食品和环境介质中双酚A前处理技术研究进展

双酚A是一种内分泌干扰物,在环境介质和食品包装材料中普遍存在,对生态环境和人体健康产生严重威胁,近年来受到人们的广泛关注。但实际样品中双酚A的浓度通常较低,且存在基质干扰,因此,直接检测比较困难,需要结合适当的前处理过程,以提高仪器的检出能力,保证分析结果的准确性和可靠性。就食品及环境介质中双酚A常用前处理技术,包括液-液微萃取、分散液-液微萃取、微波辅助萃取、加速溶剂萃取、固相萃取、固相微萃取、基质固相分散萃取、磁性固相萃取、分子印迹固相萃取和QuEChERS等技术,进行详细介绍、评价、总结和展望,为双酚A快速准确分析提供重要参考。     

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。     

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。      

食品中多环芳烃残留分析前处理方法的研究

文中设计并比较了水解-液液萃取法、水解-微波辅助萃取法、微波辅助萃取-水解法和水解一超声波萃取法4种食品中多环芳烃(PAHs)残留分析的提取方法;同时进行了净化实验。结果表明,水解-液液萃取法和水解-微波辅助萃取法的提取效果理想;采用中性氧化铝固相萃取回收率高,除杂效果明显。将水解-微波辅助萃取-中性氧化铝固相萃取净化法应用于多种食品进行分析,结果表明该方法适用于食品中PAHs残留分析。     

食品及包装材料中双酚A及其环氧衍生物残留分析的研究进展

双酚A及其环氧衍生物在食品包装材料中的迁移可能会造成人类和野生动物的内分泌系统、免疫系统、生殖系统和神经系统出现异常,是导致食品污染的重要途径之一.综述食品及包装材料中双酚A及其环氧衍生物的残留分析方法,并对未来食品中双酚A及其环氧衍生物的控制进行展望.     

固相萃取-液相色谱-串联质谱法同时测定牛奶中双酚A、双酚F和双酚S

为建立同时测定牛奶中双酚A、双酚F和双酚S含量的液相色谱-串联三重四极杆质谱联用方法,将样品用氨水 ∶ 乙腈溶液(1 ∶ 9,体积比)溶解,超声提取,PRiME HLB固相萃取柱净化,用安捷伦Poroshell 120 PFP色谱柱(100 mm×4.6 mm,2.7 μm)分离,采用负离子多反应监测模式监测,内标法定量。在此优化条件下,牛奶中双酚A、双酚F和双酚S的定量限均为2.0 μg/kg,平均方法回收率在90.4%~103.1%范围,平均相对标准偏差为2.76%~7.34%(n=6)。此方法的准确性和重复性良好,适用于牛奶中双酚A、双酚F和双酚S含量的检测。     

微波辅助萃取-超高效液相色谱-质谱法测定食品用纸容器中双酚A

建立食品用纸容器中双酚A的超高效液相色谱-质谱检测方法。采用微波辅助萃取仪对样品进行萃取,Sep-Pak C18固相萃取柱净化,甲醇-水（含有体积分数0.05%氨水）作为流动相,梯度洗脱,经Kinetex C18（2.1 mm×100 mm,2.6 μm）色谱柱分离,采用电喷雾电离,多反应监测模式下进行测定。结果表明：该方法在
1.0～100.0 μg/L质量浓度范围内线性良好,其相关系数（r²）为0.999 7。在5、10 μg/kg和50 μg/kg 3 个添加水平下,双酚A的平均回收率稳定在90.5%～98.6%之间,相对标准偏差均小于5.6%,方法检出限2.5 μg/kg。该方法操作简便,灵敏度高,适用于食品用纸容器中双酚A残留分析。     

河北省市售食品中双酚A和双酚S残留状况调查与分析

目的了解河北省市售食品(小麦粉、大米、肉类、淡水鱼、海水鱼、饮料及桶装水、肉罐头、鱼罐头和谷物罐头)中双酚A和双酚S残留状况。方法参考食品中化学污染物及有害因素监测技术手册方法,乙腈提取, GCB固相萃取柱净化,采用液相色谱-串联质谱法进行检测。结果在检测的356份样品中,双酚A共检出314份,检出率为88.2%,检测结果为小于检出限到514.8μg/kg,罐头食品是双酚A检出最高的食品类别,检出率为100%,检测结果为3.7~514.8μg/kg;双酚S共检出137份,检出率为38.5%,检测结果为小于检出限到93.8μg/kg,肉类食品(畜禽肉和鱼肉)是双酚S检出最高的食品类别,检测结果为小于检出限到268.9μg/kg。结论双酚A和双酚S在河北省不同食品中存在不同程度的残留,其污染情况值得关注。     

复合免疫亲和柱-高效液相色谱-串联质谱法测定植物源食品中的双酚A、双酚F和双酚S

目的 利用复合免疫亲和柱-高效液相色谱-三重四极杆质谱技术(HPLC-MS/MS)构建水果(苹果)、蔬菜(菠菜)、谷物(大米粉)以及婴幼儿谷类辅助食品(婴幼儿米粉)等植物源性食品中双酚A、双酚F和双酚S的分析方法.方法 样品用乙腈或含20％水的甲醇溶液提取,经复合免疫亲和柱对提取液进行净化,采用ACQUITY UPLC...     

高效液相色谱法检测运动饮料中双酚A的残留

建立一种快速、有效的高效液相色谱法测定运动饮料中双酚A残留的方法。样品经乙醇提取后,采用C18固相萃取小柱进行净化和富集。采用苯基色谱柱(4.6 mm×250 mm,5μm)分离,以乙腈∶水=40∶60(体积比)作为流动相,用PDA检测器检测,外标法峰面积定量。结果表明,双酚A标液在0.10μg/m L~1.00μg/m L浓度范围内线性良好,相关系数r~2为0.999,检出限为5.0μg/kg,定量限为15.0μg/kg,加标回收率达到92.1%~93.8%。该方法具有前处理简单、富集效果好和检测速度快的优点,适用于运动饮料中双酚A残留的定量检测。     

金属食品罐内涂层中双酚类物质的迁移及检测研究进展

鉴于双酚A及其他双酚类物质作为食品罐内涂层材料有潜在的毒性与危害,中国、欧盟、美国等国家均已严格限制它们在金属食品罐内涂料中的使用。本文介绍双酚A、双酚A二缩水甘油醚、双酚F、双酚F二缩水甘油醚的结构、应用、危害、检测方法及迁移结果,并简述固相萃取在样品前处理中的应用。     

Solid phase extraction of large volume of water and beverage samples to improve detection limits for GC-MS analysis of bisphenol A and four other bisphenols

Solid phase extraction (SPE) of large volumes of water and beverage products was investigated for the GC-MS analysis of bisphenol A (BPA), bisphenol AF (BPAF), bisphenol F (BPF), bisphenol E (BPE), and bisphenol B (BPB). While absolute recoveries of the method were improved for water and some beverage products (e.g. diet cola, iced tea), breakthrough may also have occurred during SPE of 200 mL of other beverages (e.g. BPF in cola). Improvements in method detection limits were observed with the analysis of large sample volumes for all bisphenols at ppt (pg/g) to sub-ppt levels. This improvement was found to be proportional to sample volumes for water and beverage products with less interferences and noise levels around the analytes. Matrix effects and interferences were observed during SPE of larger volumes (100 and 200 mL) of the beverage products, and affected the accurate analysis of BPF. This improved method was used to analyse bisphenols in various beverage samples, and only BPA was detected, with levels ranging from 0.022 to 0.030 ng/g for products in PET bottles, and 0.085 to 0.32 ng/g for products in cans.     

微波萃取-高效液相色谱法测定食品塑料包装材料中双酚A含量

建立了微波萃取-超高效液相色谱法(MAE-HPLC)检测塑料包装食品中双酚A的分析方法。选择甲醇为萃取溶剂,对微波萃取条件进行了优化,结果表明最佳的萃取条件为:萃取温度为80℃,萃取时间为20min。在试验选定的最佳条件下,方法线性范围0.10~20mg/L,相关系数为0.9998,方法检出限为0.1 mg/kg,样品加标回收率为88.9%~99.6%,相对标准偏差小于2.2%。     

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.     

Sensitive determination of bisphenol A and bisphenol F in canned food using a solid-phase microextraction fibre coated with single-walled carbon nanotubes before GC/MS

A reliable and sensitive method for simultaneous determination of bisphenol A (BPA) and bisphenol F (BPF) in canned food by gas chromatography-mass spectrometry (GC/MS) is described after extraction and pre-concentration by a new solid-phase microextraction (SPME) adsorbent. The potential of single-walled carbon nanotubes (SWCNTs) as SPME adsorbent for the pre-concentration of environmental contaminants has been investigated in recent years. This work was carried out to investigate the feasibility of SWCNTs as a headspace SPME adsorbent for the determination of bisphenol derivatives in canned food. Potential factors affecting the extraction efficiency, including extraction time, extraction temperature, desorption time, desorption temperature, and salinity were optimized. Calibration curves were linear (r ²≥ 0.994) over the concentration range from 0.30 to 60 µg kg^?1. For both target analytes, the limit of detection (LOD) at signal-to-noise (S/N) ratio of 3 was 0.10 µg kg^?1. In addition, a comparative study between the SWCNT and a commercial polydimethylsiloxane (PDMS) SPME fibre for the determination of bisphenol derivatives in canned food was conducted. SWCNT fibre showed higher extraction capacity, better thermal stability (over 350°C) and longer life span (over 150 times) than the commercial PDMS fibre. The method was successfully applied to determine BPA in canned food samples which were purchased from local markets. BPA was found in some of the samples within the concentration range from 0.5 to 5.2 µg kg^?1.     

LC-MS/MS analysis of bisphenol S and five other bisphenols in total diet food samples

ABSTRACT

It is already known that bisphenol S (BPS) has been used as a substitute for BPA in thermal papers in recent years. It is not clear, however, if BPS has also been used to replace BPA in can coatings as currently being speculated due to a lack of credible studies on migration of BPS from can coatings and occurrence data of BPS in foods. In this study, an LC-MS/MS method was developed for the analysis of BPS, along with several other bisphenols, and method detection limits for BPS varied from 0.0017 to 3.1 ng/g depending on the type of sample matrix and the amount of sample analysed. This method was used to analyse 159 different food composite samples from a recent Canadian total diet study. Bisphenol E (BPE), bisphenol B (BPB), and bisphenol AF (BPAF) were not detected in any of the 159 food composite samples, bisphenol F (BPF) was detected in only three samples (25–2360 ng/g), and bisphenol A (BPA) was detected in 10 samples (5.3–41 ng/g) which were all prepared from canned foods. BPS was not detected in any of the canned food composite samples but was detected in nine food composite samples prepared from meat and meat products (1.2–35 ng/g), indicating sources for BPS other than can coatings may be possible, which will be investigated in future studies.     

Molecularly Imprinted Nanosilica Solid-Phase Extraction for Bisphenol A in Fish Samples

This paper reports a method using molecularly imprinted nanosilica as the solid-phase extraction sorbent to extract bisphenol A (BPA) from fish samples. The selective extraction efficiency of BPA from its structure-analogous by molecularly imprinted solid-phase extraction (MISPE) was compared with commercial C18 SPE column. The reproducibility of MISPE and optimal flow rate of sample were studied. There was a linear correlation in the concentration range of 0.7–114.1 μg l^?1 of BPA (r?=?0.997). The limit of detection (LOD) based on three times ratio of signal to noise was 0.11 μg l^?1. Under optimal conditions, the proposed method was applied to the analysis of BPA in fish samples. The amount of BPA in bream was 4.00 μg kg^?1, and both concentrations of BPA in crucian and weever were below the LOD. The recoveries of BPA standard solution spiked with fish samples were in the range of 92.56–102.3 % with the relative standard deviation less than 10 %.     

Analytical determination of bisphenol A (BPA) and bisphenol analogues in paper products by GC-MS/MS

ABSTRACT

Bisphenol A (BPA; 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol), a suspected endocrine disruptor with a weak estrogenic activity, is used in a variety of consumer products, including food-contact materials made of paper and cardboard products. Due to restrictions on the use of BPA because of its potential health risks, BPA is gradually being replaced by other bisphenols because no limitations exist for these substances. This study presents a method for the simultaneous analysis of BPA, bisphenol AF (BPAF), bisphenol B (BPB), bisphenol E (BPE), bisphenol F (BPF) and bisphenol S (BPS) in paper and board products using gas chromatography-tandem mass spectrometry (GC-MS/MS). Paper samples were extracted by liquid extraction, as well as by Folch extraction, derivatised with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) and the results compared. The developed method showed good linearity (R² > 0.9965) and precision, yielding relative standard deviations (RSDs) of less than 16.6% for reproducibility and 19.8% for repeatability. The limits of detection and limits of quantification for the different bisphenols ranged from 0.23 to 2.70 µg kg^–1 paper and from 0.78 to 9.10 µg kg^–1 paper, respectively. Analysis of different paper products (recycled, virgin fibre) showed that all the analysed bisphenols were present in the samples, except for BPAF and BPB. A calculation of the ‘worst-case’ scenario assuming a maximum potential migration of 100% of the analytes into food showed that the analysed products can be assumed to be safe regarding the migration of bisphenols.     

Simultaneous determination of bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether and their hydrolysis and chlorohydroxy derivatives in canned foods

A new method for the simultaneous determination of bisphenol A-diglycidyl ether (BADGE), bisphenol F-diglycidyl ether (BFDGE) and their hydrolysis and chlorohydroxy derivatives in canned foods is presented. Oily and aqueous food samples were extracted with tert-butyl methyl ether and acetonitrile, respectively. The compounds in both extracts were determined by using reverse-phase gradient high-performance liquid chromatography with fluorescence detection. Optimization of extraction and chromatographic determination is outlined in detail. After validation the method was used to analyze various canned food samples, such as tuna and sardine in oil, vegetables, fruit cocktails, etc. In none of the samples were significant amounts ( >100 μg/kg) of BADGE or BFDGE found, whereas in most samples BADGE/BFDGE chlorohydroxy compounds were detected. These originate most probably from the use of organosol varnishes instead of epoxy resins. Risk assessment and regulations of these compounds by the European Union are urgently needed. Additionally, the syntheses and characterization of the not available standard compounds bisphenol A-p-glycidyl-p′-(3-chloro-2-hydroxypropyl) ether (BADGE.HCl) and bisphenol A-p-(2,3-dihydroxypropyl)-p′-(3-chloro-2-hydroxypropyl) ether (BADGE.HCl.H₂O) are presented. Received: 28 July 1999 / Revised version: 29 October 1999     

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%。