陶瓷食品接触材料中铅向酸性食品模拟物迁移的规律

目的：探究贮藏时间、贮藏温度、酸性食品模拟物pH值、食品特性对陶瓷类食品接触材料中重金属铅向酸性食品模拟物迁移的影响规律。方法：通过全浸泡迁移实验并结合电感耦合等离子体发射光谱法测得在不同温度、时间条件下,重金属铅向不同pH值的乙酸、柠檬酸和乳酸溶液中的溶出量,分析重金属铅溶出量与贮藏时间、贮藏温度、食品模拟物pH值、食品特性的关系。结果：重金属铅的溶出量随时间的延长、温度的升高而增加,平均溶出速率随温度的升高而加快,在240 h、20 ℃下4%（体积分数,下同）乙酸溶液中铅的质量浓度为3.276 mg/L,在70 ℃下为52.413 mg/L,平均溶出速率则由0.087 mg/（m2·h）增加到1.229 mg/（m2·h）;铅的溶出量与食品模拟物的pH值呈负相关关系,在24 h、20 ℃下铅向pH 2.43的4%乙酸溶液和pH 1.93的20%乙酸溶液的溶出量分别为1.876 mg/L和2.412 mg/L;此外,铅的溶出量还与食品的特性有关,同样pH值条件下,含有羟基的酸性食品模拟物中铅溶出量更多。结论：贮藏时间、贮藏温度、食品模拟物pH值、食品特性都会对铅的溶出造成影响,铅的溶出量在迁移过程初期与时间的平方根呈线性关系,中后期与时间呈线性关系;铅的溶出量与温度的关系符合阿伦尼乌斯定律;与食品模拟物pH值符合对数函数关系。     

纳米二氧化钛改性LDPE薄膜中纳米钛粒子在食品模拟物中的迁移研究

为探究纳米改性LDPE薄膜中纳米钛粒子在食品模拟物中的迁移规律,根据欧盟法规(EU)NO.10/2011,分别采用蒸馏水、3%乙酸溶液(m/V)、10%乙醇溶液(V/V)、95%乙醇溶液(V/V)作为中性、酸性、脂肪性和酒精性食品模拟物,研究在不同温度条件下(40℃和70℃)纳米钛粒子的迁移情况,并研究了微波和紫外处理对迁移结果的影响。研究发现,纳米钛粒子在四种食品模拟物中的迁移量从高到低依次为:酸性食品模拟物、中性食品模拟物、酒精性食品模拟物和脂肪性食品模拟物,并且温度的升高能够促进纳米钛粒子的迁移。纳米钛粒子的迁移量范围为0.0046 mg/kg~0.61 mg/kg。此外,微波处理也能够促进纳米钛粒子的迁移,紫外处理则没有这样的促进作用。根据欧盟规定所允许的最大迁移量5 mg/kg,迁移实验表明纳米二氧化钛改性LDPE薄膜能够作为一种安全的食品包装膜。     

电感耦合等离子体质谱法测定食品接触用搪瓷制品中16种元素的迁移量

目的建立电感耦合等离子体质谱法测定食品接触用搪瓷制品中16种元素(铝、银、砷、钡、镉、钴、铬、铜、锂、锰、钼、镍、铅、锑、钒和锌)的迁移量的方法。方法以3%乙酸(w/V)作为食品模拟物提取食品接触用搪瓷制品中16种元素,利用电感耦合等离子体质谱法测定其迁移量。结果 16种元素在1～100μg/L浓度范围内性线关系良好,相关系数大于0.999,检出限为0.01～0.8μg/L,加标回收率为91.0%～109.1%,重复性测定相对标准偏差为1.0%～5.2%。对6批次样品中16种元素的迁移量进行测试,发现13种元素(铝、砷、钡、镉、钴、铬、铜、锂、锰、镍、铅、锑、和锌)有检出, 4批次样品中6种元素(砷、镉、钴、锂、镍和铅)超标。结论该方法可以准确测定食品接触用搪瓷制品中16种元素的迁移量,检测结果显示随着迁移次数的增加,元素迁移量明显降低。重金属迁移是该类产品重要的风险源。     

纸质拼图中重金属在四种人体模拟液中迁移行为的研究

建立了电感耦合等离子体原子发射光谱法(ICPAES)测定纸质拼图中可迁移重金属As、Cd、Cr、Hg、Pb、Sb、Se、Ni含量的分析方法。分别采用人工酸性汗液、人工碱性汗液、模拟胃液和模拟唾液提取纸质拼图中可迁移重金属,然后采用电感耦合等离子体原子发射光谱法测试提取液中重金属迁移量,并考察振荡频率对重金属元素迁移量的影响。结果表明,模拟胃液对重金属迁移影响最大,其次是模拟唾液,最小是人工碱性汗液;恒温水浴振荡器振荡频率越大,重金属迁移量越大,当振荡频率高于80r/min时,重金属迁移量趋于平衡。     

电感耦合等离子体发射光谱法测定食品接触用无机材料及制品中13种重金属迁移量

目的 建立一种同时检测食品接触用无机材料及制品中13种重金属迁移量(铝、砷、钡、镉、钴、铬、铜、锰、镍、铅、锑、硒与锌)的电感耦合等离子体发射光谱(inductively coupled plasma atomic emission spectrometry, ICP-AES)法。方法 采用4%(V:V)醋酸溶液, 在特定迁移实验条件下, 避光浸泡试样, 优化仪器参数和实验条件, 用电感耦合等离子体发射光谱法同时测定浸泡液中13种元素迁移量。结果 该方法检出限为0.001~0.010 mg/L, 样品的加标回收率为90.8%~105.1%, 相对标准偏差为0.96%~3.89%。结论 该方法简便、快速、高效、灵敏度高, 为食品接触用无机材料及制品中多种痕量有害元素迁移量进行合理产品风险评估提供一种高效、可行的手段。     

食品接触材料中全氟化合物的迁移规律研究

目的研究全氟化合物从食品接触材料到食品模拟物中的迁移规律。方法根据全氟化合物制品在日常生活中的使用情况,选择4个品牌的纸杯和3个品牌的包装袋进行了试验,以全氟辛酸、全氟辛烷磺酸等为研究对象,参考食品接触材料及制品迁移试验通则的具体要求,采用不同食品模拟物、不同操作方式、不同保存时间和温度等因素考察对全氟新烷磺酸、全氟辛酸的迁移量和迁移规律的影响。目标化合物通过C_(18)色谱柱进行分离,以乙腈-5 mmol/L的乙酸铵为流动相进行梯度洗脱;流速0.2 mL/min;柱温为30℃;进样量1μL,由三重四级杆质谱进行定性和定量分析。结果数据显示在模拟物为食用油时PFOA的迁移量是最大的,超过0.01 ng/cm~2;其他情况PFOA的溶出量都低于0.002 ng/cm~2; PFOS的溶出量均较少,低于0.002 ng/cm~2。结论初步得到食品接触材料中典型全氟化合物的迁移规律基础数据,说明无论是何种品牌的纸杯或是包装袋,接触食物均会产生PFOA和PFOS的微量溶出,经过膳食暴露可能会引起健康危害。     

电感耦合等离子体发射光谱法测定食品接触用搪瓷制品中11种重金属迁移量

目的 建立电感耦合等离子体发射光谱法(inductively coupled plasma atomic emission spectroscopy, ICP-AES)同时检测食品接触用搪瓷制品中11种重金属(铝、砷、钡、镉、钴、铬、锰、镍、铅、锑、锌)迁移量的分析方法。方法 采用4%(V:V)乙酸溶液, 在特定迁移试验条件下, 避光浸泡试样, 优化仪器参数和实验条件, 用电感耦合等离子体发射光谱法同时测定浸泡液中11元素迁移量。结果 方法检出限为0.001~0.010 mg/L, 样品加标回收率为92.2%~105.5%, 相对标准偏差为0.91%~3.65%。结论 方法操作简便, 准确度好, 灵敏度高、检出限低, 为食品接触用搪瓷制品中多种痕量有害元素迁移量进行合理产品风险评估提供一种高效、可行的手段。针对国标GB 4806.3-2016《食品安全国家标准搪瓷制品》中理化指标与迁移试验提出合理建议。     

ICP-MS法测定人参药材中3种重金属溶出特性的研究

目的:对比分析在人参提取过程中不同提取工艺条件下重金属铅(Pb)、总砷(As)、汞(Hg)三种元素的溶出情况。方法:采用微波消解-电感耦合等离子体质谱法分析测定由正交实验获得的人参干浸膏中重金属铅(Pb)、总砷(As)、汞(Hg)三种元素的含量。结果:实验结果表明,提取次数和提取溶剂的乙醇浓度对Pb、As的溶出量影响显著(P<0.05),对Hg的溶出量有影响但不显著,提取时间和提取液用量影响不明显。结论:在人参提取工艺过程中需要考虑提取工艺条件对Pb、As、Hg的溶出影响来选取适当的工艺条件进行制备人参提取物。     

食品接触材料中荧光增白剂VBL和APC的迁移规律研究

采用高效液相色谱法,以VBL和APC为标准物质建立了对食品包装材料中荧光增白剂的定量检测的方法。并对食品接触材料中荧光增白剂VBL和APC在纯水、乙酸、乙醇和正己烷等4种食品模拟物中的迁移规律进行了研究,研究荧光增白剂VBL和APC迁移溶出量与食品接触介质、p H、浸泡温度和处理时间等因素的关系。结果表明,荧光增白剂VBL和APC在4种食品模拟接触物中的迁移量都是VBL溶出量较多,并且随着浸泡液p H、浸泡液温度、处理时间的增加,荧光增白剂VBL和APC的迁移溶出量都出现增加的趋势。     

食品包装材料中双酚A和壬基苯酚迁移量检测方法的研究

采用高效液相色谱-荧光检测法,研究不用食品模拟物(水性、酸性、酒性、脂肪性)中双酚A和壬基苯酚迁移情况。建立了不同食品模拟物中目标物的前处理方法,各类型食品模拟物对应的标准溶液线性良好,相关系数达0.999以上,双酚A和壬基苯酚迁移测定检测的方法检出限分别为0.01 mg/kg、0.01 mg/kg(水性、酸性、脂肪性食品模拟物);0.05 mg/kg、0.05mg/kg(酒性食品模拟物)。采取升温加速试验,对样品中双酚A和壬基苯酚迁移量进行了检测,结果表明,双酚A和壬基苯酚更容易在50%乙醇和异辛烷(油脂替代物)为模拟物的情况下迁出。     

竹木筷中过氧化氢在食品模拟物中迁移量的测定及其迁移规律的研究

目的:建立过氧化氢在不同食品模拟物中的测定方法,研究竹木筷中过氧化氢在不同食品模拟物中的迁移量及其迁移规律。方法:应用分光光度法测定过氧化氢,以不同食品模拟物（水基非酸性食品模拟物、水基酸性食品模拟物、酒精类食品模拟物、油基食品模拟物）中过氧化氢的质量对吸光度建立标准曲线,以相关系数、准确度和精密度为考察指标进行方法学验证;以食品模拟物的种类、迁移时间、迁移次数和迁移温度为考察因素,初步探索竹木筷中过氧化氢在食物模拟物中的迁移规律。结果:不同食品模拟物中过氧化氢建立的标准曲线相关系数均大于0.999,加标回收率范围84%~113%,加标平行样品间相对偏差（RSD）均小于10%。相同条件下,竹木筷中过氧化氢在油基模拟物中的迁移量最小;竹木筷中过氧化氢迁移存在一段快速迁移释放过程,而后转换为长时间缓慢迁移释放;过氧化氢的迁移为长时间反复迁移过程,试验至第8次仍有过氧化氢的迁移;随着温度的升高,过氧化氢迁移量会显著增加。结论:分光光度法测定竹木筷中过氧化氢在食品模拟物中迁移量准确可靠;市场部分竹木筷在不同食品模拟物中存在不同程度的过氧化氢迁移检出;其迁移规律为长时间,反复迁移的过程,增加温度可显著提高迁移速度;100 ℃煮沸处理可有效降低竹木筷中的过氧化氢的再迁移量。     

Solubility determination as an alternative to migration measurements

Solubility values for six UV stabilisers (Cyasorb UV-1164, Tinuvin P, Tinuvin 234, Tinuvin 326, Tinuvin 327 and Tinuvin 1577) and five antioxidants (Irgafos 168, Irganox 1010, Irganox 3114, Irganox 3790 and Irganox 565) were determined in all the liquid food simulants (3% (m/V) acetic acid–water mixture, 10% (V/V), 20% (V/V), 50% (V/V) ethanol–water mixture and vegetable oil) proposed in European Union Regulation No. 10/2011/EC, as well as in fruit juice and cola drink. The applied method was obtained by modification of the method for the determination of water solubility as described in OECD guideline Test No. 105. By using ultrasonication and shorter equilibration time, the time demand of the solubility determinations were decreased notably. Solubility values proved to be lower than the specific migration limits (as specified in 10/2011/EC) at 25°C for almost all target compounds in food simulants A, B, C and D1 as well as in fruit juice and cola drink. The exceptions were Tinuvin P and Irganox 3790 in simulant D1. The solubility in food simulant D2 was higher than 1000 µg ml^–1 for all target compounds. These results show that the solubility of some additives in food simulants can be so low that it makes migration studies for certain additive–food simulant pairs dispensable.     

Comparison of the migration of melamine from melamine-formaldehyde plastics ('melaware') into various food simulants and foods themselves

A variety of melaware articles were tested for the migration of melamine into the food simulant 3% w/v acetic acid as a benchmark, and into other food simulants, beverages and foods for comparison. The results indicate that the acidity of the food simulant plays a role in promoting migration, but not by as much as might have been anticipated, since 3% acetic acid gave migration values about double those obtained using water under the same time and temperature test conditions. In contrast, migration into the fatty food simulant olive oil was not detectable and at least 20-fold lower than with the aqueous food simulants. This was expected given the solubility properties of melamine and the characteristics of the melaware plastic. Migration levels into hot acidic beverages (apple juice, tomato juice, red-fruit tea and black coffee) were rather similar to the acetic acid simulant when the same time and temperature test conditions are used, e.g. 2 h at 70°C. However, migration levels into foods that were placed hot into melaware articles and then allowed to cool on standing were much lower (6-14 times lower) than if pre-heated food was placed into the articles and then maintained (artificially) at that high temperature in the same way that a controlled time-temperature test using simulants would be conducted. This very strong influence of time and especially temperature was manifest in the effects seen of microwave heating of food or beverage in the melaware articles. Here, despite the short duration of hot contact, migration levels were similar to simulants used for longer periods, e.g. 70°C for 2 h. This is rationalized in terms of the peak temperature achieved on microwave heating, which may exceed 70°C, counterbalancing the shorter time period held hot. There was also evidence that when using melaware utensils in boiling liquids, as for stovetop use of spatulas, the boiling action of circulating food/simulant can have an additional effect in promoting surface erosion, increasing the plastic decomposition and so elevating the melamine release.     

Comparison of the migration of melamine from melamine–formaldehyde plastics (‘melaware’) into various food simulants and foods themselves

A variety of melaware articles were tested for the migration of melamine into the food simulant 3% w/v acetic acid as a benchmark, and into other food simulants, beverages and foods for comparison. The results indicate that the acidity of the food simulant plays a role in promoting migration, but not by as much as might have been anticipated, since 3% acetic acid gave migration values about double those obtained using water under the same time and temperature test conditions. In contrast, migration into the fatty food simulant olive oil was not detectable and at least 20-fold lower than with the aqueous food simulants. This was expected given the solubility properties of melamine and the characteristics of the melaware plastic. Migration levels into hot acidic beverages (apple juice, tomato juice, red-fruit tea and black coffee) were rather similar to the acetic acid simulant when the same time and temperature test conditions are used, e.g. 2?h at 70°C. However, migration levels into foods that were placed hot into melaware articles and then allowed to cool on standing were much lower (6–14 times lower) than if pre-heated food was placed into the articles and then maintained (artificially) at that high temperature in the same way that a controlled time–temperature test using simulants would be conducted. This very strong influence of time and especially temperature was manifest in the effects seen of microwave heating of food or beverage in the melaware articles. Here, despite the short duration of hot contact, migration levels were similar to simulants used for longer periods, e.g. 70°C for 2?h. This is rationalized in terms of the peak temperature achieved on microwave heating, which may exceed 70°C, counterbalancing the shorter time period held hot. There was also evidence that when using melaware utensils in boiling liquids, as for stovetop use of spatulas, the boiling action of circulating food/simulant can have an additional effect in promoting surface erosion, increasing the plastic decomposition and so elevating the melamine release.     

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。     

Migration of melamine from can coatings cross-linked with melamine-based resins,into food simulants and foods

Resins based on melamine-formaldehyde and related analogues such as methylolated melamine are used to cross-link coatings used inside food cans and on the metal closures of glass jars. Thirteen commercially coated cans and closures representing 80% of the European market were tested using simulants under realistic industrial heat-processing conditions for canned and jarred foods. The food simulants and the retort conditions used were 3% acetic acid for 1?h at 100°C and 10% ethanol for 1?h at 130°C. The highest migration level seen for melamine into simulant was 332?µg?kg^?1. There was no detectable migration of the melamine analogues cyanuric acid (<1?µg?kg^?1) or ammelide (<5?µg?kg^?1) from any sample. Twelve of the thirteen samples released no detectable ammeline (<5?µg?kg^?1) but the coating giving the highest release of melamine did also release ammeline at 8?µg?kg^?1 with the higher of the two process temperatures used. Migration experiments into food simulant and foods themselves were then conducted using two experimental coatings made using amino-based cross-linking resins. Coated metal panels were exposed to the food simulant 10% (v/v) aqueous ethanol and to three foodstuffs under a range of time and temperature conditions both in the laboratory and in a commercial food canning facility using proprietary time and temperature conditions. The highest migration into a food was 152?µg?kg^?1 from the first coating processed for a long time at a moderate sterilisation temperature. The highest migration into simulant was also from this coating at 220?µg?kg^?1 when processed at 134°C for 60?min, dropping to 190?µg?kg^?1 when processed at 123°C for 70?min. Migration from the second coating was quite uniformly two to three times lower under all tests. These migration results were significantly higher than the levels of melamine extractable using 95% ethanol at room temperature. The experiments show that commercial canning and retorting can be mimicked in an acceptable way using laboratory tests with an autoclave or a simple pressure cooker. The results overall show there is hydrolytic degradation of the melamine cross-linked resins to release additional melamine. There is a strong influence of the temperature of heat treatment applied with foods or simulants but only a minor influence of time of heating and only a minor influence, if any, of food/simulant acidity.     

Study of silver ion migration from melt-blended and layered-deposited silver polyethylene nanocomposite into food simulants and apple juice

Colloidal silver nanoparticles were prepared via chemical reduction using polyethylene glycol (PEG) as a reducing agent, stabiliser and solvent. Silver polyethylene nanocomposites were produced via two methods, namely: melt blending and layer-by-layer (LBL) deposition of silver nanoparticles onto a polyethylene film. The silver ion release from either melt-blended or LBL-deposited nanocomposites into a food simulant and apple juice during 30 days at 4°C and 40°C was determined by atomic absorption spectroscopy. The effects of incorporating or coating of silver nanoparticles, silver concentration, contact media, temperature and time on silver ion migration were evaluated using factorial design. The diffusion coefficients of silver ions into the food simulants and apple juice were calculated using the Miltz model. The results indicated that the production method of nanocomposite, silver concentration, temperature, time and contact media showed a significant effect (p < 0.05) on silver ion migration. The quantity of silver ion migration from the nanocomposites into the food simulants and apple juice was less than the cytotoxicity-level concentration (10 mg kg^?1) in all cases over 30 days. The coating of silver nanoparticles, higher silver concentration in the nanocomposite, higher temperature and acidic property of contact liquid all promoted the silver ion release from the nanocomposite films. The migration of silver ions from nanocomposites obeyed first-order diffusion kinetics.     

食品接触材料中多环芳烃在食品模拟物中的迁移规律研究

采用气相色谱-质谱联用法,对食品接触材料中多环芳烃在水、乙酸(体积分数为3%)、乙醇(体积分数为10%)和异辛烷等4种食品模拟物中的迁移规律进行了研究,研究迁移量与实验的温度、时间和模拟物属性等参数的关系。结果表明:模拟物的属性对迁移行为有显著影响,迁移量随温度的升高和时间的增加而变大。     

端视ICP-AES法测定食品用塑料包装容器在四种食品模拟物中有害元素迁移量

建立了端视电感耦合等离子体原子发射光谱(ICP-AES)法测定食品用塑料包装容器在4种食品模拟物中有害元素铅、镉、铬、砷、锑和锗迁移量的分析方法。研究了不同食品模拟物试液的处理方法以及仪器工作参数对铅、镉、铬、砷、锑和锗测定信号的影响,消除了乙醇基质的严重抑制干扰,并优化了ICP-AES测定条件。铅、镉、铬、砷、锑和锗的检出限分别为0.0025、0.00023、0.00016、0.0033、0.0032、0.0030mg/L,测定低限:以蒸馏水、3%乙酸、10%乙醇作食品模拟物时分别为0.010、0.0010、0.0010、0.010、0.010、0.010mg/L;以精制橄榄油作食品模拟物时分别为0.020、0.0020、0.0020、0.020、0.020、0.020mg/L。加标回收率在92.0%～98.8%,相对标准偏差在1.69%～7.64%(n=8)。方法灵敏、简便、快速、准确,适用于进出口食品用塑料包装容器中有害元素迁移量的快速测定。