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83.67%～107.05%,精密度范围为2.32%～7.67%,该方法的精密度和准确度较好,可用于食品金属罐中14种双酚类物质迁移量的检测分析。对市场上9种罐头和饮料用金属罐中的14种双酚类物质的迁移量进行了同时测定,发现有7种双酚类物质检出,无双酚A及其类似物的检出。基于欧盟限量标准要求,发现午餐肉罐头中的双酚A-（2-3-二羟基丙基）缩水甘油醚（BADGE·H₂O）、牡蛎葛根饮料中的双酚A-二（2-3-二羟基丙基）醚（BADGE·2H₂O）和黑莓罐中的双酚F-（2-3-二羟基丙基醚）（BFDGE·2H₂O）存在一定的迁移风险。此外,杀菌过程影响食品金属罐中双酚类物质的迁移种类和迁移量。迁移试验结束后,经过杀菌的金属罐中仅检测出BADGE·2H₂O,而未经杀菌的金属罐中同时检测到BADGE·2H₂O和双酚A-（3-氯-2羟丙基）（2-3-二羟基丙基）缩水甘油醚（BADGE·H₂O·HCl）。另外,食品模拟物的类型影响着双酚类物质的迁移量和迁移种类,且随着迁移温度的升高和迁移时间的增加,双酚类物质的迁移量逐渐升高直至平衡。     

快餐和早点包装中邻苯二甲酸酯类塑化剂迁移 风险的研究

目的：对快餐和早点包装中邻苯二甲酸酯类(PAEs)塑化剂迁移至食品中的风险进行评估。方法：采集42批次一次性餐盒,依据GB/T 21928-2008《食品塑料包装材料中邻苯二甲酸酯的测定》,采用气相色谱-质谱法对样品中的PAEs含量进行检测;并依据GB/T 23296.1-2009选择迁移实验浸泡条件,考查样品中PAEs的迁移风险。结果: 42批次快餐和早点包装中,共计有26批次样品中检出PAEs增塑剂,占总抽检批次的61.9%。其中24批次检出含量在0~10mg/kg范围内,最高检出含量为93.5mg/kg。迁移实验中只有含量最高的样品检出DEHP迁移量为0.06mg/kg。结论：快餐和早点包装中PAEs总体暴露水平低于100mg/kg,正常使用过程中迁移风险较小。     

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。     

快餐和早点包装中邻苯二甲酸酯类塑化剂迁移风险的研究

目的对快餐和早点包装中邻苯二甲酸酯类(PAEs)塑化剂迁移至食品中的风险进行评估。方法采集42批次一次性餐盒,依据GB/T 21928-2008《食品塑料包装材料中邻苯二甲酸酯的测定》,采用气相色谱-质谱法对样品中的PAEs含量进行检测;并依据GB/T 23296.1-2009选择迁移实验浸泡条件,考查样品中PAEs的迁移风险。结果 42批次快餐和早点包装中,共计有26批次样品中检出PAEs增塑剂,占总抽检批次的61.9%。其中24批次检出含量在0~10 mg/kg范围内,最高检出含量为93.5 mg/kg。迁移实验中只有含量最高的样品检出DEHP迁移量为0.06 mg/kg。结论 快餐和早点包装中PAEs总体暴露水平低于100mg/kg,正常使用过程中迁移风险较小。     

2019年上海市微波食品包装中邻苯二甲酸酯类塑化剂迁移风险监测

目的 评估微波食品包装中的邻苯二甲酸酯类(phthalic acid esters, PAEs)塑化剂至食品中的迁移风险进行。方法 采集90批次微波加热食品, 依据GB 31604.30-2016《食品安全国家标准 食品接触材料及制品中邻苯二甲酸酯的测定和迁移量的测定》, 采用气相色谱-质谱法(gas chromatography-mass spectrometry, GC/MS)对样品中的PAEs含量进行检测, 并考察样品中PAEs的迁移风险。结果 90批次微波加热食品包装中, 共计有18批次样品中检出PAEs增塑剂, 检出率为20%。其中15批次样品检出含量在0~10 mg/kg范围内, 最高检出含量为29.86 mg/kg。迁移实验未检出有塑化剂的迁移。结论 2019年上海市微波食品包装引入塑化剂污染的风险较低, 正常使用过程中迁移风险较小。     

浅谈牛乳中的天然苯甲酸

通过检验15户散户牛乳样品和15批乳制品,结果表明:所有牛乳样品中均检出微量苯甲酸,浓度范围(1-4)mg/kg;;乳制品样品中13批检出,液态奶样品浓度范围(4-9)mg/kg,酸乳样品浓度范围(13-21)mg/kg,2批次液态奶样品1 mg/kg。     

分散固相萃取净化-气相色谱-质谱联用法测定茶叶中7种杀螨杀虫类农药残留

目的建立茶叶中7种农药残留的快速检测方法。方法采用分散固相萃取净化,气相色谱-质谱法(gas chromatography-mass spectrometry,GC-MS)测定茶叶中噻螨酮、噻嗪酮、哒螨灵、喹瞒醚、苯醚甲环唑、联苯菊酯和氟氰戊菊酯7种农药的残留。结果 7种农药在0.05~5.00 mg/kg范围有良好的线性关系,相关系数均大于或等于0.9995。3个浓度的平均加标回收率为70%~115%,相对标准偏差为5.0%~13.2%;方法检出限(limit of detection,LOD)为0.005~0.05 mg/kg,定量限(limit of quantitation,LOQ)为0.015~0.15 mg/kg。采用此方法抽检了我国不同地区市场上的110批次的茶叶样品,其中有15批次样品检出联苯菊酯,含量在24~1640μg/kg之间;有4批次样品中检出噻嗪酮,含量在35~150μg/kg之间;3批次样品检出哒螨灵,含量在70~200μg/kg之间。结论本方法符合农药残留分析标准的要求,可用于茶叶中7种农药残留的快速检测和确证分析。     

2018年天然植物饲料原料及产品中重金属污染情况调查分析

目的 植物提取物作为天然植物饲料原料的代表因其具有抗氧化、抗病毒等作用得到广泛的开发与利用,随着药物饲料添加剂的退出,植物提取物越来越广泛的应用于畜禽、水产等养殖业中,所以有必要了解天然植物原料及产品中重金属的污染状况。方法 对北京、天津、黑龙江、江苏、安徽、江西、山东、河南、湖南、广东等10个省市采集的天然植物原料及产品样本,参照国标方法中的干法消解和压力罐消解方法对样品进行消解,然后使用火焰原子吸收光谱仪(FAAS)和原子荧光光谱仪(AFS)检测样品中砷、铅、铬、汞、镉的含量。结果 分析了100份植物饲料原料及产品,其中砷的最高值为8.54 mg/kg,大于2 mg/kg的样品所占比为4%;铅的最高值为20.33 mg/kg,大于10 mg/kg的样品只有2批次;铬的最高值为927.63 mg/kg,大于5 mg/kg的样品所占比为24%;汞的检出率为4%;全部样品中镉未检出。结论 本次调查分析发现部分样品有砷、铅、铬、汞检出,少数样品中的重金属含量相对较高,因而需加强对天然植物饲料原料及产品安全风险的监测,以保证动物和动物性产品安全。     

湖北地区市售白酒中邻苯二甲酸酯类物质的监测结果及分析

目的对湖北地区市售白酒中邻苯二甲酸脂类物质的污染水平进行分析。方法按照《国家食品污染和有害因素风险工作手册》对湖北地区9个地市销售的89份白酒样品中的邻苯二甲酸二丁酯(dibutyl phthalate,DBP)、邻苯二甲酸二(2-乙基)己酯(di 2-ethyl hexyl phthalate,DEHP)、邻苯二甲酸二异壬酯(diisononyl phthalate,DINP)等17种邻苯二甲酸酯类化合物进行监控和风险评估。结果检测的89份白酒样品中,DBP超标率为29.2%;最高浓度高达23.48 mg/kg,超出国家标准限量值(0.3 mg/kg)78倍,DEHP的浓度均未超过国家标准限量值(1.5 mg/kg),DINP均未检出,其余14种邻苯二甲酸酯类物质部分有检出。结论湖北省市售白酒中存在一定程度的邻苯二甲酸酯类物质污染,需引起重视并进行连续监测。     

超高效液相色谱-串联质谱法同时检测鸡蛋和猪肉中9种双酚-二缩水甘油醚类内分泌干扰物

目的 建立可同时检测鸡蛋和猪肉中9种双酚-二缩水甘油醚类（bisphenol-diglycidyl ether, BDGEs）内分泌干扰物的超高效液相色谱-串联质谱法。方法 样品经磷酸盐缓冲液稀释后,用0.1%甲酸乙腈溶液进行提取,然后用正己烷除脂,Oasis PRiME Hydrophilic–Lipophilic Balance (HLB)固相萃取柱净化,在电喷雾电离正离子模式下使用超高效液相色谱-串联质谱仪进行检测,内标法定量。结果 鸡蛋和猪肉样品中9种BDGEs类物质在0.5~100 μg/kg浓度范围内线性关系良好,相关系数（r2）≥0.99。方法的检出限为0.1~0.5 μg/kg,定量限为0.5~1 μg/kg;在定量限、2、10 μg/kg三个添加水平下,鸡蛋和猪肉样品中9种BDGEs类物质的平均回收率为80.16%~110.26%,日内变异系数为2.13%~11.15%,日间变异系数为7.24%~18.62%。采用该方法对28份市售鸡蛋样品进行分析,10批次样品中检出BADGE·2H2O,检出率为35.71%,含量为0.020~6.45 μg/kg。4批次样品中检出BADGE·HCl·H2O,检出率为14.29%,含量为0.26~0.42 μg/kg。结论 本方法具有较高的灵敏度和准确度,适用于动物性食品中9种BDGEs类内分泌干扰物残留量的同时检测和准确定量。     

杭州市场罐头类食品的双酚A污染调查及其膳食风险评估

目的:调查检测市场上罐头类食品的双酚A含量,明确其膳食暴露风险。方法:在杭州超市采集各类罐头食品样品93个,采用高效液相色谱法测定双酚A含量,采用点评估方法评估其膳食暴露风险。结果:罐头样品双酚A的检出率为29%,平均值为121.7μg/kg,最大值为2 840μg/kg,其中油性的鱼、肉和蔬菜类罐头双酚A含量较高;一般人群来源于罐头食品的双酚A膳食暴露量为0.04—0.20μg/(kg·bw)/d,占TDI的0.4%—2.0%。结论:油性的鱼、肉和蔬菜类罐头食品双酚A含量显著高于饮料和粥类罐头食品;在没有其他重大的暴露来源时,各类人群以罐头类食品为主的双酚A膳食暴露均在可接受的范围内。     

Intake of bisphenol A from canned beverages and foods on the Belgian market

Bisphenol A (BPA), a contaminant which may be present in the coating of cans, was determined in 45 canned beverages and 21 canned food items from the Belgian market. Beverages had an average BPA concentration of 1.0 ng/ml, while canned foods had a higher average concentration of 40.3 ng/g. The amount of BPA present in food items was dependent on the type of can and sterilisation conditions rather than the type of food. For example, BPA was not detected in non-canned beverages (<0.02 ng/ml), while non-canned food items had a very low average concentration of 0.46 ng/g. Using detailed information from the Belgian food consumption survey, the BPA intake of adults through canned foods and beverages was estimated to be 1.05 µg/day or 0.015 µg/kg body weight/day (assuming an average adult weight of 70 kg). Intake assessments, based on urinary metabolite concentrations from the literature, resulted in slightly higher BPA intakes (range 0.028–0.059 µg/kg body weight/day). This suggests that sources other than canned foods and beverages contribute to BPA exposure in humans.     

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.     

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.     

Survey of bisphenol A and bisphenol F in canned foods.

Bisphenol A (BPA) and bisphenol F (BPF) have been determined in a range of canned foods. Sixty-two different canned foods were purchased from retail outlets in the UK from January to November 2000 and the contents extracted and analysed by GC-MS for BPA and BPF isomers. The following canned products were analysed: fish in aqueous media, 10 samples; vegetables, 10; beverages, 11; soup, 10; desserts, five; fruit, two; infant formula, four; pasta, five; and meat products, five. BPF isomers were not detected in any of the canned foods with detection limits of 0.005 mg kg(-1) for the 2,2' and 2,4' isomers and 0.01 mg kg(-1) for the 4,4' isomer. BPA was detected in 38 samples with a detection limit of 0.002 mg kg(-1). Of these, BPA was quantified in 37 canned foods at levels from 0.007 mg kg(-1), with one sample of meat containing a mean level of 0.38 mg kg(-1). All other samples contained <0.07 mg kg(-1) BPA.     

Comparison of four analytical techniques based on atomic spectrometry for the determination of total tin in canned foodstuffs

Different techniques for the determination of total tin in beverages and canned foods by atomic spectrometry were compared. The performance characteristics of inductively coupled plasma-mass spectrometry (ICP-MS), hydride generation-inductively coupled plasma-atomic emission spectrometry (HG-ICP-AES), electrothermal atomisation-atomic absorption spectrometry (ETA-AAS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES) were determined in terms of linearity, precision, recovery, limit of detection, decision limit (CCα) and detection capability (CCβ) (Decision 2002/657/EC). Calibration ranges were covered from ng l?1 to mg l?1 level. Limits of detection that ranged from 0.01, 0.05, 2.0 to 200 μg l?1 were reached for ICP-MS; HG-ICP-AES; ETA-AAS and ICP-AES, respectively. Precision, calculated according to ISO 5725-2 for repeatability and within-laboratory reproducibility and expressed as relative standard deviation (RSD), ranged from 1.6% to 4.9%; and recovery, based on Decision 2002/657/EC, was found to be between 95% and 110%. Procedures for the mineralisation or extraction of total tin were compared. Wet digestion, sequentially, with nitric acid and hydrogen peroxide provided the best results. The influence of possible interferences present in canned food and beverage was studied, but no interference in the determination of tin was observed. Since maximum levels for tin established by European Union legislation vary from 50 mg kg?1 in canned baby foods and infant foods up to 200 mg kg?1 in canned food, ICP-AES was chosen as the preferred technique for routine analysis thanks to its good precision, reliability and ease of use. The accuracy of this routine method was confirmed by participation in six proficiency test schemes with z-scores ranging from -1.9 to 0.6. Several canned foodstuffs and beverage samples from a local market were analysed with this technique.     

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。     

鱼类罐头相关食品标准法规中组胺指标探讨

目的探讨鱼类罐头相关食品标准法规中组胺指标,为GB 7098—2015《食品安全国家标准罐头食品》中鱼类罐头组胺指标修订提供基础数据。方法整理分析国内外法规情况、我国水产品及其制品组胺中毒情况,统计分析广东省市售高组胺鱼类罐头中组胺含量、广东省成人居民鱼类罐头消费量数据及组胺参考限量值。结果我国的鱼类罐头(仅适用于鲐鱼、鲹鱼、沙丁鱼罐头)组胺限量标准为1 000 mg/kg,高于国际组织和国外的组胺限量标准;1998—2018年我国水产品及其制品组胺中毒报道案例共18例,引起组胺中毒食物检测含量最低为120 mg/kg,最高为3 820 mg/kg;广东省主要鱼类罐头生产地区采集鱼类罐头样品136份,组胺含量范围为未检出(ND)～488.8 mg/kg,组胺含量超过200 mg/kg的占3.7%(5/136),超过400 mg/kg的占1.5%(2/136);基于广东省成人居民鱼类罐头高消费人群(P97.5)消费量为120 g/次和无作用剂量(NOAEL,50 mg)得出鱼类罐头组胺参考限量值为417 mg/kg。结论 GB 7098—2015鱼类罐头组胺指标限量值高,测定鱼品种少,建议我国开展高组胺鱼类罐头组胺风险评估,修订该标准鱼类罐头组胺指标。     

Exposure assessment of caffeine in children’s snacks in Korea

This study was conducted to develop an appropriate management strategy for the safe consumption of children’s snacks. In this study, a caffeine content analysis was performed on children’s snacks which were distributed at stores located near to schools. A total of 213 samples (63 chocolates, 40 ice cakes, 19 canned instant coffees, and 91 beverages) were analyzed for caffeine content. The caffeine content of chocolates, ice cakes, canned instant coffees, and beverages was 94.30, 35.03, 391.78, and 68.32 mg/kg, respectively. The results of the exposure assessment for caffeine were expressed as estimated daily intake (EDI) compared to the acceptable daily intake (ADI). The EDI/ADI ratio of the high risk group (95^th percentile) for caffeine intake was 7.63–27.13 %. The results of this study indicate that the EDI of caffeine from snacks sold at stores located near to schools is much lower than the ADI in general. Consequently, children’s snacks are thought to be safe for consumption.     

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。