高效液相荧光法对5种罐装食品模拟物中双酚类化合物的迁移分析

双酚A及双酚类环氧衍生物是一种内分泌干扰物,易从金属罐头涂层迁移到食品内容物中。本文建立了一个高效液相色谱-荧光检测法同时检测罐头模拟物中14种双酚类化合物的分析方法。在10～1000ng/mL质量浓度范围,双酚A和各双酚类环氧衍生物的响应峰面积与其相应浓度呈良好相关性,最低检出限在1.41～3.66ng/mL之间;在10～250ng/mL添加水平范围内,平均回收率在72.55%～102.79%之间,日内和日间相对标准偏差均小于10%。之后将此方法应用于测定食品罐头中该双酚类化合物在不同食品模拟物中的迁移情况。     

液相色谱-电喷雾电离串联质谱法测定牛奶中双酚A

建立了采用液相色谱-电喷雾电离串联质谱测定牛奶中双酚A含量的方法,并将其应用于聚碳酸酯奶瓶中双酚A向牛奶中迁移的研究。牛奶用乙腈超声提取,蒸干后残渣用乙酸乙酯提取,蒸干后用流动相溶解,LC-MS/MS法测定,采用负离子电喷雾电离、多反应监测模式测定。线性范围为0～100ng/mL,相关系数为0.9992,检出限为0.03ng/g,加标回收率为78.27%～88.36%,样品检测相对标准差在3.81%～5.26%。     

食品包装聚碳酸酯成型品双酚A检测及迁移特性研究

目的:建立食品包装材料聚碳酸酯(PC)成型品双酚A含量检测方法,探讨双酚A在不同模拟浸出液中的迁移特性。方法:采用高效液相色谱-荧光检测法(HPLC-FD),Alltima C18柱(150×4.6mm,5μm)分离,流动相为乙腈和水(58∶42,V/V),流速1.0mL/min,柱温40℃,荧光激发波长275nm,发射波长310nm。PC成型品按2mL/cm2分别用水、20%和65%乙醇(V/V)在90℃浸泡6h。结果:双酚A在0.02～4μg/mL范围内具有良好的线性关系(r=0.999),检测限为10ng/mL,方法回收率为91%～108%,相对标准偏差(RSD)小于6%(n=5)。两种典型的PC成型品中双酚A含量分别为17.14mg/kg和46.69mg/kg,在水、20%和65%乙醇中的迁移量分别为0.782～1.11、0.734～0.684、1.84～2.49mg/kg。结论:该方法快速简便,准确度高,适用于PC成型品中双酚A的检测。实验条件下PC中有微量双酚A溶出,且溶出量与PC材质有关。     

奶瓶中双酚A、烷基酚及烷基酚聚氧乙烯醚残留量的高效液相色谱-荧光测定法

建立了奶瓶中双酚A、烷基酚及烷基酚聚氧乙烯醚残留量的高效液相色谱-荧光测定方法.样品用二氯甲烷-甲醇提取后,采用高效液相色谱分离,荧光检测器检测.BPA、OP、NP、OPEO在0.05～1.0 μg/mL,NPEO在0.2～1.0 μg/mL范围呈线性.对奶瓶样品作添加回收试验,各种成分的平均回收率在81.1%～100.3%之间,相对标准偏差在2.7%～5.5%之间.方法检出限:BPA为1 mg/kg;OP、NP、OPEO为2 mg/kg ;NPEO为5 mg/kg.结果表明,该法简便、灵敏、精确度高,适用于奶瓶中双酚A、烷基酚及烷基酚聚氧乙烯醚的残留分析.     

食品包装材料中双酚A迁移量的测定

建立采用高效液相色谱法对塑料食品包装材料中双酚A向食品模拟物迁移量的检测方法。使用4种食品模拟物：水、质量分数为4%乙酸溶液、体积分数30%的乙醇溶液和脂肪类模拟物(正己烷、异辛烷和橄榄油)。结果表明,双酚A在与食品塑料包装接触过程中,无论在何种情况下都会向食品模拟物中迁移,尤其向醇类模拟物中迁移最严重;在温度超过60℃时,双酚A向食品模拟物中的迁移率骤增;在微波加热条件,高火700W功率时双酚A向食品模拟物中的迁移速率最快。该方法检测限为0.3ng/mL,线性范围为0.5～100ng/mL,线性相关系数为0.9997,回收率在92.0%～102.4%之间,相对标准偏差≤2.84%(n=5)。     

食品模拟物中双酚A迁移量的间接竞争免疫PCR检测方法

通过抗原-抗体的特异性反应,结合荧光PCR,建立了食品接触材料中双酚A在食品模拟物中迁移量的快速、灵敏的间接竞争免疫PCR检测方法。通过优化包被抗原浓度、探针DNA的量、抗体质量浓度等一系列条件,双酚A的线性质量分数范围在0.01~10 pg/g之间,检测低限为3.0 fg/g,4种食品模拟物中双酚A的添加回收率在82.8%~115.2%,该方法特异性好、灵敏度高,适用于食品接触材料中双酚A及其他小分子化学物的痕量迁移检测,为其迁移行为及迁移模型的建立提供了技术支撑。     

分散液相微萃取-液相色谱法测定奶瓶中的双酚A

建立了分散液相微萃取提取婴儿奶瓶中溶出痕量双酚A(BPA)的方法,并用高效液相色谱测定了其含量。奶瓶浸泡液用0.5 mL氯仿作萃取剂,0.5 mL甲醇作分散剂,以3 500 r/min离心10 min,吸取萃取剂20μL,进样,采用高效液相色谱法(HPLC)测定BPA的含量。色谱柱为Inertsil C18柱(5μm,4.6×150 mm),流动相为甲醇∶水(V∶V)=70∶30,流速为0.8 mL/min,检测波长为280 nm。该方法 BPA在0.05 mg/L~0.25 mg/L范围内线性关系良好(R=0.999 7),BPA检出限(S/N=3)为0.50μg/L。该法用于婴儿奶瓶中BPA含量的检测,测得婴儿奶瓶中双酚A的含量范围在0~18.93μg/L,平均加标回收率为96.44%,RSD为4.57%(n=4)。方法结果满意,可适用于婴儿奶瓶、矿泉水等食品和饮料容器中溶出BPA的含量测定。     

高效液相色谱紫外检测法测定纺织品中5种双酚类物质北大核心

采用高效液相色谱紫外检测法建立了纺织品中双酚类物质(双酚A、双酚B、双酚F、双酚AF和双酚S)的测定方法。样品以甲醇为溶剂,超声辅助萃取,采用ZORBAX EclipsePlus C18色谱柱分离,甲醇/水为流动相,梯度洗脱,外标法定量。研究了不同极性的萃取溶剂、提取方式、温度条件下样品中双酚类物质的提取效果,考察了不同吸收波长下目标物的灵敏度。在优化试验条件下,5种双酚类物质在质量浓度2.5~50.0μg/mL范围内与峰面积线性关系良好(R^(2)≥0.999),定量下限(S/N=10)为2.5μg/mL,不同添加水平下,双酚类物质的回收率为80.5%~100.6%,相对标准偏差(RSDs)为2.6%~5.6%。该方法操作简单,灵敏度高,适用于纺织品中5种双酚类物质的分析检测。     

高效液相色谱-质谱法测定聚碳酸酯水杯中双酚A迁移量

目的 建立高效液相色谱-质谱法(high performance liquid chromatography-mass spectrometry, HPLC-MS)测定聚碳酸酯(polycarbonate, PC)水杯中双酚A迁移量的方法。方法 选用水、4%乙酸溶液、10%乙醇和异辛烷溶液作为食品模拟液, 准确量取迁移试验中得到的食品模拟液1 mL, 通过0.22 μm微孔滤膜后, 用高效液相色谱-质谱联用仪对双酚A进行分离测定。结果 该方法相对标准偏差不大于3.24%(n=6), 回收率在87.7%~105.0%之间; 检出限为 1 μg/L。结论 该方法样品前处理方法简便, 检出限高, 操作简单, 线性关系好, 适合于PC水杯及不同塑料制品中迁移双酚A的检测分析。     

浊点萃取-高效液相色谱法测定牛奶中的 双酚A和壬基酚

目的 建立浊点萃取-高效液相色谱相结合检测牛奶中双酚A和4-n-壬基酚的分析方法。方法 应用浊点萃取(CPE)对牛奶中的双酚A和4-n-壬基酚进行萃取富集。研究确立了牛奶体积为10mL时,冰乙酸体积为200 μL,无水硫酸钠质量为0.900 g,离心参数为9917.355 g（10000 r/min）、8℃、10 min的最佳破乳条件; 最佳浊点萃取条件为: Tween 20的浓度为100g/L,无水硫酸钠的质量为0.020g,正丁醇的体积为200μL,平衡温度为60℃,平衡时间为30min。结果 双酚A在0.05-2.00mg/L,壬基酚在0.1~5.00mg/L范围内呈良好的线性关系,线性相关系数均大于0.999,双酚A的加标回收率在85.60～91.20 %之间,壬基酚在71.30~73.30%之间,RSD为3.42～9.85 %,方法的检出限分别为7.36 μg/kg、93.19μg/kg。结论 该方法具有有机试剂用量少、灵敏度高、绿色环保以及操作简单等特点, 对于牛奶中的双酚A和壬基酚有着良好的检测效果。     

Release of Bisphenol A from Polycarbonate—A Review

The release of Bisphenol A (BPA) from polycarbonate baby bottles into food and food simulants is reviewed in the perspective of the current intensive discussions on the risks of this substance. Potential factors that have been reported to influence the release of BPA are reviewed. Unlike most polymers polycarbonate is hydrolyzed under alkaline conditions by scale formation, residual alkaline detergents and boiled water. Data suggest that brushing of the bottle did not raise the release of BPA. Claims that used bottles release more BPA than new bottles and that mineral composition of the aqueous food simulant affect release could not be substantiated. There are indications that aminolysis of polycarbonate by milk and ethanolysis of polycarbonate by 50% ethanol might take place under relevant test conditions.

The relatively few migration data following the test conditions of European food contact material legislation, comply with the specific migration limit. Two test conditions were identified that reflect real use and exposure, and might cause higher release of BPA compared to the test conditions of European food contact material legislation. Further detailed studies are necessary to verify whether these two exposure scenarios are more severe.     

Migration of 2-butoxyethyl acetate from polycarbonate infant feeding bottles

An enforcement campaign was carried out to assess the migration of 2-butoxyethyl acetate (2-BEA) from polycarbonate infant feeding bottles intended for repeated use. Migration was measured by three successive migration tests into two of the European Union official food simulants: distilled water and 3% acetic acid testing at 40°C for 10 days. The Danish Veterinary and Food Administration (DVFA) has assessed that a migration above 0.33 mg for 2-BEA and a group of eight related substances kg^-1 foodstuff from plastics articles used exclusively for infants is unacceptable. Migration of 2-BEA was found from eight of 12 bottles. However, migration above the target value of 0.33 mg kg^-1 was not observed in the third decisive test from any of the 12 different brands of polycarbonate feeding bottles. A migration of between 0.05 and 0.26 mg kg^-1 from seven of 12 bottles was measured to 3% acetic acid in the third test, whereas no migration to distilled water was observed in the third test. The average recovery of 2-BEA after the 10-day exposure at the target value of 0.33 mg kg^-1 was 77% into distilled water and 36% into 3% acetic acid. The limited recovery was understandable as 2-BEA was partly hydrolysed in the aqueous food simulants and 2-butoxyethanol, a hydrolysis product and one of the related substances was identified. Quantification was carried out using gas chromatography after liquid/liquid extraction of the food simulant.     

Migration of model contaminants from PET bottles: influence of temperature, food simulant and functional barrier

To simulate post-consumer recycled plastics, selected model contaminants were incorporated into PET bottles using a time saving method. Migration into 3% acetic acid, a cola-type beverage and 95% ethanol was followed during 1 year of storage at 20 and 40°C. Aroma compounds previously found in post-consumer PET material were used as model contaminants. Benzaldehyde was found to migrate to the highest extent. Storage at 40°C affected the bottle material and this might be one reason for the high migration values of these bottles. Migration into ethanol was up to 20 times higher than into 3% acetic acid or a cola-type beverage. Bottles with a functional barrier resisted migration into food simulants even when filled with 95% ethanol and stored for 1 year at 40°C. Differential scanning calorimetry measurements showed that ethanol was interacting with the plastic material. This resulted in a lower glass transition temperature of bottles stored with ethanol compared with bottles stored empty or with other food simulants.     

Effect of amines in the release of bisphenol A from polycarbonate baby bottles

The key block for the production of polycarbonate (PC) is bisphenol A (BPA). Recent studies have proven that this monomer is able to migrate from PC baby bottles into food simulants and, although this is a polemical subject, numerous investigations indicate that BPA may have an effect on the human health. For these reasons, BPA safety regarding human exposure has recently become an alarming issue.Amines are a class of chemicals which are present in foodstuffs, such as milk. For this reason PC baby bottles, while being used, are continuously in contact with several amines, some of which are able to cause PC aminolysis, resulting in the release of BPA.In this work, 16 substances (14 with amine groups and 2 with amide groups) were tested in order to verify if they were able to increase BPA release by increasing PC depolymerization. High-performance liquid chromatography (HPLC) with fluorescence detection (FLD) and gas chromatography coupled to mass spectrometry (GC–MS) were used to quantify and identify the BPA, respectively. Although most of the substances tested did not increase the release of BPA from PC, some of them had a significant effect and high levels of this monomer were measured in the solutions. Of all of the amines tested that originating the worst case of BPA release was 1,4-diaminobutane. Also known as putrescine, 1,4-diaminobutane is a biogenic amine that results from protein degradation and it may be present in milk. In this case, BPA concentration in the solution was more than 5000 times the level found in the control sample.     

Increased migration levels of bisphenol A from polycarbonate baby bottles after dishwashing, boiling and brushing

Baby bottles are often made of polycarbonate plastic. Impurities remaining in the bottle from the monomer bisphenol A can migrate from the plastic bottles into baby food, thereby causing a health concern. Previous migration testing of new baby bottles showed only trace migration levels of the substance. In the present work, polycarbonate baby bottles were subjected to simulated use by dishwashing, boiling and brushing. Migration testing performed with both new and used bottles revealed a significant increase in migration of bisphenol A due to use. This finding might be explained by polymer degradation. Bisphenol A was determined in 200-ml samples of water food simulant by a method based on solid-phase extraction followed by gas chromatography coupled with mass spectrometry. The detection limit was 0.1 μg l^-1. Twelve different polycarbonate baby bottles were tested by filling them with hot water (100°C) for 1 h. The mean bisphenol A level from new bottles was 0.23 + -0.12 μg l^-1, while the mean levels from bottles subjected to simulated use were 8.4 + -4 μg l^-1 (dishwashed 51 times) and 6.7 + -4 μg l^-1 (dishwashed 169 times), respectively. None of the bottles released bisphenol A at levels that exceed the recently established provisional tolerable daily intake (0.01 mg kg^-1 body weight/day) in the European Union.     

Migration of bisphenol A from plastic baby bottles,baby bottle liners and reusable polycarbonate drinking bottles

Human exposure to bisphenol A (BPA) has recently received special attention. It has been shown that exposure to BPA may occur through the consumption of beverages or foods that have been in contact with polycarbonate (PC) plastic containers or epoxy resins in food packaging. A BPA migration study was conducted using a variety of plastic containers, including polycarbonate baby bottles, non-PC baby bottles, baby bottle liners, and reusable PC drinking bottles. Water was used to simulate migration into aqueous and acidic foods; 10% ethanol solution to simulate migration to low- and high-alcoholic foods; and 50% ethanol solution to simulate migration to fatty foods. By combining solid-phase extraction, BPA derivatization and analysis by GC-EI/MS/MS, a very low detection limit at the ng l^?1 level was obtained. Migration of BPA at 40°C ranged from 0.11 µg l^?1 in water incubated for 8 h to 2.39 µg l^?1 in 50% ethanol incubated for 240 h. Residual BPA leaching from PC bottles increased with temperature and incubation time. In comparison with the migration observed from PC bottles, non-PC baby bottles and baby bottle liners showed only trace levels of BPA. Tests for leachable lead and cadmium were also conducted on glass baby bottles since these represent a potential alternative to plastic bottles. No detectable lead or cadmium was found to leach from the glass. This study indicated that non-PC plastic baby bottles, baby bottle liners and glass baby bottles might be good alternatives for polycarbonate bottles.     

Migration of bisphenol A from polycarbonate baby bottles under real use conditions

Migration of the potential endocrine disrupter, bisphenol A (BPA), from 31 polycarbonate (PC) baby bottles into aqueous food simulants was studied under real repetitive use, using a sensitive and fully validated liquid chromatographic method with fluorescence detection. Confirmation of the presence of BPA was performed by liquid chromatography-mass spectrometry (LC-MS). The effects of cleaning in a dishwasher or with a brush, sterilization with boiling water and the temperature of migration were examined. It was shown that temperature was the crucial factor for the migration of BPA from the plastic bottles to water. All samples released BPA in the concentration range 2.4-14.3 µg kg^-1 when filled with boiled water and left at ambient temperature for 45 min. The decrease of BPA release in the sterilization water and in the food simulant over 12 cycles of use indicated that the hypothesis of polymer degradation in water is dubious. Estimated infantile dietary exposure, regarding the use of PC baby bottles, ranged between 0.2 and 2.2 µg kg^-1 bw day^-1, which is below the Tolerable Daily Intake of 50 µg kg^-1 bw recently established by EFSA.     

Migration of bisphenol A from polycarbonate baby bottles under real use conditions

Migration of the potential endocrine disrupter, bisphenol A (BPA), from 31 polycarbonate (PC) baby bottles into aqueous food simulants was studied under real repetitive use, using a sensitive and fully validated liquid chromatographic method with fluorescence detection. Confirmation of the presence of BPA was performed by liquid chromatography–mass spectrometry (LC–MS). The effects of cleaning in a dishwasher or with a brush, sterilization with boiling water and the temperature of migration were examined. It was shown that temperature was the crucial factor for the migration of BPA from the plastic bottles to water. All samples released BPA in the concentration range 2.4–14.3 µg kg^?1 when filled with boiled water and left at ambient temperature for 45 min. The decrease of BPA release in the sterilization water and in the food simulant over 12 cycles of use indicated that the hypothesis of polymer degradation in water is dubious. Estimated infantile dietary exposure, regarding the use of PC baby bottles, ranged between 0.2 and 2.2 µg kg^?1 bw day^?1, which is below the Tolerable Daily Intake of 50 µg kg^?1 bw recently established by EFSA.     

采用ICP-MS研究聚酯类食品包装材料中锑向食品模拟物的迁移规律

目的 建立聚酯(PET)和4种食品模拟物中锑的电感耦合等离子体质谱(ICP-MS)测定方法.用该方法研究PET中的锑向水、10％(V/V)乙醇溶液、3％(W/V)乙酸水溶液和精炼橄榄油4种食品模拟物迁移的行为与浸泡时间、温度、食品模拟物属性、锑初始含量等参数的关系.方法 在不同的温度下,将不同的PET浸泡于食品模拟物中,于一定的时间点吸取少量浸泡液,用ICP-MS测定其含量.结果 ICP-MS方法回收率在94.3％ ～96.1％之间,相对标准偏差在1.38％ ～3.31％之间.结论 锑迁出量随温度升高而增加;随着时间的延长,锑迁出量逐渐增加,一定时间后达到迁移平衡;大部分PET材料本底含量越高迁出量越高;PET中锑易于在酸性食品模拟物中迁出,应少食用PET包装的酸性食品.     

SiOx layer as functional barrier in polyethylene terephthalate (PET) bottles against potential contaminants from post-consumer recycled PET

The barrier effect of a silicon oxide (SiOx) coating on the inner surface of PET bottles, in terms of the ability to reduce the migration of post-consumer compounds from the PET bottle wall into food simulants (3% acetic acid and 10% ethanol), was investigated. The barrier effect was examined by artificially introducing model substances (surrogates) into the PET bottle wall to represent a worst-case scenario. Test bottles with three different spiking levels up to approximately 1000 mg kg(-1) per surrogate were blown and coated on the inner surface. The SiOx-coated bottles and the non-coated reference bottles were filled with food simulants. From the specific migration of the surrogates with different bottles wall concentrations, the maximum surrogate concentrations in the bottle wall corresponding to migration of 10 microg l(-1) were determined. It was shown that the SiOx coating layer is an efficient barrier to post-consumer compounds. The maximum bottle wall concentrations of the surrogates corresponding to migration of 10 microg l(-1) were in the range of 200 mg kg(-1) for toluene and approximately 900 mg kg(-1) for benzophenone. Consequently, the SiOx coating allows use of conventionally recycled post-consumer PET flakes (without a super-clean recycling process) for packaging aqueous and low alcoholic foodstuffs (under cold-fill conditions) and protects food from migration of unwanted contaminants from post-consumer PET.