安全性评估体系构建

食品接触材料中所有可能迁移到食品中的物质均需要评估,包括单体、起始物和添加剂等有意添加物,以及杂质、生产过程中产生的副反应产物和降解物等非有意添加物。食品接触材料的安全性评估主要分为上市前的安全性评估和上市后的监测评估。目前,国际上食品接触材料上市前的安全性评估主要有美国和欧盟两种评估模式,两种方法各有优缺点。我国目前尚未建立食品接触材料上市前安全性评估的基本参数。构建我国食品接触材料安全性评估体系是国家食品安全风险评估专家委员会确定的"十三五"期间的重点工作。本文介绍了我国食品接触材料安全性评估体系的构成、预期目标以及食品接触材料风险评估面临的挑战。     

食品接触材料中非有意添加物及其来源研究进展

食品接触材料（Food Contact Materials, FCMs）在生产、使用和回收过程中都可能引入非有意添加物（Non-Intentionally Added Substances,NIAS）。NIAS的复杂性和未知性给FCMs的安全评估和监管带来严峻的挑战。近些年来,FCMs中NIAS的迁移作为影响食品安全的重要因素而备受关注。本文介绍了FCMs中NIAS的研究流程、分类及主要来源;从目标物及研究目的出发,归纳总结了NIAS的主要分析策略;重点描述了近年来不同类型FCMs中主要NIAS及其来源的研究进展,以期为今后FCMs中NIAS的深入研究提供科学指导。     

气相色谱-质谱联用法测定塑料食品接触材料中3种非邻苯塑化剂含量及其迁移量

建立了气相色谱-质谱联用法测定塑料食品接触材料中3种非邻苯塑化剂含量及其迁移量的方法。结果表明,3种目标化合物在质量浓度0.1～10 mg/L的范围内线性关系良好,相关系数r均大于0.999。3种非邻苯塑化剂在塑料食品接触材料中含量的定量限为10 mg/kg,迁移量定量限为0.1 mg/kg。选取4种塑料食品接触材料及4种食品模拟物为基质,在高、中、低3水平下加标回收率为82.7%～110%,相对标准偏差为0.279%～7.97%。利用该方法检测市售80批次塑料食品接触材料,有10批次PVC保鲜膜的。己二酸二(2-乙基己基)酯(Di(2-ethylhexyl) adipate, DEHA)和环己烷-1,2-二羧酸二异壬酯(Diisononyl hexahydrophthalate, DINCH)含量及迁移量有检出,接触油脂性食品时需考虑迁移风险。该方法前处理简单、重复性好,可为今后对食品接触材料中非邻苯塑化剂的安全性评价提供科学依据和技术支持。     

GC/MS法同时检测无烟气烟草制品中的1,2-丙二醇、丙三醇和三甘醇

为了准确测定无烟气烟草制品中保润剂的含量,以1,4-丁二醇为内标建立了同时检测无烟气烟草制品中1,2-丙二醇、丙三醇、三甘醇的气相色谱/质谱/选择离子监测(GC/MS/SIM)方法,采用该方法和CORESTA推荐的GC/FID法测定了30个无烟气烟草制品样品,并将2种方法的检测结果进行了比较.结果表明:①该方法的检出限和定量限分别为1.25～2.75 μg/g和4.10-9.05 μg/mL,回收率89.3%～100.3%,相对标准偏差(RSD)1.16%～4.37%;②所测无烟气烟草制品中1,2-丙二醇、丙三醇、三甘醇的含量分别在0.011-40.817,0.024～39.044和0.012～0.099 mg/g之间;③GC/FID法检出13个样品中舍1,2-丙二醇,检出率43.3%;14个样品中含丙三醇,检出率46.7%,其中能够准确定量的有9个样品;未检出三甘醇;④GC/MS/SIM法检出29个样品中含1,2-丙二醇,检出率96.7%,其中能够准确定量的有16个样品;28个样品中含丙三醇,检出率93.3%,其中能够准确定量的有25个样品;21个样品中含三甘醇,检出率70.0%,其中能够准确定量的有11个样品;⑤GC/FID和GC/MS/SIM法共同检出的13个样品中的1,2-丙二醇含量和9个样品的丙三醇含量的皮尔逊(Pearson)相关系数均大于0.99,概率P值均小于显著性水平0.05,配对t检验概率P值均大于显著性水平0.05.结论:两种方法的定量结果一致,但GC/MS/SIM法灵敏度更高,定性更准确,GC/MS/SIM法更适合无烟气烟草制品中1,2-丙二醇、丙三醇、三甘醇的定性定量分析.     

GC/MS法同时测定电子烟烟气释放物中的5种醇类化合物

为了准确测定电子烟烟气释放物中醇类化合物的量,以1,4-丁二醇为内标建立了同时检测电子烟烟气释放物中1,2-丙二醇、1,3-丁二醇、丙三醇、二甘醇和三甘醇的气相色谱/质谱(GC/MS)方法,采用该法测定了16种电子烟样品。结果表明:①该法的检出限和定量限范围在0.08~0.32μg/口和0.27~1.07μg/口之间;回收率在90.0%~99.5%之间,相对标准偏差(RSD)为1.20%~4.93%。②所测样品中均检出1,2-丙二醇、丙三醇,均未检出二甘醇和三甘醇;4个样品中检测出1,3-丁二醇。该法灵敏度高、定性准确,适合电子烟样品烟气释放物中1,2-丙二醇、1,3-丁二醇、丙三醇、二甘醇和三甘醇的定性定量分析。      

Investigation into the migration potential of coating materials from cookware products

Twenty-six non-stick-coated cookware samples were purchased, covering a variety of products, coating/metal types and food contact applications. The polymer coatings were identified to be polyethersulphone, polytetrafluoroethylene (PTFE), bisphenol A/epichlorohydrin and one coating for which no good match was obtained with infra-red library spectra. All of the products intended for stove-top use had a polymer coating containing PTFE. The coatings were analysed as purchased and after heating at 250°C for 30 min to simulate actual conditions of use. Total solvent extractables were measured and the overall migration was determined into simulants. None of the products exceeded an overall migration limit of 10 mg dm^-2. Coating materials were analysed by headspace gas chromatography-mass spectrometry (GC-MS), by liquid extraction followed by GC-MS and by liquid extraction followed by liquid chromatography-mass spectroscopy with a particle-beam interface. Benzene was detected in two samples, at 1.4 and 2.4 µg dm^-2. These levels in the coatings are too low to give any detectable migration into foods. There was no detectable release of perfluorochemicals. Several other substances were identified and the worst-case migration was calculated. The origin of many of the substances detected was considered to be by pick-up from the printed packaging materials in which the cookware was sold. Potential consumer exposure was calculated. None of the substances identified had the potential to exceed their tolerable daily intake (TDI) value. To confirm these worst-case calculations, the migration of certain phthalates and of bisphenol A was measured into food simulants. Migration levels were very low.     

非靶向筛查技术用于食品接触用小家电的检测与评价

目的 建立一种食品接触用小家电整机筛查和评估技术。方法 模拟厨房家电制作或接触食物的使用场景,采用气相色谱-质谱法和超高效液相色谱-四极杆-飞行时间质谱法,构建整机非靶向筛查技术,并应用于食品接触用家电产品:不粘电热锅、酸奶机、折叠水壶、测温勺、咖啡机、搅拌杯和制冰机。结果 所测样品中挥发性物质均未检出;酸奶机、折叠水壶和测温勺中检出半挥发性物质和不挥发性物质包括芥酸酰胺等20个化合物,7种检出物包括折叠水壶中的溶剂黄56、月桂酰胺,测温勺中的2-甲基-N-[(2-甲基丙氧基)-甲基]-2-丙烯酰胺、N-丁基苯磺酰胺、硬脂酸甲酯、3-(3,5-二叔丁基-4-羟基苯基)丙酸甲酯和3,5-二叔丁基-4-羟基苯乙酮的暴露量超过安全暴露阈值,需引起健康风险关注。结论 本研究开发的整机筛查方法快速有效,适用于家电产品的食品安全评价。     

Migration of styrene and ethylbenzene from virgin and recycled expanded polystyrene containers and discrimination of these two kinds of polystyrene by principal component analysis

ABSTRACT

The migration of styrene and ethylbenzene from virgin and recycled expanded polystyrene (EPS) containers into isooctane was investigated using gas chromatography-mass spectrometry (GC-MS). EPS containers were in two-sided contact with isooctane at temperatures of 25 and 40°C. It was shown that recycled EPS gave greater migration ratios compared with virgin EPS, which indicated that styrene and ethylbenzene migrated more easily from recycled EPS. In addition, an analytical method to distinguish between virgin and recycled EPS containers was established by GC-MS followed by principal component analysis (PCA). The relative peak area of the identified compounds was used as input data for PCA. Distinct separation between virgin and recycled EPS was achieved on a score plot. Extension of this method to other plastics may be of great interest for recycled plastics identification.     

气质联用仪测定鞋类材料中的17种有机锡含量

使用外标法,建立了气相色谱-质谱对鞋类材料中可能含有的17种有机锡化合物总量的测试方法。该方法使用甲醇/乙醇混合溶液超声辅助萃取,通过四乙基硼酸钠衍生后,使用气相色谱-质谱进行定性和定量分析。实验表明,在取消原有内标物质的基础上,改变了有机相的萃取剂和气质联用仪的色谱条件,17种有机锡化合物完全可以被准确地检测。     

Analysis for organic residues from aids to polymerization used to make plastics intended for food contact

Polymers intended for food contact use have been analysed for organic residues which could be attributed to a range of substances employed as polymerization aids (e.g. initiators and catalysts). A wide range of polymers was extracted with solvents and the extracts analysed by gas chromatography-mass spectrometry (GC-MS). The overwhelming majority of substances identified were not derived from aids to polymerization but were oligomers, additives and adventitious contaminants. However, a small number of substances were identified as initiator residues. These included tetramethylsuccinonitrile (TMSN) which was observed in two polymers and it derived from recombination of two azobisisobutyronitrile (AIBN) initiator radicals. Methyl benzoate, benzoic acid, biphenyl and phenyl benzoate were detected in one poly(methyl methacrylate) sample and in two polyvinylchlorides and they are thought to be derived from benzoyl peroxide initiator. TMSN was subsequently targeted for analysis of poly-(methyl methacrylate) plastics using proton nuclear magnetic resonance spectrometry (¹     

Evaluation of some screening methods for the analysis of contaminants in recycled polyethylene terephthalate flakes

A range of different analytical techniques were used to test recycled polyethylene terephthalate (PET) flakes for potential chemical contaminants. The techniques used were headspace gas chromatography coupled to mass spectrometry (GC-MS), liquid extraction followed by GC-MS, supercritical-fluid extraction followed by GC-MS, and migration testing followed by elemental analysis using inductively coupled plasma mass spectroscopy (ICP-MS). The PET samples were 50 representative samples taken from 600 that had been collected throughout Europe and which had been screened for potential contaminants using a single technique of high-temperature GC-MS. Six of the 50 samples tested had been spiked with a selection of model contaminants, three samples were virgin PET flakes and two of the samples were from supercleaning processes. All samples were analysed 'blind' in this exercise. The qualitative results showed that most of the contaminants came from the first use, being flavour-aroma compounds from soft drinks. The quantitative analysis found concentrations under a few mg kg^-1 in the polymer, except for the spiked samples. Element migrations were low and only calcium, silicon and sodium had median migrations above 50 μg l^-1. This in-depth analysis of recycled PET flakes did not identify any significant contaminants that had not already been detected by the high-temperature static GC-MS screening method, thus demonstrating its utility.     

GC-MS测定不同采收期酸枣仁中脂肪油成分

利用气相色谱-质谱联用(gas chromatography-mass spectrometry,GC-MS)技术分析经甲酯化的不同采收期酸枣仁的脂肪油成分组成及相对质量分数的变化。结果表明:3个时期酸枣仁的脂肪油成分总含量增加,经过GC-MS分析共检测出29种脂肪油成分,包括不饱和脂肪酸类、饱和脂肪酸类、碳氢化合物和醇类化合物这4大类组分。3个时期酸枣仁中均有其特殊的脂肪油成分,同时各时期也有相同的脂肪油成分,其中亚油酸甲酯(33.01%~34.27%)和油酸甲酯(43.66%~45.43%)为各个时期中的主要脂肪油物质。