包装纸中丙烯酰胺及芳香胺迁移量的检测研究

目的建立同时测定包装纸中丙烯酰胺和6种芳香胺迁移量的检测方法。方法通过筛选固相萃取小柱种类,优化净化方法和液相色谱条件,从而形成丙烯酰胺和6种芳香胺迁移量的固相萃取-高效液相色谱检测方法。结果丙烯酰胺在0.2~20 mg/L的浓度范围内线性关系良好(R2=0.9989),检测波长为220 nm,检出限为0.01 mg/L;芳香胺在0.2~20 mg/L的浓度范围内线性关系良好(R20.998),检测波长为240和280 nm,检出限也为0.01 mg/L。纯水样品中,各化合物的加标回收率在90%以上,相对标准偏差为2.3%~5.9%。实际样品中,芳香胺的加标回收率在86.9%以上,相对标准偏差为2.0%~6.1%;丙烯酰胺的加标回收率为78.7%~81.9%,相对标准偏差为4.2%~6.2%。结论该方法处理步骤简单,分离效果好,精密度高,从提高检测效率、节约成本的角度来看,该方法值得推广成为常规检测方法。     

基于GC-MS/MS法测定食品包装纸中24种有害物质

目的 利用气相色谱串联质谱联用仪（GC-MS/MS）建立食品包装纸中24种有害物质（17种邻苯二甲酸酯（PAEs）和7种多氯联苯（PCBs））同时测定的方法。方法 样品处理后准确加入30 mL异丙醇和内标溶液,超声萃取40 min,使用气相色谱串联质谱仪进行检测,并采用内标法定量。结果 在0.02~1.0 μg/mL范围内,24种化合物的拟合曲线线性良好,相关系数R2在0.9945~1.0000之间,方法检出限和定量限分别为0.0005~0.0028 mg/L和0.0016~0.0089 mg/L,6种不同品牌的食品包装纸种的最高残留量为26.53 mg/kg。对24种化合物进行低、中、高3个水平浓度的加标回收试验,发现平均回收率在85.6%~109.7%之间,日内和日间的相对标准偏差分别小于6%（n=5）和9%（n=3）,回收率、重复性及精密度良好。结论 该方法简便、快速、结果准确可靠,适用于同时测定食品包装纸中24种有害物质,是一种高通量测试方法。     

干性食品包装纸中重金属迁移量测定影响因素的系统研究

建立了溶剂浸泡-石墨炉原子吸收光谱法测定干性食品包装纸中重金属铅、砷、镉、铬和镍溶出量的测定方法,优化确立了溶剂种类、试验质量、乙酸浓度、提取温度和提取时间等因素对迁移量的影响。结果表明:各元素的检测限分别为0.0172,0.0235,0.0021,0.0735,0.0645mg/kg,加标回收率分别在88.0%～92.4%,93.4%～108.9%,107.1%～121.3%,94.5%～106.9,99.8%～123.0%,精密度RSD分别为6.89%,3.55%,21.46%,1.32%,5.00%,表明此方法能够满足对干性食品包装纸中重金属迁移量的测定。     

食品接触材料中壬基酚和辛基酚的测定与风险分析

目的研究食品接触材料中壬基酚和辛基酚的含量和迁移量的情况,并分析食品暴露风险。方法采用液相色谱-质谱联用法建立食品接触材料中壬基酚和辛基酚含量和迁移量的检测方法,并对相关检测数据进行统计分析。结果在优化条件下,壬基酚和辛基酚在5~200μg/L范围内线性关系良好,相关系数均大于0.999,壬基酚和辛基酚含量和迁移量的检测方法定量下限分别为0.1 mg/kg和10μg/kg,在添加水平为10,100,200μg/L时,样品中壬基酚和辛基酚含量的平均加标回收率为85.6%~89.2%,迁移量的回收率为94.3%~100.6%,相对标准偏差均小于15%。对30批次保鲜膜和复合包装袋样品进行检测,结果显示,6批次样品检出壬基酚或辛基酚,占总体样品的20%;其中1批次样品检出壬基酚迁移量,占阳性样品的16.7%。结论保鲜膜和复合包装袋可能含有壬基酚和辛基酚,且容易迁移到食品模拟物中,迁移量随着温度的升高和时间的延长而增加。保鲜膜和复合包装袋中的壬基酚和辛基酚存在一定风险,应引起足够重视。     

高效液相色谱法测定镀膜金属罐水基模拟物中的游离苯酚

建立了基于高效液相色谱-荧光检测器的食品用金属罐中游离苯酚的测定方法。在0. 001mg/L～0. 20mg/L范围内,方法线性关系良好,相关系数为0. 9999,加标回收率为98. 52%～110. 11%,平均回收率为104. 08%,精密度相对标准偏差为6. 0%(n=8),方法检出限为0. 0012mg/L,定量限为0. 005mg/L。方法简便、快捷,灵敏,适用于食品用金属罐中游离苯酚的迁移测定。     

食品接触材料及制品1,4-丁二醇迁移量测定方法

目的建立测定1,4-丁二醇的气相色谱检测方法,确认食品接触材料及制品中1,4-丁二醇迁移量是否满足国标限量要求。方法对可降解塑料产品进行迁移试验,采用气相色谱法对迁移液中1,4-丁二醇进行分离、定性和定量检测。结果该法对1,4-丁二醇迁移量的方法检出限为0.4 mg/kg,1,4-丁二醇的含量为0~10 mg/kg时,与色谱峰面积具有良好的线性关系,相关系数大于0.995,样品加标回收率为95.2%~108.7%,测定结果的相对标准偏差为5.9%~9.7%(n=10)。结论该方法适用于食品接触材料及制品1,4-丁二醇迁移量的检测。     

顶空-气相色谱法测定食品接触用塑料制品中2-甲基-1,3-丁二烯含量及迁移量

采用内标法定量,建立了顶空-气相色谱法测定食品接触用塑料制品中2-甲基-1,3-丁二烯含量的试验方法。实验结果表明,该方法在0.4～2.0 mg/kg范围内线性良好(r2 0.999),检出限为0.08 mg/kg。按照建立的方法进行了三个不同添加量加标回收试验,回收率在95.2%～110.0%之间,相对标准偏差(RSD)在2.82%～3.01%之间(n=6)。该方法前处理简单,定性准确,灵敏度高,运用此方法同时研究了食品接触用塑料制品中2-甲基-1,3-丁二烯迁移量,探索了四种不同食品模拟物中的迁移现象。     

啤酒易拉罐中苯酚和双酚A的迁移检测

目的建立一种测定啤酒易拉罐中苯酚和双酚A迁移量的方法,应用于市售易拉罐啤酒污染物的检测。方法选用体积分数为10%的乙醇为食品模拟物,在迁移温度为60℃,迁移时间为10 d的条件下开展迁移研究,采用高效液相色谱-荧光法对迁移样液进行检测。结果在文中的试验方法下,苯酚和双酚A在7 min内可实现完全分离,方法的检出限(LOD)分别为6.0和1.5μg/L。苯酚在20~400μg/L质量浓度范围内线性良好(相关系数为0.9999),双酚A在5~100μg/L质量浓度范围内线性良好(相关系数为0.9998)。通过对空白样品进行加标回收试验,苯酚回收率为90.0%~98.5%,相对标准偏差(RSD)为2.7%~6.2%;双酚A回收率为84.0%~102%,RSD为3.2%~5.3%。将该方法应用于7种易拉罐啤酒中苯酚和双酚A迁移量的检测,结果均未检出苯酚,双酚A检出量在6.9~14.8μg/kg之间。结论该方法准确度高、灵敏度好,能够满足啤酒易拉罐中苯酚和双酚A迁移量检测的要求。     

GC-MS 法同时快速测定食品包装纸中的 5 种有害物质

建立了食品包装纸中乙二醇单甲醚、乙二醇单乙醚、乙二醇、乙二醇乙醚乙酸酯和二乙二醇 5 种成分的同时快速测定方法。 样品用甲醇超声提取,提取液过滤膜后,采用气相色谱-质谱联用仪(GC-MS)在选择离子监测模式下进行分析,内标法定量,并对样品前处理条件及色谱质谱条件进行优化。 结果表明:5 种化合物在其质量浓度范围内呈良好线性关系,相关系数均大于 0. 999,方法检出限为 1. 52 ~ 2. 76 mg / kg;在低、中、高 3 个加标水平时,回收率为 84. 47% ~ 105. 01% ,日内、日间重复性的相对标准偏差(RSD)均小于 4% 。 该方法操作简便、快速、准确,可用于食品包装纸中 5 种成分的批量检测。     

透析法样品前处理-离子色谱法测定复杂基质食品中甜蜜素含量

目的:建立透析法样品前处理-离子色谱法测定复杂基质食品中甜蜜素含量的分析方法。方法:样品经玻璃透析纸透析提取,离子色谱净化柱净化后,以DionexIon Pac~(TM)AS19(4mm×250mm)为分析柱,梯度淋洗液选择为高纯度氢氧化钾溶液,电导检测器,外标法进行定量。结果:甜蜜素在0.50～10.0ug/m L范围内线性关系良好,R~2为0.9996;加标回收率在93.3%～110.0%之间,相对标准偏差在0.11%～1.86%的范围内,方法检出限0.2mg/kg,方法定量限0.5mg/kg。结论:该方法具有样品前处理简单、无污染、灵敏度高、准确可靠等优点,可用于基质复杂食品中甜蜜素的测定。     

Mineral oil contents in paper and board recycled to paperboard for food packaging

Types of paper and board fed into the recycling process to manufacture paperboard for food packaging were analysed for saturated and aromatic mineral oil hydrocarbons. The focus was on the hydrocarbons eluted from gas chromatography before n‐C₂₄, as these are relevant for migration into dry foods via the gas phase at ambient temperature. Newspapers and leaflets printed by similar techniques were identified as the predominant sources of mineral oil, whereas office paper, books and corrugated board were the starting materials of lowest mineral oil content. Paperboard produced from the latter sources would contain about five times less mineral oil than the average observed today, but the migration into food could still exceed the limit derived from the available acceptable daily intake by a factor of up to 20. On average, European newspapers produced by offset printing contained 4.1 g/kg <C₂₄ mineral oil with 21% aromatic hydrocarbons. One out of four Japanese newspapers only contained 430 mg/kg <C₂₄ saturated and less than 15 mg/kg aromatic hydrocarbons. However, the maximum migration from paperboard exclusively produced from such newspaper would still far exceed the limit. Copyright © 2010 John Wiley & Sons, Ltd.     

Migration of Cyclic Monomer and Oligomers from Polyamide 6 and 66 Food Contact Materials into Food and Food Simulants: Direct Food Contact

Cyclic monomer and oligomers are the major migrating substances from polyamide (PA) food contact materials. An increase of caprolactam (+44%) and cyclic oligomer content (+27%, incl. caprolactam) in PA6 was observed by thermal treatment, here by extrusion of a PA6 film from a granulate. Migration experiments with a PA6 and a PA66 packaging film were carried out into food simulants according to directives 85/572/EEC and 82/711/EEC. Contact conditions (2 h/100°C) were chosen for a heat treatment of the food in the packaging, in this case production of scalded sausage. Aqueous and ethanolic food simulants clearly revealed to be the worst case for migration of cyclic PA6 and PA66 monomer and oligomers. Migration of cyclic oligomers into oil was one order of magnitude lower. No migration could be observed into isooctane (<8 µg dm^?2). The substitutes for oil, 95% ethanol and isooctane, were inapplicable for simulating migration of cyclic oligomers into oil. Caprolactam showed different migration behaviour compared with cyclic oligomers, migrating into oil and water to the same extent depending on contact conditions. Fifty percent of the extractable caprolactam migrated from a PA6 sausage casing into scalded sausage (4.2 mg kg^?1), residual 41% apparently were extracted by the boiling medium or during pretreatment (soaking) of the casing. Potential migration of caprolactam and cyclic oligomers from a PA6 tea bag was found to be 18% of the specific migration limit for caprolactam and 36% of the overall migration limit. Copyright © 2014 John Wiley & Sons, Ltd.     

纸质食品包装制品中挥发性MOSH组分SPME-HSGC-MS追踪检测

目的 对一次性纸质食品包装制品(盒、袋、桶、杯等)中挥发性饱和烃矿物油(MOSH)组分的含有情况进行检测分析，以确定纸质食品包装材料及制品中各挥发性MOSH组分向外挥发的性能以及对所包装食品(食品模拟物)的潜在危害性。方法 将样品裁切(5 mm×5 mm)后，取适量样品采用固相微萃取法进行萃取富集，然后使用顶空气相色谱-质谱进行检测，通过NIST质谱库检索、特征离子碎片检索以及标准样品比较相结合的方法进行定性。同时，为确定各样品中挥发性MOSH组分的迁移性能，在时隔6个月之后，对以上样品采用同样的方法进行取样、检测、分析。最后，根据2次检测的结果，判断市售一次性纸质食品包装材料及制品中挥发性MOSH组分的迁移性，以确定其对食品安全性的影响情况。结果 结果表明，所测的16种样品中均含有挥发性MOSH组分，并且其含量随着时间而降低;同时发现，没有印刷图文或印刷图文面积极小的纸质包装制品中挥发性MOSH组分向外迁移的速度较低。结论 SPME-HSGC-MS适用于纸质包装材料或制品中挥发性(半挥发性)MOSH组分的检测与分析。为降低由纸质食品包装材料及制品中挥发性MOSH组分对人体产生的危害性，建议纸质包装材料或制品制作完成后，在不增加仓储压力的情况下，放置一段时间，并加大其存储空间的通风，再用于食品包装。     

Migration of Mineral Oil into Noodles from Recycled Fibres in the Paperboard Box and the Corrugated Board Transport Box as well as from Printing Inks: A Case Study

From the toxicological evaluation of mineral oils as used in offset printing inks by the Joint Food and Agriculture Organization of the United Nations/World Health Organization Expert Committee on Food Additives (JECFA), a specific migration limit of 0.6 mg/kg in food can be derived. Experimental packs for taglioline (fine noodles) were investigated, aiming at respecting this limit. This ended with four conclusions. First, during the 65 day test (shelf life of 2 years), the transport box of corrugated board contaminated the bottom packs in the box with 6.1 mg/kg mineral oil saturated hydrocarbons (MOSH) and had the potential of contaminating all the 10 packs on average at about 10 mg/kg. Second, the migration from an improved recycled paperboard (five times less mineral oil than average) still amounted to 4.9 mg/kg, indicating that optimization of recycling is not promising to respect the 0.6 mg/kg limit. Third, a printing ink containing 3 g/kg MOSH (about 100 times less than conventional offset inks) still contaminated the taglioline with 0.6 mg/kg MOSH. Finally, the taglioline were contaminated with 2.5 mg/kg MOSH already before packing, illustrating that there are other sources of mineral oil violating the 0.6 mg/kg limit. Copyright © 2011 John Wiley & Sons, Ltd.     

Migration of di‐(2‐ethylhexyl)adipate (DEHA) and acetyl tributyl citrate (ATBC) plasticizers from PVC film into the food stimulant of isooctane

Chemical migration from food packing is influenced by several factors such as nature of chemicals, complexity of food, temperature, packing material used and properties of the migrating substances. Chemical compounds that are incorporated within polymeric packaging materials may interact with food components during processing or storage and migrate into the food by jeopardizing the food safety. This migration is higher if food remains in contact with packing material for extended time. Polyvinyl chloride (PVC) film such as di‐(2‐ethylhexyl) adipate (DEHA) and acetyl tributyl citrate (ATBC) are still widely used as a food packing material due to its flexibility, transparency and low water permeability. The present study covers the main migration phenomena of both plasticizers (di‐(2‐ethylhexyl) adipate (DEHA) and acetyl tributyl citrate (ATBC)) from PVC‐film into isooctane food stimulant using a direct gas chromatographic method. An exposure period of 48 h at 30 °C and 4 °C was used. The obtained results showed DEHA levels ranging of 7.2 mg/dm² while, no ATBC migration from PVC‐film was observed. Results are discussed in relation to EU legislation proposed upper limit for DEHA specific migration (18 mg/L or 3 mg/dm²) and overall migration limit (OM) of 10 mg/dm².     

Novel Test Approach for Evaluating and Modelling Barrier Properties of Food Contact Materials Against Mineral Oil Contaminants

A method for testing the mineral oil barrier properties of packaging materials has been developed as a response for the concerns on contamination of food by mineral oil compounds. The aim was to provide an efficient tool to evaluate packaging materials with respect to this. The method is a modification of the so‐called cup test using model compounds comparable with mineral oil components with different length and configuration of the hydrocarbon chain. The model compounds are introduced in the gas phase as penetrants. The absorbed amounts, which have migrated through the barrier, are analysed from a food simulant or powdered sugar. The method has been validated for coated and non‐coated boards. Compared with folding boxboard without polymer coating, polyethylene terephthalate‐coated board reduces the amount of the C16 compound in food simulant after 7‐day tests by a factor of 30. An extended migration model describing sorption mechanisms to both food simulant and fibres in the packing material has been developed. The model simulations for folding boxboard indicate that fibres absorb a significant proportion of the compounds when molecular weight increases. This retards the migration significantly compared with the speed expected by diffusion mechanism only. Copyright © 2016 John Wiley & Sons, Ltd.     

Mass transport studies of different additives in polyamide and exfoliated nanocomposite polyamide films for food industry

The development of new food packaging films through the incorporation of nanoparticles, and the effect of the nanoparticles on the process of migration of the substances used in manufacturing the new films is expected to lead to an improvement in the shelf life of food and thus, consumer safety and health. In recent years, attention has focused on nanocomposites because these compounds often exhibit unexpected hybrid properties derived from synergistic reactions between nanoparticles and the polymeric matrix. The exfoliation of nanoclays in polyamide film provides a film with better barrier properties than that obtained through the intercalation of nanoclays. Migration of chemicals from food packaging into food may produce potential adverse health effects because of exposure to toxic compounds. The present study addressed the migration of caprolactam, 5‐Chloro‐2‐(2,4‐dichlorophenoxy)phenol (triclosan) and trans,trans‐1,4‐diphenyl‐1,3‐butadiene (DPBD) from polyamide and polyamide‐nanoclays to different types of food simulants. The values for limit of detection (LOD) obtained for caprolactam, triclosan and DPBD was 0.5 mg/L, 0.02 mg/L and 0.01 mg/L, respectively. Furthermore, instrumental precision was evaluated through repeatability injections, resulting in relative standard deviations lower than 3.08%. Diffusion coefficients were calculated according to a mathematical model based on Fick's Second Law, and the results were discussed in terms of the parameters that may have the greatest effect on migration. The presence of polymer nanoparticles was found to slow down the rate of migration of substances from the matrix polymer into the food up to six times. Copyright © 2009 John Wiley & Sons, Ltd.     

食品接触材料聚乙烯和聚丙烯中9种抗氧化剂在食品模拟物中的迁移规律研究

在不同条件下,将含有已知量抗氧化剂的聚乙烯和聚丙烯薄膜,在水、乙酸(3 g/L)、体积分数为10%,50%和95%的乙醇等5种食品模拟物中浸泡,在规定的时间点抽取一定量的浸泡液,采用超高效液相色谱法检测抗氧化剂含量,研究了迁移量及迁移率与时间、温度、模拟物属性、抗氧化剂初始浓度和聚丙烯材料的厚度等参数的关系。结果表明:食品模拟物的属性对抗氧化剂的迁移行为影响最大;迁移量和迁移率随温度的升高而增加;材料厚度增加,则抗氧化剂迁移量增加,而迁移率降低;薄膜中抗氧化剂初始浓度越高,则迁移量越大,迁移率越低。     

基于ICP-MS法的包装用水基型胶粘剂中硼酸/硼砂残留量的快速检测

目的为保证包装用水基型胶粘剂产品质量安全,研究建立一种包装用水基型胶粘剂中硼酸/硼砂的ICP-MS快速测定方法。方法样品用稀硝酸溶液涡旋震荡,使水基型胶粘剂完全分散破乳,取上层溶液经高速离心后用ICP-MS进行测定,优化了萃取硝酸溶液浓度和涡旋震荡萃取时间。结果获得的最佳萃取硝酸溶液体积分数为15%,涡旋震荡萃取时间为20 min。方法的检出限为9.43μg/kg,样品加标回收率为97.0%~103.0%,相对标准偏差小于3.0%(n=6)。结论建立的方法操作简便快速,灵敏度高,结果准确可靠,可适合于包装用水基型胶粘剂中硼酸/硼砂含量的快速测定;实际检测样品中有少量硼酸/硼砂残留,但均符合GB 9685规定的最大迁移限量6(mg/kg)的要求。     

纸质包装材料中挥发性有机物迁移量的测定

目的研究纸质包装材料中挥发性有机物向食品模拟物中的迁移量。方法选取改性聚苯醚作为食品模拟物,首次建立模拟物MPPO直接顶空进样-气相色谱/质谱联用法测定包装用纸中23种有机挥发物质迁移量的方法。结果该法测定23种挥发性物质的相关系数R均大于0.998,相对标准偏差为1.4%~4.6%(n=7),检出限为0.03~0.60 mg/m2,加标回收率为81.2%~110.2%。结论该法无需前处理,简单快速,灵敏度高,重现性好,能满足包装用纸中23种有机挥发性物质迁移量的测定要求。