食品包装污染物双酚类物质在食品模拟体系中的迁移规律研究

采用4 种食品模拟物包括超纯水、30 g/L乙酸水溶液、10%乙醇水溶液和异辛烷对食品金属罐中4 种双酚物（包括双酚A、双酚F、双酚A二缩水甘油醚和双酚F二缩水甘油醚）迁移情况进行研究,并建立半经验的双酚物迁移规律数学模型。结果表明：4 种双酚物同时在10%乙醇溶液中出现最大迁移,且贮存温度和时间对迁移量变化有显著影响。根据模拟实验得到的迁移数据和Fick第二定律建立数学模型,初步确定扩散系数DP,再根据DP估计得到包材的特征参数AP的范围为35.38～48.48。     

金属三片罐生产过程中双酚类物质迁移规律的研究

按照金属三片罐的实际生产工艺,跟踪研究了制罐内涂、外涂、彩印、上光、罐内补涂以及全喷工序过程的中间品,各自相应内壁涂膜中9种双酚物向3%(m/v)乙酸和10%(v/v)乙醇模拟液中的迁移情况。结果表明:双酚F二环氧甘油醚及其衍生物在两种模拟液中都未检出;而双酚A-(2,3-二羟丙基)甘油醚和双酚A-双(2,3-二羟丙基)甘油醚在两种模拟液中均有迁出;10%乙醇中还检测到双酚A二环氧甘油醚及其他衍生物。在10%乙醇体系中,迁出的双酚物在全喷后增加显著。3%乙酸体系中,迁出的双酚物在补涂和全喷后增加明显。结果表明补涂与全喷这两个工艺对三片罐的食品安全性造成潜在影响,可在加工过程中作为关键控制点进行控制。     

LC-MS/MS分析罐装食品和饮料中的双酚A-缩水甘油醚(BADGE)、双酚F-缩水甘油醚(BFDGE)及其衍生物

双酚A—缩水甘油醚(BADGE)和双酚F—缩水甘油醚(BFDGE)经常被用于罐装食品和饮料中,但它们及它们的衍生物存在着潜在的致突变性、遗传毒性和抗雄激素作用,欧盟已对其总量作了限制。本文的目的就是开发一种能同时定量测定罐装食品和饮料中BADGE、BFDGE及其衍生物的快速灵敏的LC—MS/MS方法。     

罐头涂料铁罐双酚A二缩水甘油醚及其衍生物迁移规律研究

研究了罐头涂料铁罐双酚A二缩水甘油醚及其衍生物在特定食品模拟物中的迁移规律。采用50%(v/v)乙醇溶液为食品模拟物,应用高效液相色谱-串联质谱法进行双酚A二缩水甘油醚及其衍生物的定性定量分析,并应用基于Fick扩散第二定律的D.Chung模型和基于概率与数理统计方法的Weibull模型进行了预测。结果表明:贮存条件对迁移总量变化影响显著,温度越高越快达到平衡,迁移平衡值为1.28 mg/kg;D.Chung模型中扩散系数D与贮存温度符合阿伦尼乌斯动力学模型,该模型预测值与实验值的拟合优度(R~2)小于0.23,而Weibull模型拟合优度(R~2)能达到0.90以上。因此,Weibull模型比D.Chung模型更接近实际迁移结果,为评估涂料铁罐的安全性提供参考。     

浅谈我国婴幼儿配方食品系列安全标准新、旧变化

概述了近年来我国婴幼儿配方食品安全标准的变化,包括婴幼儿配方食品及其接触材料安全标准的变化.文中关于婴幼儿配方食品接触材料的安全标准变化主要从双酚A、双酚A-二缩水甘油醚及其衍生物等三类化合物的化学毒性、国内外法律规范以及我国现行标准等方面进行了阐述;有关婴幼儿配方食品安全标准的变化主要综述了蛋白质、碳水化合物等六大类...     

食品罐内涂层中双酚A及其环氧衍生物的迁移及检测研究进展

食品罐内涂层中的双酚A及其环氧衍生物会向食品内容物迁移,对人体健康造成危害。本文综述了近年来国内外食品罐内涂层中双酚A及其环氧衍生物的迁移规律、与食品的反应及提取与分析方法等方面的最新研究进展,并在分析目前不足之处的基础上展望了未来研究的方向。     

食品罐内壁涂层中双酚A-二缩水甘油醚双水合物的迁移特性的数值仿真与实验研究

对金属罐内壁涂层中的有害物质(双酚A-二缩水甘油醚双水合物,以下简称BADGE·2H2O)向食品模拟液在给定条件下的迁移特性进行了数值仿真,并与对应条件下的实验结果进行了对比、分析。结果表明:温度、初始浓度、涂层厚度对物质迁移的影响较大;对于给定的温度,温度越高,则迁移达到平衡时所需要的时间越短,迁移量越大;对于给定的初始浓度和涂层厚度,初始浓度越大,涂层厚度越厚,则迁移量越大;同时,在不同温度下,BADGE·2H2O从食品罐内壁涂层向水性模拟液迁移的数值解与实验值最大差值为0.023μg/mL。数值仿真与实验结果有较好的一致性。     

国内市场上罐装啤酒中双酚类物质迁出量调查

建立并利用固相萃取-高效液相-荧光法对国内市场上31种罐装啤酒中双酚物的含量进行了调查。方法的检测限为0.02～0.09μg/L,在0.02～50.00μg/L的检测范围内相关系数大于0.99,加标回收率和标准差分别为80.67%～101%和1.01%～4.84%。样品中除双酚E(BPE)没有检出外,双酚A(BPA)、双酚A二缩水甘油醚(BADGE)、双酚F二缩水甘油醚(BFDGE)、双酚B(BPB)和双酚F(BPF)的平均检出浓度分别为2.99、0.41、0.18、0.12、0.12μg/L,检出率分别为100%、83.9%、6.4%、12.9%和6.4%。BPA和BADGE是罐装啤酒中存在的最主要的双酚物,其平均每日摄入量分别估计为0.0160、0.0022μg/kg.bw.d,低于欧盟关于BPA50μg/kg.bw.d的规定。样品中BPA没有超过欧盟规定的0.6mg/L,BADGE的迁移也未高于9mg/L,但是BFDGE的检出是不允许的。目前尚无关于BPF、BPE和BPB的迁移限值。     

肉类罐头食品中双酚A二缩水甘油醚及其衍生物的迁移

本实验应用高效液相色谱-电喷雾串联质谱法分析检测肉类罐头食品中双酚A二缩水甘油醚(BADGE)及其衍生物的残留,重点研究了肉类罐头中的内容物、存储时间(6个月、9个月、12个月)以及存储温度(4、20、100℃)对双酚A二缩水甘油醚(BADGE)及其衍生物的迁移量的影响,单因素方差分析(One-way ANOVA)检验实验结果表明,不同内容物罐头中从内壁涂层迁移至样品的BADGE及其衍生物存在显著性差异(p<0.05),Student-Newman-Keuls法检验表明存储12个月后目标化合物的迁移量与6个月、9个月存在显著性差异,存储温度为4、20℃时化合物迁移量没有显著差异,但是罐头加热到100℃后目标化合物迁移量是最大的。     

石墨烯固相萃取-液相色谱-质谱联用法测定食品接触材料中9种双酚-二环氧甘油醚的迁移量

基于石墨烯固相萃取,以实际样品为研究对象,建立了食品接触材料中内分泌干扰物双酚A-二缩水甘油醚(BADGE)及其衍生物BADGE·H2O、BADGE·HCl、BADGE·2H2O、BADGE·2HCl、BADGE·H2O·HCl和双酚F-二缩水甘油醚(BFDGE)及其衍生物BFDGE·2HCl、BFDGE·2H2O等9种双酚-二环氧甘油醚迁移量的高效液相色谱-串联质谱(HPLC-MS/MS)检测方法。样品以叔丁基甲醚为提取溶剂,超声提取,提取液经石墨烯固相萃取柱富集、净化。质量分数0.1%乙酸的5 mmol/L醋酸铵溶液和甲醇为流动相,经COSMOSIL C18分析柱分离后,采用电喷雾串联四级杆质谱检测。9种双酚-二环氧甘油醚中2种在0.5~50 ng/m L范围内线性关系良好;2种在5.0~100.0 ng/m L范围内线性关系良好;其他5种在2.0~100.0 ng/m L范围内线性关系良好(r20.992 2)。对牛肉、橘片两种罐头食品进行3个水平的添加回收实验,9种目标化合物的回收率分别为:60.0%~97.6%(牛肉)和65.7%~111.3%(橘片),相对标准偏差小于20%。方法的检测低限为0.1~1.0μg/kg。该方法操作简单,灵敏度高,成功应用于食品接触材料中双酚-二环氧甘油醚迁移量的快速检测。     

Stability of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether in water-based food simulants

Varnishes used for the inner coatings of food cans are often based on epoxy resins or vinylic organosols. The epoxy resins can be produced from bisphenol A (BPA) and bisphenol F (BPF), and these also contain bisphenol A diglycidyl ether (BADGE) or bisphenol F diglycidyl ether (BFDGE) as stabilising components. These compounds may break down during storage and also by the influence of food simulants. The stability of BADGE and BFDGE were studied using reverse-phase gradient high-performance liquid chromatography (RP-HPLC) with ultraviolet detection (UV). Three experimental conditions for spiked simulants were compared: (1) the storage at 25 °C (C1), (2) the storage at 40 °C (C2) and (3) the storage at 25 °C after 15 min heating at 120 °C (C3). Distilled water, 3% acetic acid and 10% ethanol were used as food simulants. It was observed that BADGE is more stabile than BFDGE. The loss of BADGE and BFDGE were minimal in 10% ethanol (39 and 46% at 25 °C, 60 and 69% at 40 °C, respectively) and highest in 3% acetic acid (60 and 63% at 25 °C, 76 and 82% at 40 °C, respectively). At experiment (C3), the hardest conditions, significant degradation was not shown in comparison with conditions (C1) and (C2), contrariwise BADGE and BFDGE in 10% ethanol were minimal degradated at conditions (C3) from all these experiments (loss of 5 and 8%, respectively).     

Migration from can coatings: Part 3. Synthesis, identification and quantification of migrating epoxy-based substances below 1000 Da

Bisphenol A-derived glycidyl ethers as well as its reaction products with other lacquer components can migrate into the packed food from epoxy-based can coatings. A sensitive and selective method is presented using high-performance liquid chromatography coupled with ultraviolet light, fluorescence and electrospray ionization-mass selective detection for the identification and quantification of all migrants with a bisphenol A backbone and a molecular weight below 1000 Da, an estimated boundary for the absorption in the gastrointestinal tract. The identification of migrants was confirmed by microreactions of technical bisphenol A diglycidyl ether with solvents and phenols, which provided the fragmentation pattern of the mass selective detection and relative retentions of 42 different bisphenol A-related substances. It was shown by calibration of different isolated and synthesized bisphenol A derivatives that the fluorescence response relies on the amount of bisphenol A moiety in the respective molecule. Therefore, all migrating bisphenol A-related substances below 1000 Da were determined as bisphenol A diglycidyl ether equivalents using a calibration (fluorescence detection) of the commercially available bisphenol A diglycidyl ether monomer. The limit of quantification was set at 5 μg bisphenol A diglycidyl ether equivalents kg^-1 (or 0.8 μg dm^-2). This method was validated for epoxy coatings (0.1 μg dm^-2 limit of detection and 24 μg bisphenol A-related substances below 1000 Da dm^-2 standard deviation, corresponding to 4.4% relative standard deviation). The quantification could be extended by combining the fluorescence response and structural information gained from the mass spectra, which provides more accurate results for each migrant. The calculation is based on the calibration of the bisphenol A chromophore content of the molecule. According to this method, the amount of migrating bisphenol A-related substances below 1000 Da in the acetonitrile extract (assuming a worst case) varied from about 0.4 to 0.7 mg dm^-2 in the examined coatings. The determined amounts comply with about 50% of the total migrate below 1000 Da.     

Improved sample extraction and clean-up for the GC-MS determination of BADGE and BFDGE in vegetable oil.

A straightforward method was established for the determination of migration contaminants in olive oil with a special focus on the two can-coating migration compounds bisphenol A diglycidyl ether (BADGE) and bisphenol F diglycidyl ether (BFDGE). The preferred sample preparation was a single liquid-liquid extraction of compounds from the oil into 20% (v/v) methanol in acetonitrile, followed by clean-up with solid-phase extraction on aminopropyl bonded to silica. This purification procedure selectively removed all free fatty acids from the extracts without removing phenolic compounds of interest. The solid-phase extraction columns were used many times by implementing a procedure of washing out the strongly retained fatty acids with 2% acetic acid in methanol. Gas chromatography coupled with full scan (m/z 33-700) electron ionization mass spectrometry was used for the determination of several model compounds in olive oil samples. BADGE and BFDGE could be determined in the 0.05-2 mg kg(-1) range in oil samples with a relative SD of <6% (six replicates). The method was used in an enforcement campaign for the Norwegian Food Control Authority to analyse vegetable oil samples from canned fish-in-oil.     

Development and Validation of a LC-FD Method for the Simultaneous Determination of Eight Bisphenols in Soft Drinks

Bisphenol A (BPA) is a chemical widely used as a monomer in the production of polymers of plastics. It acts as an endocrine-disrupting agent and thus its contaminations of food and beverage should be carefully monitored in order to assess consumers’ risk. In this study, we propose a liquid chromatography-fluorescence detection (LC-FD)-validated method for the simultaneous determination of BPA and seven analogues, i.e., bisphenol AF, bisphenol B, bisphenol E, bisphenol F, BPA diglycidyl ether, bisphenol F diglycidyl ether, and Bisphenol M in soft drinks. A one-step solid-phase extraction (SPE) was effective at reducing the interferences, obtaining good purification of the samples, and consequently good recoveries of all analytes. The separation was obtained on a C18 column by using acetonitrile/water 55:45 (v/v) under isocratic conditions. Method validation was performed according to the European Commission Decision 2002/657/EC criteria, providing good results regarding the analytical parameters of linearity, selectivity, sensitivity, precision, recovery, decision limit (CCα), detection capability (CCβ), limit of detection (LOD), limit of quantification (LOQ), stability, and robustness. The method allows the detection of BPA and BADGE at levels much lower than their legal limits in the food, which are 0.06 and 9.00 mg kg^?1, respectively.     

A LC-MS/MS method for the determination of BADGE-related and BFDGE-related compounds in canned fish food samples based on the formation of [M+NH(4)](+) aducts

A new and simple liquid chromatography tandem mass-spectrometry method for the determination of different bisphenol A (BPA) derivatives such as bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether (BFDGE) and their reaction products with water and hydrochloric acid in different fish food products was developed. The extraction procedure and the chromatographic conditions were optimised for complex food matrices such as fish products. Food samples were homogenised and extracted with a 1:1 solution of acetonitrile-hexane, the solvent was eliminated in a N(2) stream and the extract was reconstituted with 0.5mL of a 0.01M solution of ammonium formate. The sample solution obtained was directly measured by LC-MS/MS without any further purification under the developed conditions. The use of a mobile phase composed by ammonium formate-methanol in a binary gradient mode produced [M+NH(4)](+) aducts for the different BADGEs and BFDGEs. These aduct's fragmentations were employed for the LC-MS/MS quantification of BPA derivatives in canned fish samples. The results of the validation were appropriate: the method was linear for BADGE and its hydrolysed derivatives up to 1000μgkg(-1), for the remaining compounds linearity achieved up to 100μgkg(-1). Quantification limits were in the range 2-10μgkg(-1). RSD (intra and inter-day) was 6-12% and the recovery was comprised between 89% and 109%. Under the optimised conditions, the chromatographic separation was performed in 8min per sample. The method was applied to the determination of BADGE, BFDGE and their reaction products in different samples of canned fish from Spanish origin. Migration results obtained were in compliance with the EU regulations.     

Are Canned Beverages Industries Progressively Switching to Bisphenol AF?

Seven bisphenols, endocrine‐disruptor chemicals, were analytically determined for risk assessment in 52 large‐consumption beverages collected from the Italian market. The analytes under examination were bisphenol A, bisphenol F, bisphenol E, bisphenol B, bisphenol AF, bisphenol A diglycidyl ether, and bisphenol M. The concentration levels of all bisphenols detected ranged from <LOQ to 1,358 ng/mL in beers and from <LOQ to 76 ng/mL in energy drinks. The results of this monitoring study demonstrate the high presence of some congeners in beers, such as bisphenol AF, for which a European regulation is not yet available. Although the concentrations of the investigated bisphenols and that are under European regulations for migration into the food (Bisphenol A and BADGE) resulted below the legal limits in all screened beverages, the importance of their presence in foods should not be underestimated. Indeed, the safety of these analogues has not entirely been demonstrated and they could contribute to the total daily intake of endocrine disruptors, with special regards to specific demographics.     

食品包装材料中有害物质双酚A二缩水甘油醚 体外代谢研究

目的通过模拟体内代谢,对双酚A二缩水甘油醚(BADGE)的体外基本代谢情况进行研究。方法采用肝微粒体、肝S9 2种体外代谢试剂,通过模拟体内肝脏代谢,对BADGE的代谢行为及其代谢产物进行研究。通过代谢试剂浓度及代谢时间条件的优化,采用高效液相色谱-串联质谱(HPLC-MS/MS)作为检测手段对BADGE的体外代谢产物进行分析确证。结果体外代谢最佳孵化时间为60 min,最佳体外代谢试剂浓度为0.5mg/m L,在肝S9及肝微粒体2种体外代谢试剂的作用下,BADGE发生显著的代谢反应。结论本研究与传统的动物试验相比,节约了时间、精力,对食品包装材料的毒理学研究和安全性评价有重要的推动作用。     

Determination of bisphenol A diglycidyl ether (BADGE) and its derivatives in food: identification and quantification by internal standard

Bisphenol A diglycidyl ether (BADGE) and its reaction products with water and hydrochloric acid have recently been subject to new regulations concerning their migration from food packaging into foodstuff. A method for the simultaneous identification and quantification of these substances and their precursor bisphenol A in food is described introducing bisphenol A di-(3-hydroxypropyl)ether as an internal standard. Analysis was carried out using RP-HPLC gradient elution with fluorescence detection. Additional information in the case of suspect samples was obtained using RP-HPLC with mass selective detection. The described method is validated for the analysis of foodstuffs as well as fatty food simulants. The limits of detection were between 10 and 30 µg/kg of food; recovery experiments gave identical behaviour for all analytes and the internal standard. The enforcement of the specific migration limit set by regulatory standards of the European Union for BADGE and its hydrolysis and hydrochlorination products is possible for producers as well as food quality surveillance institutions.     

超高效液相色谱-串联质谱法同时测定鱼、肉类罐头食品中的BADGE、NOGE及其衍生物

建立了一种罐头食品中的BADGE(bisphenol A diglycidyl ether,双酚A-二环氧甘油醚)、NOGE(novolacglycidyl ether,酚醛清漆甘油醚)及其衍生物含量的超高效液相色谱-串联质谱检测法。前处理包括正己烷/丙酮微波辅助萃取,Varain-PS-DVB固相萃取柱净化等。样品经BEH C18色谱柱(100 mm×2.1 mm,1.7μm)分离,以乙腈和0.2%甲酸水为流动相,进行梯度洗脱,在API 4000-QTRAP质谱仪电喷雾正离子、多反应监测(MRM)模式下进行检测。分析物检出限达到0.010 2 ng/g到0.197 2 ng/g,三水平加标回收率在65.7%～99.1%。