超高效液相色谱/静电场轨道阱高分辨质谱法同时测定塑料食品接触材料中光稳定剂和抗氧化剂的特定迁移量

建立了超高效液相色谱/静电场轨道阱高分辨质谱同时测定塑料食品接触材料中多种光稳定剂和抗氧化剂特定迁移量的方法。采用30 g/L乙酸、体积分数分别为10%、20%、50%的乙醇和油类模拟物(异辛烷)这5种食品模拟物对塑料食品接触材料进行处理,对处理液进行超高效液相色谱/静电场轨道阱高分辨质谱分析,外标法定量。该方法测定的40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0.998,定量限为0.01~1.00μg/L。考察了上述5种食品模拟物中光稳定剂和抗氧化剂的特定迁移量,平均加标回收率为81.46%~94.53%,相对标准偏差为3.25%~9.99%。应用该方法对市售塑料食品接触材料进行了测定,结果在部分样品中检出了不同含量的光稳定剂和抗氧化剂。该方法灵敏度高,定量限低,满足塑料食品接触材料中光稳定剂和抗氧化剂特定迁移量的检测要求。     

高效液相色谱法同时测定食品接触材料中抗氧化剂和紫外吸收剂的迁移量

采用高效液相色谱技术,建立了食品接触材料中多种抗氧化剂和紫外吸收剂迁移水平的检测方法。该方法测定的23种目标化合物具有较好的线性关系,相关系数（r²）≥ 0.9998,检出限和定量限分别在0.01到0.22 mg/L之间和0.03到0.85 mg/L之间。依据欧盟指令（EU）No. 10/2011,考察了5种食品模拟物30 g/L乙酸、10%（v/v）乙醇、20%（v/v）乙醇、50%（v/v）乙醇和油类模拟物（异辛烷）中抗氧化剂和紫外吸收剂的迁移量。该方法回收率在92.8%~117.7%之间,相对标准偏差在0.95%~9.72%之间。探讨了不同实验条件对抗氧化剂和紫外吸收剂回收率的影响。结果表明,该方法准确、稳定,完全满足欧盟指令（EU）No 10/2011和GB 9685-2008对食品接触材料及制品中抗氧化剂和紫外吸收剂特定迁移量（SML）的限量要求,并利用该方法测定了30批次食品接触材料中抗氧化剂和紫外吸收剂的迁移水平。     

Determination of Dihydroxybenzenes in Plastic Food Packaging Materials and in Food Simulating Liquids Using Capillary Electrophoresis

A capillary electrophoresis method has been developed to determine 1,2-dihydroxybenzene and 1,3-dihydroxybenzene in the food simulants distilled water, 3% acetic acid, 15% ethanol, and olive oil. Both substances, used as monomers and additives to make food packaging plastics, could be analyzed within 15 min. The 1,4-dihydroxybenzene isomer was unretained and eluted with the electroosmotic flow, and so the CE method can give only a semi-quantitative estimate of this isomer if it is present as a migrant. The analytical recovery for the 1,2- and 1,3-isomers from spiked simulants was good at 87% to 98% except for 1,2-dihydroxybenzene which could only be recovered to the extent of 58% from olive oil. Calibration graphs were linear and the limit of detection for each substance was 0.6 mg/kg, which is well below migration limits for these substances. It is concluded that CE offers a rapid and reliable analysis for the control of migration from plastics intended for food contact which employ 1,2-dihydroxybenzene or 1,3-dihydroxybenzene during manufacture, and offers a screening method for 1,4-dihydroxybenzene migration.     

高效液相色谱-紫外检测法同时测定食品接触材料中7种苯多酸及其衍生物的特定总迁移量

建立了高效液相色谱-紫外检测(HPLC-UV)同时测定5种食品模拟物(10%(v/v)乙醇、20%(v/v)乙醇、50%(v/v)乙醇、3%(w/v)乙酸和橄榄油)中偏苯三甲酸、偏苯三甲酸酐、间苯二甲酰氯、间苯二甲酸、对苯二甲酰氯、邻苯二甲酸、对苯二甲酸的特定总迁移量(SML(T))的方法。用食品模拟物浸泡待测样品,冷却至室温并混匀,水基食品模拟物经亲水性聚四氟乙酸针头过滤器过滤后进样;橄榄油用0.1%(w/v)乙酸铵水溶液提取后,下层清液用亲水性聚四氟乙烯针头过滤器过滤后进样。用Synergi Polar-RP色谱柱(250 mm×4.6 mm, 4 μm)分离,梯度洗脱,检测波长为232 nm。5种食品模拟物中的定量限为0.1~0.2 mg/kg;水基食品模拟物在0.5~12 mg/L、橄榄油食品模拟物在0.5~12 mg/kg范围内线性关系良好(r² > 0.99991); 1.25、2.5、6.25 mg/kg水平的加标回收率为94.3%~105%,相对标准偏差为0.1%~2.3%。结果表明,该方法的色谱分离和线性关系较好,回收率和准确度高,完全满足欧盟(EU)No 10/2011法规附表2中7种苯多酸及其衍生物的SML(T)的限量要求,并已应用于实际样品的检测。     

A rapid HPIC method for the quantitative determination of tetramethylammonium chloride in some aqueous solutions used as food simulants

Summary The present paper reports a rapid HPIC method for the determination of tetramethylammonium chloride in aqueous matrices which are used as food simulants in migration tests. These simulants were: bidistilled water, an aqueous solution of 3% acetic acid, an aqueous solution of 15% ethyl alcohol, a mixed aqueous solution of 3% acetic acid and 15% ethyl alcohol. The method, as developed, has been applied to the determination of unreacted tetramethylammonium chloride residues which are able to migrate from finished epoxy resins which are used as food packaging materials.Research partially supported by National Research Council of Italy, Special Project RAISA, sub-project 4, Paper N^o 695.     

Specific determination of 20 primary aromatic amines in aqueous food simulants by liquid chromatography-electrospray ionization-tandem mass spectrometry

A multi-analyte method without any pre-treatment steps using reversed-phase liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) was developed and applied for the determination of 20 primary aromatic amines (PAA) associated with polyurethane (PUR) products or azo-colours. The method was validated in-house for water and 3% acetic acid food simulants using spiked migrates from plastic laminates. Detection limits ranged from 0.27 to 3 microg amine/L food simulants, and RSD values of within-laboratory reproducibility at the 2 microg PAA/L level ranged from 3.9 to 19%. PAA migration from plastic laminates and black nylon cooking utensils were determined with the method, and high levels of 4,4'-methylenedianiline and aniline were found in migrates from about half of the tested cooking utensils. The method fulfils present legislative demands in the EU for screening and verification of PAA migration from food contact materials.     

气相色谱-质谱法测定聚氯乙烯包装材料和食品模拟物中的46种增塑剂

建立了46种增塑剂在聚氯乙烯(PVC)食品包装材料中的含量及其在水、3%乙酸、10%乙醇和橄榄油4种食品模拟物中迁移量的气相色谱-质谱(GC-MS)测定方法。食品包装材料、水质模拟物和橄榄油中增塑剂分别采用溶解-沉淀法、正己烷液-液萃取和凝胶渗透色谱(GPC)法提取。采用GC-MS法,在选择离子监测模式(SIM)下对46种增塑剂进行定性,采用外标法进行定量测定。各种增塑剂在0.1～2.0 mg/L质量浓度范围内呈线性,相关系数为0.9910～0.9999,各组分检出限均在0.005～0.05 mg/kg之间。在2种食品模拟物中,3个浓度添加水平下46种增塑剂的加标回收率在69.51%～107.21%之间,精密度(RSD, n=6)为3.53%～18.95%。该方法可满足PVC食品接触制品及4种不同性质的食品模拟物中多种类增塑剂的快速筛查和准确定性、定量测定要求。     

Effect of gamma irradiation on caprolactam migration from multilayer polyamide 6 films into food simulants: development and validation of a gas chromatographic method

A GC method to determine caprolactam in water, 15% ethanol, and olive oil food simulants was developed and validated. Linear ranges varied from 0.96 to 642.82 microg/mL for water, 0.64 to 800.32 microg/mL for 15% ethanol, and 1.06 to 1062.34 microg/g for olive oil, with correlation coefficients higher than 0.999. Method precision studies showed RSD values lower than 5.45%, while method accuracy studies showed recovery from 72 to 111% for all simulants. The effect of gamma irradiation on caprolactam migration from multilayer polyamide 6 (PA-6) films intended for cheese into water, 15% ethanol, olive oil, and 3% acetic acid simulants was also studied. For migration assay, non-irradiated and irradiated (12 kGy) films were placed in contact with the simulant and exposed at 40 degrees C for 10 days. The validated method was used to quantify caprolactam migration from multilayer PA-6 films into the simulants, which ranged from 1.03 to 7.59 mg/kg for non-irradiated films, and from 4.82 to 11.32 mg/kg for irradiated films. Irradiation caused almost no changes in caprolactam levels, with the exception of olive oil, which showed an increase in the caprolactam level. All multilayer PA-6 films were in accordance with the requirements of the legislation for caprolactam migration.     

Repeated migration of additives from a polymeric article in food simulants

The migration of three additives from polypropylene samples into a series of five liquid food simulants was investigated at 60 °C in a repeated migration regime. This regime was simulated by 20 migration periods each of 8 h and using initially additive free food simulants. Between these migration periods the bare samples were stored in an air conditioned room at around 23 °C for 16 h at working days and for 64 h during weekends. An asymptotic decrease of the additive level in the food simulants in the successive migration periods, from a maximum values towards zero, was observed when the additives easily solve in the food simulants. In contrast when the additives solve poorly in the food simulants this additive level decrease is almost linear and shows a slow decrease rate. In the first case the leaching/migration of the additives is controlled mainly by their diffusion in the matrix of the polymer. In the latter case this process is controlled mainly by the partitioning of the additives between the polymer and food simulants. Two approaches were used to model theoretically these results.In the first approach the mass transport equation was solved by using as input parameters overestimated diffusion and partitioning coefficients as estimated for polypropylene homopolymer, the used food simulants and the three additives according to the recommendations of a practical guidance document in support of migration modelling as stipulated in the Regulation (EU) 10/2011. As expected the results of these calculations overestimate the vast majority of the migration levels determined experimentally. However there are also situations in which this approach leads to underestimations of the real migration levels.In the second approach numerical fitting was applied with the same equation and using the diffusion and partition coefficients as adjustable parameters to obtain a best-fit between experimental and calculated results. It was found that the so obtained “realistic” diffusion coefficients are all lower than the overestimated ones mentioned above. Moreover these “realistic” coefficients depend not only on the nature of the additive but also on the nature of the food simulant in contact with the polymer. This suggests that interaction of food simulants with the polypropylene occurs, which changes the properties of the polymer and thus the mobility of the additive molecules in its matrix. For the “realistic” partition coefficients it was found that they all are higher than the conservative ones mentioned above. Using these “realistic” parameters a good fit between calculated and experimental migration results was found.     

A novel method for the determination of migration of contaminants from food contact materials

A neutron activation method has been developed for the analysis of high density polyethylene, low density polyethylene, polypropylene, polyethylene terephthalate and polystyrene food contact plastics. The method provides determination of over 50 elements at concentrations below 1 mg kg^–1. This technique has now been extended to study migration from food contact materials into standard food simulants (olive oil, acetic acid, ethanol and water). Samples of plastic are irradiated in a thermal neutron flux to produce radionuclides of the elements present in the plastic. Over a period of time the radionuclides of these elements may travel from the plastic into the food simulants, and hence the migration can be determined. Gamma ray spectrometry is performed on the simulants at the end of the test to quantify the migration. Any activity present must be due only to the migration of radionuclides of elements in the plastic and nothing else. This eliminates the need for a blank determination, which is required with existing migration methods. Preliminary studies have shown that detection limits of around 0.002 mg kg^–1 can be achieved for Sb in a retail polyethylene terephthalate (PET) bottle. This can be compared to levels of 0.005     

微波条件下双酚A向食品模拟物的迁移研究

采用气相色谱-质谱联用法研究了微波条件对食品接触材料中双酚A在水、乙酸（3%,体积分数）、乙醇（10%,体积分数）、橄榄油4种食品模拟物中迁移行为的影响。在微波加热下,食品快速升温并能将热量传递给外部包装,从而加速包装材料中双酚A向食品的迁移。研究了不同微波温度、时间和功率下双酚A在4种食品模拟物中的迁移规律,结果表明：微波对双酚A迁移有显著影响,迁移量随着微波温度、时间和功率的增加而增加。在相同加热温度和时间条件下,微波加热方式中双酚A在4种食品模拟物种的迁移量均高于水浴加热。     

微波消解/电感耦合等离子体质谱法同时测定食品纸包装材料与食品模拟物中24种元素

建立了微波消解/电感耦合等离子体质谱(ICP-MS)同时检测食品纸包装材料及3种食品模拟物(纯水、4%乙酸、10%乙醇)中Li,Be,B,Al,V,Cu,Mn,Zn,Cr,Ni,As,Sr,Zr,Se,Mo,Ag,Cd,Sn,Sb,Te,Ba,Hg,Tl,Pb 24种元素的分析方法,并对元素的迁移行为进行了研究。包装材料样品经微波消解后利用ICP-MS检测;迁移试验中的食品模拟物直接利用ICP-MS检测。在优化实验条件下,24种元素在0~1 000μg/L范围内线性关系良好;方法检出限(MLOD)为0.000 3~0.465 mg/kg;在1.0~1 000 mg/kg加标水平下的平均回收率为90.5%~125.3%;相对标准偏差(RSD,n=3)为1.2%~6.8%。该方法前处理简便、灵敏准确、适用范围广,可用于食品纸包装材料中元素含量的测定及迁移行为的研究,从而为食品纸包装材料的质量监督提供了科学依据。     

超高效液相色谱-串联质谱法检测水系模拟物中11种工业用抗氧化剂

建立了水系模拟物中11种工业用抗氧化剂的超高效液相色谱-串联质谱检测方法。水系模拟物经ProElut PLS固相萃取柱浓缩富集,采用ACQUITY UPLCTM BEH C18超高效液相色谱柱(100 mm×2.1 mm,1.7μm)分离,水和乙腈作为流动相进行梯度洗脱,电喷雾离子源电离,负离子多反应监测模式下进行监测,外标法定量。11种化合物在5.0~100μg/L范围内呈良好线性关系,相关系数r0.995,方法检出限为0.2~1.0μg/L,定量限为0.5~3.0μg/L。5.0、10.0和20.0μg/L添加水平下的加标回收率为61.4%~109.4%,RSD为3.9%~18.2%(n=6)。该方法操作简单、稳定、可靠,可以满足水系模拟物中11种抗氧化剂的定性确证和定量检测。     

Determination of antioxidants by solid-phase extraction method in aqueous food simulants

An analytical method for the determination of specific migration levels of phenolic antioxidants and one phosphite antioxidant in the aqueous food simulants established by European legislation has been developed. This method involves solid-phase extraction (SPE) of the antioxidants with silica C₁₈ cartridge and their determination by liquid chromatography (LC) with diode-array detection. The achieved results in the studies of elution volume determination, breakthrough volume and accuracy are showed. Recoveries in the range of 78–104% and a relative standard deviation between 2.0 and 7.7% have been achieved.     

高效液相色谱-串联质谱法快速测定水基食品模拟物中28种受限芳香族伯胺的迁移量

建立了高效液相色谱-串联质谱(HPLC-MS/MS)联用方法用于快速测定水基食品模拟物(10%乙醇、30 g/L乙酸和20%乙醇)中28种芳香族伯胺的迁移量。用水基食品模拟物浸泡待测样品中一定时间(在100 ℃条件下)后,冷却至室温并混匀,所得浸泡液经亲水性聚四氟乙烯针头式过滤器过滤后,直接进行HPLC-MS/MS测定。采用Agilent Zorbax SB-Phenyl柱,以水和0.1%甲酸-25%乙腈-甲醇溶液为流动相进行梯度洗脱分离;质谱具电喷雾离子源,在正离子和分段式多反应监测(MRM)模式下检测。结果表明,方法定量限为0.002～10 μg/L,在5～100 μg/L或10～100 μg/L范围内线性关系良好(r2＞0.995);在10、20、40 μg/L水平的加标回收率为76.6%～114%,相对标准偏差为1.53%～8.97%。该方法样品前处理简单快速,色谱分离效果和线性关系好,检出限较低、回收率和准确度高,且完全满足欧盟(EU)No 10/2011法规中对芳香族伯胺特定迁移量的限量要求。该方法已成功应用于30批次出口欧盟的食品接触材料相关制品中芳香族伯胺特定迁移量的检测。     

聚苯乙烯提取物的检测与评价

随着材料科学的迅速发展,聚合物材料以不同的形态越来越广泛地应用于食品包装中。但是由于聚合物材料自身的特性及其改性加工,导致了很多低分子量化合物的形成,因而给食品安全性带来很大隐患,也危害着人们的身体健康。为了解决这一问题,在选用材料前,必须分析聚合物材料中低分子化合物的迁移情况,考虑迁移过程对包材使用的影响。实验中选用正庚烷、8%乙醇、50%乙醇和蒸馏水作为食品模拟液,用气相色谱测定聚苯乙烯提取物的迁移量,进而将实验数据分析比较。结果显示,迁移量随着温度的升高和时间的延长而不断增加,溶剂种类的影响为:正庚烷>50%乙醇>8%乙醇>蒸馏水。     

高效液相色谱-紫外法快速测定塑料类食品接触材料及制品中7种对苯二甲酸酯或苯甲酸酯的特定迁移量

建立了高效液相色谱-紫外检测（HPLC-UV）法快速测定从塑料类食品接触材料及制品迁移至10%（v/v）乙醇、3%（m/v,即3 g/100 mL）乙酸、4%（v/v）乙酸、20%（v/v）乙醇、50%（v/v）乙醇、95%（v/v）乙醇和橄榄油7种食品模拟物中对苯二甲酸二甲酯、对苯二甲酸二辛酯、苯甲酸甲酯、苯甲酸乙酯、苯甲酸丙酯、苯甲酸丁酯和新戊二醇二苯甲酸酯的特定迁移量。考察了多种提取溶剂、QuEChERS dSPE EMR-Lipid试剂盒和Captiva EMR-Lipid试剂盒对橄榄油食品模拟物中7种对苯二甲酸酯或苯甲酸酯的提取或净化效果。以甲醇和水为流动相进行梯度洗脱,7种对苯二甲酸酯或苯甲酸酯在苯基柱上于17 min内达到基线分离。检测波长为237 nm,进样量为10 μL。7种对苯二甲酸酯或苯甲酸酯在7种食品模拟物中的定量限为0.2~8.1 mg/kg、1~80 mg/L或8~160 mg/kg,相关系数r≥0.9998。在2或8、60、80或160 mg/kg 3个加标水平的回收率为91.7%~106%,相对标准偏差为0.1%~3.1%。该方法样品前处理简便,色谱分离和线性关系好,回收率和重复性较好,已应用于实际样品的检测。     

Kinetics of the hydrolysis of bisphenol A diglycidyl ether (BADGE) in water-based food simulants

Summary The first-order degradation kinetics of bisphenol A diglycidyl ether (BADGE; CAS No. 1675-54-3) has been studied in three water-based food simulants (3% (W/V) acetic acid, distilled water and 15% (V/V) ethanol) at various temperatures. BADGE and its first and second hydrolysis products were determined by reversed-phase high-performance liquid chromatography with fluorescence detection. Nonlinear regression was used to fit the experimental data at 40, 50 and 60°C with the proposed kinetic equations; Arrhenius' equation was then fitted to the rate constants obtained and the kinetic models were tested by comparing experimental data obtained at 70°C with the kinetic curves calculated using the rate constants predicted for this temperature. The half-life of BADGE was longest in ethanol and shortest in acetic acid. The rings opening in acetic acid appears to happen by means of active hydrogens whereas in the other simulants it is mainly influenced by the formation of acid/base adducts. The results imply that resins which comply with existing legislation on the migration of unreacted monomer may still contaminate foodstuffs.     

PVC塑料包装中化学物总迁移的研究

食品包装安全是食品安全的一个重要环节.食品容器、包装等接触材料与食品长期接触会发生"迁移",分为总迁移(overall migration)和特定迁移(specific migration)[1].其中,特定迁移是指某一特定物质在食品包装或容器与食品接触过程中发生的迁移;总迁移是从塑料材料或制品样品到试验媒介的组分总体迁移量.就物质而言,有可知物与未知物,就过程而言,有包装向食品的迁移,也有食品向包装的渗透、吸收等.进行总迁移实验有助于更全面了解一种材料与食品接触会发生的总体变化,对特定迁移的研究起有辅助与补充作用.欧盟对于食品模拟物、样品及前处理[2]、迁移测试方法[3]都有相应规定[4],本实验采用整体浸泡法,研究了PVC材料中化学物在不同食品模拟物中的总迁移.1 实验部分1.1 实验试剂和器材     

Analysis of 16 phthalic acid esters in food simulants from plastic food contact materials by LC‐ESI‐MS/MS

An RP LC‐ESI‐MS/MS method for the determination of the migration of 16 primary phthalic acid esters from plastic samples has been developed using distilled water, 3% acetic acid, 10% alcohol, and olive oil as food simulants. Detection limits were 1.6–18.5 μg/kg in distilled water, 1.4–17.3 μg/kg in 3% acetic acid, 1.4–19.2 μg/kg in 10% alcohol, and 31.9–390.8 μg/kg in olive oil. The RSDs were in the range of 0.07–11.28%. The real plastic products inspection showed that only few analyzed samples were phthalates contaminated. Bis‐2‐ethylhexyl ester and dibutyl phthalate were the common items migrated from the plastic products into food and feeds, but the migration concentrations were far below the limits set by European Union (1.5 mg/kg for bis‐2‐ethylhexyl ester and 0.3 mg/kg for dibutyl phthalate).