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。     

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。     

双酚A环氧衍生物在罐头食品中的迁移规律与污染情况研究

罐头内壁涂层双酚A环氧衍生物在食品中的迁移存在安全隐患。本文模拟食品的贮存条件,研究了双酚A环氧衍生物在罐头食品中的迁移规律。实验结果表明,双酚A环氧衍生物在食品中的迁移主要受pH、温度、贮存时间的影响。在酸性条件下双酚A环氧衍生物的迁移量随浸泡时间的增长而增加,在高温下(40℃)迁移总量迅速增加。对34个罐头食品内容物进行检测,共8个样品检出双酚A环氧衍生物,检出率为23.5%。其中饮料罐头的检出率达85.7%,在酸性的饮料罐头中双酚A环氧衍生物的含量随贮存时间的增长而增加。     

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。     

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。     

食品中双酚A缩水甘油醚和酚醛清漆甘油醚的测定

建立蕃茄、凉荼、猪肉、牛奶和植物油中双酚A缩水甘油醚(BADGE)和酚醛清漆甘油醚(NOGE)系列化合物及其氢氧化和氯化衍生物的高效液相色谱—串联质谱测定方法.蕃茄和凉茶样品用乙酸乙酯和正己烷(4∶1)提取;猪肉和牛奶样品先用乙腈提取,再经低温过滤脱脂;植物油样品用甲醇提取,再经低温过滤脱脂.在正离子模式下以电喷雾电离—串联质谱仪进行测定.在20,50,100μg/kg3个浓度水平进行添加—回收率试验,平均回收率为63.6％～120％.该方法准确、高效,适合食品中BADGE和NOGE系列化合物的测定.     

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。     

食品包装迁移物双酚类物质稳定性与转化规律的研究

选用三片罐食品迁移物双酚A二环氧甘油醚(BADGE)及其6种双酚类物质衍生物为实验对象,探究了这些物质在模拟物体系中经不同灭菌方式后的稳定性以及各物质的转化产物。在此基础上,选取不同的储藏条件来进一步研究各物质之间的转化规律。结果表明:BADGE、BADGE·H_2O和BADGE·HCl在常压灭菌后以及储藏过程中会发生水合,转化成相应的水化物。BADGE·2HCl、BADGE·2H_2O和BADGE·H_2O·HCl在常压条件下,性质比较稳定。BADGE·HCl、BADGE·2HCl和BADGE·H_2O·HCl在经过高压灭菌后,三种氯化物在醇性模拟液中,会转变为BADGE及其水化物。本研究为金属包装材料中双酚类物质的迁移分析提供参考依据。     

南昌市罐装食品中双酚类化合物污染调查与分析

目的了解南昌市市售罐装食品中双酚类化合物污染状况,进一步完善了江西省食品安全风险监测体系。方法在南昌市范围内采集5类共65份样品,采用液相色谱-串联质谱法(liquid chromatography tandem mass spectrometry,LC-MS/MS)进行分析。结果 65份样品总检出率为69.2%,蔬菜类罐头和肉类罐头尤为突出,检出率高达100%,在所有样品均未发现双酚F及其衍生物。但BADGE·2H2O、BADGE·H2O·HCl检出率较高,最大检出值高达761、110μg/kg。结论南昌市罐装食品中双酚类化合物存在一定程度污染。     

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。     

Survey of bisphenol a diglycidyl ether (BADGE) in canned foods.

2,2-Bis(4-hydroxyphenyl)propane bis(2,3-epoxypropyl) ether (BADGE) is used in the manufacture of lacquers for coating the inside of food and beverage cans. In June 1996 the EC Scientific Committee for Food temporarily increased the specific migration limit applying to BADGE to 1 mg/kg pending consideration of additional toxicological data. In order to find out if there is migration of BADGE from can coatings into foods, a 'worst case' sampling exercise has been conducted to survey those canned foods where the propensity for migration of BADGE was judged to be highest. The foods surveyed include canned fish in oil, meat and milk and, altogether, BADGE was determined in 181 retail samples. Analysis for BADGE was conducted, in duplicate, by HPLC with fluorescence detection with confirmation of BADGE identity by GC/MS analysis using selected ion monitoring. BADGE was found at levels exceeding 1 mg/kg in seven of the 15 canned anchovy samples and five of the 22 sardine samples purchased during the period September 1995-July 1996. Infrared analysis of the can coatings provided strong evidence that the higher BADGE levels found were associated with use of PVC organosol lacquers, although in some cases cans coated with organosols gave low BADGE results. For canned sardine samples found to contain greater than 0.5 mg/kg BADGE in the total contents, a replicate can was opened and separate analyses performed on the drained fish and the oil. The results clearly showed that BADGE concentrations in the oil were about 20 times higher than in the drained fish. Further samples of canned sardines and anchovies were purchased in June/July 1997 and, in all cases, BADGE levels were found to be below 1 mg/kg. In the other retail canned foods, BADGE was not detectable (DL = 0.02 mg/kg) or detected at concentrations well below the temporary SML of 1 mg/kg.     

Bisphenol A (BPA) and its source in foods in Japanese markets

The determination of bisphenol A (BPA) and/or bisphenol A diglycidyl ether (BADGE) in foods sold in Japanese markets and in water leached from six epoxy resin cans with similar diameters was carried out using high-performance liquid chromatography (HPLC) with electrochemical detection (LC/ECD), LC-mass spectrometric detection (LC/MS) and LC-tandem mass spectrometric detection (LC/MS/MS). BPA concentrations were 0-842 ng g^-1 for 48 canned foods, 0-14 ng g^-1 for 23 foods in plastic containers, and 0-1 ng g^-1 for 16 foods in paper containers. No BADGE was detected in three canned foods. There was no difference in leaching concentrations of BPA into glycine buffers at pHs 8 and 11, and water. The amounts of BPA leached into water from six epoxy resin cans held at 121°C for 20 min were almost the same as the cans' contents and were much higher than the amounts leached from cans held at or below 80°C for 60 min. The amount leached depended on the type of can, but not on the amount of BADGE leached from the cans. Considerably more BPA than BADGE leached to water from six cans. Two cans whose contents had high concentrations of BPA showed no BADGE leaching even at 121°C, suggesting the different kinds of epoxy resin can linings from others. The results imply that the main source of human exposure to BPA is food from cans with linings that contain high percentages of BPA as an additive or an unforeseen contaminant.     

食品金属罐中14种双酚类物质迁移量的同时测定及杀菌过程对其迁移的影响

为了调查国内食品金属罐中双酚类物质的迁移水平,本文建立了同时测定食品金属罐中14种双酚类物质迁移量的高效液相色谱法,并研究了杀菌过程对双酚类物质迁移的影响及食品金属罐中双酚类物质的迁移规律.结果表明,14种双酚类物质在4种食品模拟物(4％体积乙酸、10％体积乙醇、50％体积乙醇和异辛烷)中线性关系良好,加标回收率为83...     

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%。     

Occurrence of bisphenol-F-diglycidyl ether (BFDGE) in fish canned in oil

The levels of bisphenol-F-diglycidyl ether (BFDGE) were quantified as part of a European survey on the migration of residues of epoxy resins into oil from canned fish. The contents of BFDGE in cans, lids and fish collected from all 15 Member States of the European Union and Switzerland were analysed in 382 samples. Cans and lids were separately extracted with acetonitrile. The extraction from fish was carried out with hexane followed by re-extraction with acetonitrile. The analysis was performed by reverse phase HPL C with fluorescence detection. BFDGE could be detected in 12% of the fish, 24% of the cans and 18% of the lids. Only 3% of the fish contained BFDGE in concentrations considerably above 1mg/kg. In addition to the presented data, a comparison was made with the levels of BADGE (bisphenol-A-diglycidyl ether)analysed in the same products in the context of a previous study.     

Estimates of per capita exposure to substances migrating from canned foods and beverages.

A study was undertaken by European industry to estimate the consumption of canned beverages and foodstuffs. European can production data were used with adjustments for imports into and out of the EU. It was further assumed that can production, with adjustments, equalled consumption. Owing to the lack of actual consumption country-by-country or household-by-household data throughout Europe, only per capita estimates of consumption were possible. Data were compiled country-by-country for seven major can-producing EU Member States and for eight different types of canned food and two types of canned beverage (beer and soft drinks). The per capita consumption of canned foods was 1.1 cans/person/week, and consumption of canned fish was estimated as 2.2 kg/person/year. The estimate of per capita consumption of canned food was 62 g/person/day or 22.6 kg/person/year. Canned beverages account for about 60% of the consumption of canned foodstuffs. The usefulness of per capita consumption of beverages is questionable because consumption habits may vary more widely than those for canned foods. However, as the migration into beverages is insignificant, these data were added for completeness. Per capita consumption of canned beverages is 67 cans/person/year or 61 g/person/day. From the average can sizes, the surface area of the cans consumed was estimated. The per capita surface area exposure was 0.55 dm(2)/person/day for canned foods and 0.55 dm(2)/person/day for canned beverages, giving 1.1 dm(2)/person/day. Migration of a substance at 0.02 mg dm(2) gives an exposure of 0.01 mg/person/day assuming a per capita consumption, using a surface area model. Migration at 0.12 mg kg(-1) in food gives an exposure of 0.007 mg/person/day using a weight model. Both models assumed migration into all food types at the same level, which is highly unrealistic. Exposure to BADGE from canned foods has been used as a case study. The best estimate for a worst case per capita exposure to BADGE and relevant derivatives was between 6 and 10 micro g/person/day, depending upon the approach and assumptions used.     

Migration of bisphenol-A diglycidyl ether (BADGE) and its reaction products in canned foods

Bisphenol-A diglycidyl ether (BADGE) is used as an additive or starting agent in coatings for cans. The presence of hydrochloric acid in the organosol (PVC-based) lacquers results in formation of chlorohydroxy compounds of BADGE. These compounds, as well as BADGE itself, are potential migrants into the preserved food and are of toxicological concern. In the present investigation the presence of BADGE and the chlorohydroxy compounds (BADGE.HCl and BADGE.2HCl) in various kinds of canned foods from 30 brands have been determined by HPLC with fluorescence detection. BADGE was found in levels up to 5.1mg/kg in the food and only in food from cans containing BADGE.HCl and BADGE.2HCl in the lacquers. BADGE was found both in fish in oil and in fish in tomato sauce, however, the highest amounts were found in the fatty foodstuffs. BADGE.HCl and BADGE.2HCl were found in concentrations up to 2.4mg/kg and 8.3mg/kg, respectively. Unlike BADGE, BADGE.2HCl was found in similar concentrations in fish in oil and in fish in tomato sauce. In aqueous and acidic foodstuffs BADGE readily hydrolyses into mono- and dihydrolysed products (BADGE.H₂O and BADGE.2H₂O). In this study BADGE.H₂O was not found in any food sample, whereas BADGE.2H₂O was found in levels up to 2.6mg/kg. The Scientific Committee for Food (SCF) of the European Commission has proposed that a limit of restriction of 1mg/kg food shall include BADGE itself and BADGE.H₂O, BADGE.HCl, BADGE.2HCl and BADGE.HCL.H₂O. The present results indicate that the migration of BADGE.HCl and BADGE.2HCl, compounds with almost no data on toxicity, implies a greater problem than BADGE.H₂O and BADGE.2H₂O.     

Monitoring of bisphenol-A-diglycidyl-ether (BADGE) in canned fish in oil

A survey at the European level was initiated on the quantification of bisphenol-A-diglycidyl-ether (BADGE) in canned fish in oil in order to assess the exposure of BADGE. A total of 382 canned fish samples were collected from all 15 Member States and Switzerland and analysed for BADGE in fish. The fish was extracted first with hexane and reextracted with acetonitrile, followed by a membrane filtration and reverse phase HPLC analysis with fluorescence detection. The analysis of the fish showed that about 3% of the samples contained BADGE at a level above 1mg/kg. The samples exceeding the limit by a larger margin were mostly from anchovy cans and cans manufactured in 1991-1995.     

Chlorohydrins of bisphenol A diglycidyl ether (BADGE) and of bisphenol F diglycidyl ether (BFDGE) in canned foods and ready-to-drink coffees from the Japanese market

BADGE.2HCl and BFDGE.2HCl were determined in 28 samples of ready-to-drink canned coffee and 18 samples of canned vegetables (10 corn, 5 tomatoes and 3 others), all from the Japanese market. HPLC was used as the principal analytical method and GCMS for confirmation of relevant LC fractions. BADGE.2HCl was found to be present in one canned coffee and five samples of corn, BFDGE.2HCl in four samples of canned tomatoes and in one canned corn. No sample was found which exceeded the 1mg/kg limit of the EU for the BADGE chlorohydrins. However the highest concentration was found for the sum of BFDGE.2HCl and BFDGE.HCl.H₂O at a level of 1.5mg/kg. A Beilstein test confirmed that all cans containing foods contaminated with BADGE.2HCl or BFDGE.2HCl had at lest one part coated with a PVC organosol.     

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.