基于确定性迁移模型研究聚乙烯食品接触材料中紫外吸收剂的迁移规律

目的 研究不同条件下低密度聚乙烯(Low density polyethylene,LDPE)食品接触材料中3种紫外吸收剂[2-(2′-羟基-5′-甲基苯基)苯并三唑(UV-71]、2-羟基-4-甲氧基苯并苯酮(UV-9)、2-羟基-4-正辛氧基苯并苯酮(UV-531))的迁移,基于确定性迁移模型得出吸附扩散的重要参数—分配系数和扩散系数,并研究其迁移规律。方法 采用双螺杆挤出机将LDPE粉料和3种紫外吸收剂混合并挤出造粒后,在175 ℃～180 ℃,70 Pa下,注塑为膜。针对高浓度酒精类食品生产加工储运场景,采用50%、70%、95%乙醇作为食品模拟物,在20 ℃、40 ℃、60 ℃下进行迁移试验。用超高效液相色谱仪测定不同时间点紫外吸收剂的迁移量,根据Piringer模型对数据进行拟合,得出扩散系数和分配系数,研究温度、食品模拟物、紫外吸收剂含量对迁移的影响。结果 温度对迁移影响最大,随着温度升高紫外吸收剂扩散系数增加,分配系数降低;乙醇含量对紫外吸收剂的扩散系数影响不显著,而随着乙醇含量的增加分配系数逐渐减小;紫外吸收剂的含量对迁移影响最小,扩散系数和分配系数变化不明显(除UV-71的分配系数随含量的增加而降低)。结论 采用Piringer 确定性模型研究LDPE中3种紫外吸收剂向高浓度酒精类食品模拟物迁移的扩散系数和分配系数,为食品接触材料中紫外吸收剂的风险评估提供了有效方法。     

影响Scathard-Hildebrand统计热力学理论预测PVC中增塑剂迁移平衡分配系数的因素

为探究Scathard-Hildebrand热力学模型对PVC塑料中有害物迁移预测的适用性和准确性。搜集相关文献中有效迁移实验数据,将计算得出的分配系数实验值Fexp与模型预测分配系数模拟值Fsim进行对比,并探讨温度、迁移物分子量、迁移物醇-水分配系数、模拟液特性等因素对分配系数校正值(模拟值与实验值之比的对数值ln(Fsim/Fexp))的影响。结果表明,PVC材料中迁移物分配系数校正值ln(Fsim/Fexp)与以上几种因素均存在着一定的线性关系。影响因素的分析可为预测模型的修正提供有力的依据。     

影响聚丙烯塑料中抗氧剂BHT向食品中迁移规律因素研究

目的为降低食品包装材料对食品的污染风险,研究影响2,6-二叔丁基-4-甲基苯酚(butylated hydroxytoluene,BHT)向食品中迁移规律的因素并有效预测迁移量。方法研究了含BHT的聚丙烯母料的比表面积和模拟液的溶解度参数对BHT向模拟液中迁移规律的影响,并把Scatchard-Hilderbrand热力学理论模型预测平衡分配系数(D_(r0))与实验值(D_r)进行比较分析。结果模拟中BHT的浓度(C_t)与浸泡时间(t)符合C_t=a×(1-e~(-b×t))方程式,且塑料比表面积越大,迁移速率和迁移平衡分配系数(模拟液/塑料)越大;平衡分配系数(D_r)与比表面积(S)符合方程lnD_r=-2.944+2.157e~(-53.6S),平衡分配系数实验值与Scatchard-Hilderbrand热力学理论模型计算值随模拟液的溶解度参数变化趋势基本一致,实验值与计算值的比值随模拟液与聚丙烯的溶解度参数差值减小而增大。结论塑料的比表面积和模拟液的极性对Scatchard-Hilderbrand热力学理论预测聚丙烯中BHT向模拟液中迁移平衡分配系数有一定的影响,在向溶解度参数为7.0~13.0(cal/cm~3)~0.5范围内的模拟液中平衡分配系数的预测均有良好的适用性。     

热力学数学模型对塑料中化学物向食品模拟液中迁移平衡时分配系数的预测研究

目的分配系数能够直接反映出塑料包装材料中有害化学物向食品迁移的水平,研究分配系数与塑料包装材料、迁移物及食品(模拟物)三者之间的关系有重要意义。方法以Scatchard-Hildebrand统计热力学理论为基础,从热力学平衡角度分析了化学物在包装材料/食品体系中的迁移和分配过程,建立了一个预测化学物迁移平衡时分配系数的热力学数学模型。通过所建立的初级数学模型对聚乙烯薄膜中四种抗氧化剂,即2,6-二叔丁基-4-甲基苯酚(BHT)、二丁基羟基茴香醚(BHA)、Irganox1010和Irganox1076向脂肪类食品模拟物异辛烷迁移平衡时状态进行模拟计算,并与已公开发表的实验数据进行了对比。结果聚乙烯薄膜中四种抗氧剂向异辛烷中迁移平衡的分配系数模拟值与实验值随温度变化趋势一致。结论该热力学模型符合迁移理论,对PE/抗氧剂/脂肪类食品体系分配系数的预测有一定的适用性。     

模拟液的极性对聚丙烯中抗氧化剂迁移的影响

研究了4种抗氧化剂BHA、BHT、Irganox1076、Irgafos168从聚丙烯塑料迁移至6种不同极性的模拟液时,模拟液极性对抗氧化剂迁移规律的影响。结果表明,抗氧化剂与聚丙烯塑料相溶性越差,与模拟液相溶性越好,迁移平衡分配系数越大;同时,模拟液极性越接近聚丙烯时,迁移扩散系数越高,扩散系数受分子量影响越小,反之,则迁移扩散系数受分子量影响较大,扩散系数随分子量的增大而减小;无水乙醇模拟液中,抗氧化剂分子量越大,平衡分配系数受温度影响越大,迁移焓变随分子量增大而增大,而正己烷模拟液中变化正好与之相反。     

Scatchard-Hildebrand热力学模型在预测PE中有害物质迁移分配系数的应用

为更加准确预测PE塑料中化合物向食品中迁移的分配系数。以PE中抗氧剂为代表,从大量文献中筛选PE中有害迁移物向食品模拟液迁移测试的可靠实验数据,将分配系数实验值F_(exp)与模型预测分配系数计算值F_(sim)对比分析,并对Scatchard-Hildebrand热力学模型进行实验校正,研究了温度(T)、迁移物分子量(M)和醇-水分配系数(log P)以及模拟液极性(ln Ps)与修正系数Ks(Ks=ln(F_(sim)/F_(exp))的关系。结果表明除个别化合物因其分子结构特殊外,PE中化学物向脂肪类食品模拟液中迁移分配系数预测模型的修正系数Ks与M、log P、ln Ps均呈显著的线性相关性,得到修正后的Scatchard-Hildebrand热力学模型F'_(sim)=exp(V迁移物/RT·[φ_(模拟液)~2(δ_(迁移物)-δ_(模拟液))~2-φ_(聚合物)~2(δ_(迁移物)-δ_(聚合物))~2]-7.289-0.021M-1.317ln Ps+0.901log P),其在一定程度上能够预测PE中有害物质向脂肪类食品模拟物中迁移的分配系数。     

基于有限差分法的食品包装材料不稳定性数值模拟

基于有限差分方法数值模拟了塑料食品包装材料化学物向食品(模拟物)的迁移及迁移物在食品内的不稳定性。利用数值计算软件Matlab进行数值模拟得出了不同损耗模式下的迁移预测曲线。结果表明,扩散系数D决定了迁移的动力学过程,分配系数K_(PF)表征平衡时化学物在包装材料和食品内的浓度比值,平衡时食品内的化学物浓度随化学物在包装材料内的初始浓度C_(in)的增加而增加。化学迁移物在食品内存在不稳定现象,这将导致实验结果低估其向食品的迁移。利用损耗函数得到了2种不同损耗模式下的迁移预测曲线。     

影响聚丙烯塑料中抗氧剂BHA向食品中迁移规律因素研究

食品包装材料中有害化学物的迁移是污染食品和危害人们身体健康的主要途径之一,研究影响有害物质向食品中迁移规律的因素可有效降低食品包装材料对食品的污染风险。试验研究了含BHA的聚丙烯母料的比表面积和模拟液的溶解度参数对BHA向模拟液中迁移规律的影响,并把Scatchard-Hilderbrand热力学理论模型预测平衡分配系数(D_(r0))与试验值(D_r)进行比较分析,研究结果表明:模拟液中BHA的浓度符合C_t=a(1-e~(-b t))方程式,且塑料比表面积越大,迁移速率和迁移平衡分配系数(模拟液/塑料)越大,同时模拟液的溶解度参数与塑料的溶解度参数差值越小,其迁移速率越大,迁移平衡分配系数的试验值与Scatchard-Hilderbrand热力学理论模型计算值越接近。     

快餐和巧克力包装纸中矿物油迁移行为的研究

为研究快餐和巧克力包装纸中矿物油向食品中的迁移行为,选取3种不同的食品包装纸分别置于水、4%乙酸溶液、10%乙醇溶液、95%乙醇溶液和固体Tenax TA中,通过气相色谱检测食品模拟物中矿物油的含量,分析温度和时间对矿物油迁移率的影响,建立迁移模型。结果表明,迁移温度越高,接触时间越长,五种食品模拟物中矿物油迁移率越大;在五种食品模拟物中矿物油迁移率大小顺序为：95%乙醇>Tenax TA>10%乙醇>4%乙酸>水;分配系数K_P/F的数值随温度升高而减小,扩散系数D与之相反。该迁移试验和迁移模型的建立可更好地预测快餐和巧克力包装纸中矿物油的迁移趋势。     

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。     

Determination of the mass transport properties of chemical additives in polypropylene material/simulated food system

The mass transport process (migration) of five additives from three different types of polypropylene (PP) films into selected food simulants was studied. The migration tests were carried out at different time-temperature conditions, and the concentration of additives in polymer matrix and food simulants were analysed by high-performance liquid chromatography (HPLC). With all data, the mass transport properties for migration kinetics (partition and diffusion coefficients) were determined. Results showed that the partition coefficient was affected significantly by the temperature and simulants’ properties, whereas little affected by the types of PP film and molecular weight of substance. The polarity, structure and shape of substances can also have an influence in their partition between the polymer matrix and food simulants. Additionally, comparison results between the experimental diffusion coefficients and the calculated values by Piringer model suggested that the current migration model with the default modelling parameters for PP does not describe realistically the diffusion coefficients of additives. The calculated diffusion coefficients were greater than the experimental values, as a consequence, the migration of chemical additives will be overestimated. For more realistic migration calculations, more accurate modelling parameters in Piringer model should be established and the effect of food on migration should be high interest in future work.     

Determination of key diffusion and partition parameters and their use in migration modelling of benzophenone from low-density polyethylene (LDPE) into different foodstuffs

The mass transport process (migration) of a model substance, benzophenone (BZP), from LDPE into selected foodstuffs at three temperatures was studied. A mathematical model based on Fick’s Second Law of Diffusion was used to simulate the migration process and a good correlation between experimental and predicted values was found. The acquired results contribute to a better understanding of this phenomenon and the parameters so-derived were incorporated into the migration module of the recently launched FACET tool (Flavourings, Additives and Food Contact Materials Exposure Tool). The migration tests were carried out at different time–temperature conditions, and BZP was extracted from LDPE and analysed by HPLC-DAD. With all data, the parameters for migration modelling (diffusion and partition coefficients) were calculated. Results showed that the diffusion coefficients (within both the polymer and the foodstuff) are greatly affected by the temperature and food’s physical state, whereas the partition coefficient was affected significantly only by food characteristics, particularly fat content.     

Evaluation of a predictive mathematical model of di-(2-ethylhexyl) adipate plasticizer migration from PVC film into foods

The diffusion coefficient of the plasticizer di-(2-ethylhexyl)adipate (DEHA) in Cheddar cheese (Df) was determined by measuring the extent to which DEHA penetrated cheese that was placed in intimate contact with artificially DEHA-contaminated cheese. Slices (20 microns) of cheese from the boundary layer, into which DEHA had migrated, were microtomed at -40 degrees C, and analyzed for DEHA by gas chromatography (GC). Mean values of Df determined by graph fitting experimental and calculated data were 1.5 x 10(-9) cm2 s-1 at 5 degrees C and 3.0 x 10(-8) cm2 s-1 at 25 degrees C. The partition coefficient (K) of DEHA between cheese and PVC film was derived from the partition coefficients of DEHA between acetonitrile (ACN) and cheese lipid, ACN and cheese solid, and ACN and PVC film. The mean values of K between cheese and PVC film were estimated to be 0.70 at 5 degrees C and 0.58 at 25 degrees C. The estimated values of Df and K were then used in a mathematical model (Till et al. 1982) to predict migration levels of DEHA into cheese. Good agreement with previously published experimental data was obtained. Extrapolation of the prediction of DEHA migration into fatty foods, such as salami and avocado, was also successful (ratio of experimental to predicted results within a factor of two). The values of Df and K for cheese are, however, inappropriate for modelling non-fatty foods such as meat, cakes, fruit and vegetables. Predicted values for these foods were typically 3-10-fold too high. More accurate predictions would probably be obtained if values of Df more relevant to these foods are used. The predictions were relatively insensitive to the value of K.     

Buckminsterfullerene's (C60) octanol-water partition coefficient (Kow) and aqueous solubility

To assess the risk and fate of fullerene C60 in the environment, its water solubility and partition coefficients in various systems are useful. In this study, the log Kow of C60 was measured to be 6.67, and the toluene-water partition coefficient was measured at log Ktw = 8.44. From these values and the respective solubilities of C60 in water-saturated octanol and water-saturated toluene, C60's aqueous solubility was calculated at 7.96 ng/L(1.11 x 10(-11) M) for the organic solvent-saturated aqueous phase. Additionally, the solubility of C60 was measured in mixtures of ethanol-water and tetrahydrofuran-water and modeled with Wohl's equation to confirm the accuracy of the calculated solubility value. Results of a generator column experiment strongly support the hypothesis that clusters form at aqueous concentrations below or near this calculated solubility. The Kow value is compared to those of other hydrophobic organic compounds, and bioconcentration factors for C60 were estimated on the basis of Kow.     

复合包装中VOCs的迁移模型

本文将复合包装材料的结构分为材料层、边界层、聚集层和材料分界层,分别讨论了VOCs在每层中的迁移过程,并依据VOCs在层到层间的迁移应遵循质量守恒的原理,获得了VOCs迁移的综合模型.进一步通过实验和模型拟合得到了VOCs的迁移规律,并发现VOCs的迁移量随着放置时间的增加而减少,并逐渐趋于平衡;VOCs的迁移率与温度有关,温度越高,VOCs的迁移率就越高.     

Effects of chain length, chlorination degree, and structure on the octanol-water partition coefficients of polychlorinated n-alkanes

Log octanol-water partition coefficients (log Kow) of 40 synthesized polychlorinated n-alkanes (PCAs) with different chlorination degrees were determined using reversed-phase high performance liquid chromatography (RP-HPLC). In addition, log Kow values of a technical mixture namely Cereclor 63L as well as 15 individual in house synthesized C10, C11, and C12 chloroalkanes with known chlorine positions were estimated. Based on these results, the effects of chain length, chlorination degree, and structure were explored. The estimated log Kow values ranged from 4.10 (polychlorinated n-decanes with 50.2% chlorine content) to 11.34 (polychlorinated n-octacosanes with 54.8% chlorine content) for PCAs and from 3.82 (1,2,5,6,9,10-hexachlorodecane) to 7.75 (1,1,1,3,9,11,11,11-octachlorododecane) for the individual chloroalkanes studied. The results showed that log Kow value was influenced linearly at a given chlorine content by chain length, while a polynominal effect was observed in dependence on the chlorination degree of an alkane chain. Chlorine substitution pattern influenced markedly the log Kow value of chloroalkanes.     

Partitioning of fluorotelomer alcohols to octanol and different sources of dissolved organic carbon

Interest in the environmental fate of fluorotelomer alcohols (FTOHs) has spurred efforts to understand their equilibrium partitioning behavior. Experimentally determined partition coefficients for FTOHs between soil/water and air/water have been reported, but direct measurements of partition coefficients for dissolved organic carbon (DOC)/water (K(doc)) and octanol/ water(K(ow)) have been lacking. Here we measured the partitioning of 8:2 and 6:2 FTOH between one or more types of DOC and water using enhanced solubility or dialysis bag techniques, and also quantified K(ow) values for 4:2 to 8:2 FTOH using a batch equilibration method. The range in measured log K(doc) values for 8:2 FTOH using the enhanced solubility technique with DOC derived from two soils, two biosolids, and three reference humic acids is 2.00-3.97 with the lowest values obtained for the biosolids and an average across all other DOC sources (biosolid DOC excluded) of 3.54 +/- 0.29. For 6:2 FTOH and Aldrich humic acid, a log K(doc) value of 1.96 +/- 0.45 was measured using the dialysis technique. These average values are approximately 1 to 2 log units lower than previously indirectly estimated K(doc) values. Overall, the affinity for DOC tends to be slightly lower than that for particulate soil organic carbon. Measured log K(ow) values for 4:2 (3.30 +/- 0.04), 6:2 (4.54 +/- 0.01), and 8:2 FTOH (5.58 +/- 0.06) were in good agreement with previously reported estimates. Using relationships between experimentally measured partition coefficients and C-atom chain length, we estimated K(doc) and K(ow) values for shorter and longer chain FTOHs, respectively, that we were unable to measure experimentally.     

Characterizing the migration of antioxidants from polypropylene into fatty food simulants

The migration (diffusion and equilibrium) processes of antioxidants (AOs) from polypropylene (PP) films of different thicknesses into n-heptane and 95% ethanol as fatty food simulants were analysed at 20, 37 and 60°C. Heptane fully extracted the AOs from the polymer while a partition equilibrium described the migration to ethanol. The kinetics of migration were also studied via the diffusion coefficients. As expected, diffusion was found to be faster when the polymer was in contact with heptane, due to polymer swelling by the solvent. The kinetics of the process in ethanol was described by different theoretical expressions which are discussed. Equations disregarding partition equilibrium failed to describe the process and the diffusion coefficient values obtained through them were much smaller than the actual ones and dependent on film thickness. The results also showed the significance of food simulant selection in the analysis of food-packaging interactions and migration variability with thickness.     

Migration of antimony from PET trays into food simulant and food: determination of Arrhenius parameters and comparison of predicted and measured migration data

Migration experiments with small sheets cut out from ovenable PET trays were performed in two-sided contact with 3% acetic acid as food simulant at various temperatures. The fraction of diffusible antimony (Sb) was estimated to be 62% in the PET sample under study. Apparent diffusion coefficients of Sb in PET trays were determined experimentally. Measurement of migration between 20 and 150°C yielded a linear Arrhenius plot over a wide temperature range from which the activation energy (E _a) of 188?±?36?kJ?mol^?1 and the pre-exponential factor (D ₀) of 3.6?×?10¹⁴?cm²?s^?1 were determined for diffusing Sb species. E _a was similar to previously reported values for PET bottles obtained with a different experimental approach. E _a and D ₀ were applied as model parameters in migration modelling software for predicting the Sb transfer in real food. Ready meals intended for preparation in a baking oven were heated in the PET trays under study and the actual Sb migration into the food phase was measured by isotope dilution ICP-MS. It was shown that the predictive modelling reproduces correctly experimental data.