塑料制品中酞酸酯向食品模拟物迁移的研究

为了解食品用塑料中酞酸酯类环境激素向食品迁移的规律,研究4种不同模拟食品物条件下塑料中酞酸酯类化合物的溶出量随时间、温度、振荡频率和pH的变化规律。结果表明,不同食品模拟物条件下酞酸酯的溶出量排序为异辛烷、15%乙醇、3%乙酸和水,而酞酸酯的溶出量随着时间和温度的增加而逐渐增大;随振荡频率的升高而增大,但影响不如时间、温度显著;酸性和碱性条件下,酞酸酯的溶出量明显增加。     

筷子涂层中重金属元素的暴露研究

目的研究筷子涂层中12种重金属元素(锌、铜、镍、镉、铅、汞、铬、钼、硒、砷、钡、锑)在体液模拟物和食品模拟物中的暴露。方法以胃液模拟物、唾液模拟物作为体液模拟物,以4%乙酸(V/V)、水、95%乙醇(V/V)作为食品模拟物,利用电感耦合等离子体质谱(inductively coupled plasma mass spectrometry,ICP-MS)法测定筷子涂层中12种重金属元素的溶出量和迁移量。结果对20批次筷子涂层中12种重金属元素的含量进行测试发现10种重金属元素(锌、铜、镍、镉、铅、铬、钼、硒、砷、钡)有检出,其中铅元素含量高达347660.8mg/kg。对检出的重金属元素进一步分析其在体液模拟物中的溶出量和食品模拟物中的迁移量,发现高含量的元素能通过体液模拟物溶出和食品模拟物迁移。结论筷子涂层中重金属元素可能通过3种途径暴露至人体,分别是胃液溶出、唾液溶出、食品中迁移,且涂层涂覆的位置可对重金属元素的暴露途径产生影响;胃液模拟物中溶出量是唾液模拟物中溶出量的10倍以上;4%乙酸(V/V)食品模拟物中的迁移量最多可高于水和95%乙醇(V/V)食品模拟物中的迁移量近1000倍,且随着迁移次数的增加迁移量逐渐降低。     

食品包装PE材料中荧光增白剂迁移规律的分析

以PE塑料薄膜为研究对象,采用高效液相色谱法研究食品包装塑料材料中荧光增白剂在纯水、乙酸、乙醇、植物油4?种不同模拟物中的迁移规律,研究荧光增白剂溶出量与食品接触介质、乙酸质量浓度、乙醇体积分数、浸泡温度以及处理时间等因素的关系。结果表明：纯水基质食品模拟物对香豆素类荧光增白剂有一定溶解性,酸性食品模拟物相比于水模拟物有更强的溶解性,而含醇类食品模拟物和脂肪类食品模拟物对大部分荧光增白剂都具有较好的溶解效果;荧光增白剂的溶出量随着乙酸和乙醇含量的增加而增加;较高的温度对塑料包装材料中荧光增白剂的迁移溶出具有显著影响,并且随着接触时间的延长,塑料包装材料中的荧光增白剂向食品中迁移的可能性也不断增大。     

酸性食品模拟物对金属罐甲醛迁移的适用性研究

建立食品模拟物中甲醛的迁移量和真实食品中甲醛含量的HPLC测定方法，调查了60℃、10 d迁移条件下4%(体积分数)乙酸对涂层金属罐的腐蚀情况。以环氧涂层中典型的挥发性物质甲醛为研究对象，研究了6种食品模拟物模拟21种金属罐装酸性食品的适用性。结果表明，在模拟食品长期贮存条件(60℃,10 d)下，19%的金属罐灌装乙酸溶液后发生了腐蚀；对于发生乙酸腐蚀的空罐样品，建议采用5 g/L柠檬酸作为此类产品用空罐中甲醛迁移量的食品模拟物。对于未发生乙酸溶液腐蚀的空罐样品，采用3 g/L与5 g/L柠檬酸及10%(体积分数)乙醇作为食品模拟物会导致超过80%的酸性罐装食品中甲醛含量的低估，此时推荐4%(体积分数)乙酸作为此类产品用空罐的甲醛迁移量测试的食品模拟物。     

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。     

淋膜纸杯中Al、Mg向酸性食品模拟物的迁移及数学模拟

为了研究淋膜纸杯中Al和Mg向酸性食品中的迁移规律以及数学模拟软件模拟迁移的有效性,对8种淋膜纸杯样品采用湿法消解的方法消解,之后利用电感耦合等离子体原子发射光谱(ICP-OES)检测8种淋膜纸杯中Al和Mg的初始含量及其向酸性食品模拟物(3%乙酸溶液)中迁移的量。淋膜纸杯中Al和Mg的初始含量分别为841.6～3 482.0,179.1～19 720.1mg/kg。在迁移条件为40℃/12h,8种样品中Al和Mg向3%乙酸溶液中迁移量分别为0.077～0.212,0.065～0.862mg/kg,而在70℃/8h下8种样品中Al和Mg向3%乙酸溶液中迁移量分别为0.074～0.180,0.064～2.209mg/kg,淋膜层低密度聚乙烯(LDPE)的厚度、迁移温度和时间以及纸的厚度和密度都能影响2种金属元素的迁移。使用迁移模拟软件AKTS-SML对8种淋膜纸杯样品进行迁移模拟,扩散系数采用Piringer模型,纸与LDPE之间的分配系数设置为1 000,LDPE与食品模拟物(3%乙酸)之间的分配系数设置为1,Al和Mg在40℃/12h下迁移模拟结果分别为0.760～3.075,0.162～17.750mg/kg;70℃/8h下迁移模拟结果分别为0.757～3.059,0.161～17.660mg/kg,软件模拟的迁移结果比试验所得到的都要高,迁移模拟结果在一定程度上能取代Al和Mg的迁移试验,确保消费者安全。     

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。     

微波条件下陶瓷食品接触材料中有害重金属迁移行为的研究

目的 研究微波条件下陶瓷食品接触材料中有害重金属的迁移行为。方法 向陶瓷餐具中装入乙酸溶液, 进行常规处理和微波加热处理, 最后用火焰原子吸收分光光度计检测, 研究微波功率、加热时间和迁移液pH值对陶瓷餐具中铅、镉向乙酸溶液迁移的影响, 并将该方式与常规方式作对比。结果 铅、镉的迁移量随微波功率和加热时间的增加而增大, 并基本在加热15 min后达到迁移平衡; 微波功率不但影响铅、镉的迁移速度, 还影响其达到迁移平衡时的浓度; 铅、镉的迁移量随迁移液pH值的降低而增大。结论 通过短时间的微波加热, 即可使铅、镉的迁移量达到甚至显著超出(22?2)℃温度下浸泡24 h?20 min的迁移量。     

双酚A在食品模拟物中的迁移规律研究

采用高效液相色谱法,对食品接触材料中双酚A在蒸馏水、质量浓度3%乙酸、体积分数为10%乙醇和异辛烷等4种食品模拟物中的迁移规律进行了研究,研究双酚A迁移量与试验的温度、时间、pH和模拟物属性等参数的关系。结果表明:模拟物的属性对双酚A的溶出迁移行为有显著影响,双酚A的溶出迁移量随温度的升高和时间的增加而变大。     

食品塑料包装材料中光稳定剂在食品模拟物中迁移规律的研究

建立了高效液相色谱法测定食品塑料包装材料中光稳定剂UV-9和UV-531特定迁移量的分析方法.该方法采用外标法定量,两种目标化合物在相应的范围内均具有良好的线性关系,相关系数均大于0.999,检出限均为0.5μg/L.分别选取体积分数为10％、20％和50％的乙醇溶液,以及质量分数为40 g/L的乙酸溶液和正己烷5种食品模拟物浸泡含有光稳定剂UV-9和UV-531的塑料食品包装材料,在一定的时间点取样测试浸泡液中光稳定剂含量,研究迁移量与模拟物之间的关系.结果表明,在不同食品模拟物下包装材料中光稳定剂的迁移量不同,其特定迁移量顺序为正己烷>50％乙醇溶液>20％乙醇溶液>10％乙醇溶液>4％乙酸溶液.     

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.     

Release of carbon nanoparticles of different size and shape from nanocomposite poly(lactic) acid film into food simulants

ABSTRACT

Poly(lactic) acid (PLA) film with 2 wt% mixed carbon nanofillers of graphene nanoplates (GNPs) and multiwall carbon nanotubes (MWCNTs) in a weight ratio of 1:1 with impurities of fullerene and carbon black (CB) was produced by layer-to-layer deposition and hot pressing. The release of carbon nanoparticles from the film was studied at varying time–temperature conditions and simulants. Migrants in simulant solvents were examined with laser diffraction analysis and transmission electron microscopy (TEM). Film integrity and the presence of migrants on the film surfaces were visualised by scanning electron microscopy (SEM). The partial dissolution of PLA polymer in the solvents was confirmed by swelling tests and differential scanning calorimetry (DSC). Nanoparticle migrants were not detected in the simulants (at the LOD 0.020 μm of the laser diffraction analysis) after migration testing at 40°C for 10 days. However, high-temperature migration testing at 90°C for 4 h provoked a release of GNPs from the film into ethanol, acetic acid and oil-based food simulants. Short carbon nanotubes were observed rarely to release in the most aggressive acetic acid solvent. Obviously, the enhanced molecular mobility at temperatures above the glass transition and partial dissolution of PLA polymer by the food simulant facilitate the diffusion processes. Moreover, shape, size and concentration of nanoparticles play a significant role. Flexible naked GNPs (lateral size 100–1000 nm) easily migrate when the polymer molecules exhibit enhanced mobility, while fibrous MWCNTs (> 1 μm length) formed entangled networks on the film surfaces as the PLA polymer is partly dissolved, preventing their release into food simulants. The impurities of fullerenes and CB (5–30 nm) were of minor concentration in the polymer, therefore their migration is low or undetectable. The total amount of released migrants is below overall migration limits.     

快餐包装纸中矿物油向固体食品模拟物的迁移

研究从市场上收集到的24 种快餐包装纸中的矿物油向固体食品模拟物Tenax的迁移规律。在多个不同的迁移条件（40 ℃/0.5、1、2、3 h,40 ℃/10 d和70 ℃/2 h）,探究矿物油的迁移行为及其影响因素,以评价其安全性。选择正己烷-乙醇（1∶1,V/V）混合溶液对Tenax进行过夜萃取,采用质量分数0.3%硝酸银固相萃取柱对饱和烃矿物油（mineral oil saturated hydrocarbons,MOSH）和芳香烃矿物油（mineral oil aromatic hydrocarbons,MOAH）进行分离纯化,最后用气相色谱-氢火焰离子化检测法和气相色谱-质谱法分别进行定量和定性分析。结果表明：随着温度的升高,多种快餐包装纸中矿物油向Tenax的迁移量也随之增加。涂蜡纸中MOSH迁移量均有所检出,其数值为110.49～615.40 mg/kg,而MOAH部分均未检出,这可能是因为涂蜡纸表面涂覆的石蜡层属于MOSH类,导致其MOSH部分的迁移量较高。网购餐盘纸和常规餐盘纸中MOSH迁移量约为其特定限量值（0.6 mg/kg）的10～400 倍,MOAH的迁移量约为其特定限量值（0.5 mg/kg）的10～70 倍,而使用优质胶印油墨的原生纤维餐盘纸均未超过其限量值。最后,通过对印有胶印油墨的原生纤维餐盘纸中矿物油进行溯源分析,发现经过迁移的矿物油一部分可能来源于其所用油墨,其他来源可能来自于回收纤维、黏合剂、添加剂和加工助剂等。     

微波加热对多环芳烃在食品模拟物中迁移行为的影响

采用气相色谱-质联法,研究了微波加热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%)等3种食品模拟物中迁移行为的影响。结果表明:微波加热对迁移行为有显著的影响,迁移量随加热时间的增加而增加。     

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.     

食品模拟体系中淀粉基膜材增塑剂的迁移

本文采用酯化淀粉以三乙酸甘油酯为增塑剂,经流延法制备了酯化淀粉薄膜,并利用傅里叶红外光谱衰减全反射技术(ATR-FTIR)和热重分析仪(TGA)分析了淀粉基膜材与不同食品模拟体系接触后其表层增塑剂和整体增塑剂的变化情况。结果表明,基于与淀粉基膜材、增塑剂之间的亲和性差异,食品模拟体系对淀粉基膜材产生不同的溶胀作用,导致不同程度的增塑剂迁移;与淀粉基膜材亲和性越高的食品模拟体系,对淀粉基膜材表层和内部的溶胀更迅速,并可溶解更多的增塑剂分子,从而导致淀粉基膜材中更大程度的增塑剂迁移;表层增塑剂和整体增塑剂的迁移情况差异表明,溶剂溶胀和增塑剂迁移由膜材表层向内部发生。基于以上结果可推断,在实际应用过程中,选择合适的应用领域、设计调整材料结构可主动抑制增塑剂迁移,实现这类新型包装材料的安全使用。     

Migration of silver from commercial plastic food containers and implications for consumer exposure assessment

Food storage containers with embedded silver as an antibacterial agent promise longer durability of food. For risk assessment the release of this silver into the stored food and resulting human exposure need to be known. For the purpose of exposure assessment, silver migration from commercial plastic containers with declared content of ‘nano-’ or ‘micro-silver’ into different food simulants (water, 10% ethanol, 3% acetic acid, olive oil) was quantitatively determined by ICP-MS and the form of the released silver was investigated. The highest migration of silver was observed for the acidic food simulant with 30 ng silver cm^?2 contact surface within 10 days at 20°C. In a second and third use cycle, migration dropped by a factor of up to 10, so that the maximum cumulated release over three use cycles was 34 ng cm^?2. The silver release over time was described using a power function and a numerical model that simulates Fickian diffusion through the plastic material. The released silver was found to be in ionic form, but also in the form of silver nanoparticles (around 12%). Consumer exposure to the total amount of silver released from the food containers is low in comparison with the background silver exposure of the general population, but since natural background concentrations are only known for ionic silver, the exposure to silver nanoparticles is not directly comparable with a safe background level.