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。     

高效液相色谱-串联质谱法同时测定食品接触材料中七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-串联质谱(HPLC-MS/MS)联用方法同时测定食品模拟物(10%乙醇、20%乙醇、50%乙醇、3%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)]。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%乙酸铵溶液提取后,下清液用亲水性聚四氟乙酸针头过滤器过滤后进样。用Synergi Polar-RP柱等度洗脱分离;质谱具电喷雾离子源,在负离子多反应监测(MRM)模式下运行;方法在5种食品模拟物中的定量限为0.004~0.04 mg/kg;在0.5~12 mg/L范围内线性关系良好(r0.9975);1.25,2.5,6.25 mg/kg水平的加标回收率为91.2%~121%,相对标准偏差为0.6%~4.5%。该方法满足欧盟(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。     

有机相阴离子交换固相萃取HPLC-UV法快速测定食品接触材料中4种尼泊金酯的特定迁移量

建立了有机相阴离子交换固相萃取/高效液相色谱紫外法(HPLC-UV)快速测定10%乙醇、3%乙酸、20%乙醇、50%乙醇和橄榄油食品模拟物中尼泊金甲酯、尼泊金乙酯、尼泊金异丙酯和尼泊金丙酯的特定迁移量(SM)。橄榄油食品模拟物样品采用有机相阴离子交换固相萃取法净化,水基食品模拟物样品经亲水性聚四氟乙烯针式过滤器过滤后直接进样。以甲醇和纯水为流动相,4种尼泊金酯在ZORBAX SB-Phenyl柱上等度洗脱,12.5 min内达到基线分离;紫外外标校准曲线法定量。4种尼泊金酯在0.5~100 mg/L范围内线性关系良好(r2≥0.999 8),在10、50、100 mg/kg 3个浓度水平下的加标回收率为97.9%~103%,相对标准偏差为0.02%~2.2%,在5种食品模拟物中的定量下限为0.1~0.5 mg/kg。结果表明,该方法的色谱分离和线性关系好,回收率和准确度高,满足欧盟(EU)NO 10/2011法规附表1中4种尼泊金酯SM的限量要求,并已应用于实际样品的检测。     

高效液相色谱-串联质谱法同时检测食品接触材料中9种抗氧剂的特定总迁移量

建立了高效液相色谱-串联质谱(HPLC-MS/MS)联用方法同时测定塑料制品食品模拟物(10%乙醇、20%乙醇、50%乙醇、3%乙酸和橄榄油)浸泡液中9种抗氧剂的特定总迁移量[SML(T)]。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(10%乙醇、3%乙酸、20%乙醇、50%乙醇)用含0.05%三(2-羧乙基)膦盐酸盐(TCEP)60%的四氢呋喃水基食品模拟物溶液稀释5倍后,经亲水性聚四氟乙烯针头过滤器过滤后进样;橄榄油用甲醇正庚烷提取后,下清液用亲水性聚四氟乙烯针头过滤器过滤后进样。用C8柱梯度洗脱分离;质谱具电喷雾离子源,在负离子多反应监测(MRM)模式下运行;方法在5种食品模拟物中的定量限为0.01~0.3 mg/kg;水基食品模拟物在0.03~0.72 mg/L,0.06~1.44 mg/L,0.1~2.4 mg/L或0.3~7.2 mg/L,橄榄油食品模拟物在0.15~3.6 mg/kg,0.3~7.2 mg/kg,0.5~12.0 mg/kg或1.5~36 mg/kg范围内线性关系良好(R≥0.99240);0.3~21 mg/kg水平的加标回收率为74.4%~132%,相对标准偏差为0.8%~20%。方法满足欧盟(EU)NO 10/2011法规附表2中9种抗氧剂SML(T)的限量要求,并已应用于实际样品的检测。     

Determination of the migration of 8 benzophenones in food contact materials and products by HPLC-MS / MSEI北大核心CSCD

建立了高效液相色谱-串联质谱法测定食品接触材料及制品中8种二苯甲酮类物质迁移量的方法。样品经过食品模拟物浸泡后，水、4%乙酸、10%乙醇、20%乙醇、50%乙醇模拟物直接进样，95%乙醇模拟物用水按照1:4比例稀释后进样，橄榄油和异辛烷模拟物用甲醇-水混合溶液萃取后进样。采用C₁₈柱分离，用甲醇-0.1%甲酸水溶液为流动相梯度洗脱，质谱采用正离子多反应监测（MRM）模式运行。本方法在8种食品模拟物中的定量限为0.01～0.20 mg/kg;在0.04～0.80 mg/kg, 0.2～2.0 mg/kg, 0.6～3.0 mg/kg线性范围内相关系数良好（R≥0.9958）;加标实验结果显示相对标准偏差（RSD）为0.61%～7.8%。该方法可用于食品接触材料及制品中二苯甲酮类物质迁移量的测定。     

气相色谱-质谱联用法测定纸吸管中二甘醇二苯甲酸酯的迁移量

建立气相色谱-质谱联用法测定纸吸管在水、4%乙酸溶液、10%乙醇溶液和50%乙醇溶液四种食品模拟物中二甘醇二苯甲酸酯（DEDB）迁移量的方法，并探讨了DEDB向模拟物中迁移的规律。以乙酸乙酯作萃取剂，萃取食品模拟物中的DEDB，萃取液经HP-5MS色谱柱（30 m×0.25 mm,0.25μm）分离，采用气相色谱-质谱联用法检测，内标法定量。在质量浓度为0.2～10.0 mg/L范围内，DEDB与内标物的质量浓度比和与苯甲酸苄酯监测离子丰度比线性关系良好，相关系数r为0.999 0，方法检出限为0.05 mg/L，定量限为0.2 mg/L。样品加标回收率为91.2%～103.6%，相对标准偏差为3.1%～8.5%(n=6)。在相同的温度和时间下，DEDB迁移量从小到大的顺序依次为：水、4%乙酸溶液、10%乙醇溶液、50%乙醇溶液。该方法简便、快速，适用于纸吸管中DEDB迁移量的测定。     

气相色谱-串联质谱法测定食用油中两种非邻苯二甲酸酯类增塑剂

建立了气相色谱-串联质谱同时测定食用油中对苯二甲酸二（2-乙基己基）酯和偏苯三甲酸三（2-乙基己基）酯两种非邻苯二甲酸酯类增塑剂的方法。样品采用乙腈提取,于-20℃冷冻除脂净化,用气相色谱-串联质谱选择反应监测模式测定。两种化合物的检出限为0.03 mg/kg,定量限为0.1 mg/kg,线性范围为0.1~10 mg/kg。3个添加水平（0.1、0.3和1.0 mg/kg）下的回收率为81.04%~108.31%,相对标准偏差为0.70%~9.91%。该方法简便、准确,适用于食用油中对苯二甲酸二（2-乙基己基）酯和偏苯三甲酸三（2-乙基己基）酯的检测。     

顶空-气相色谱法同时测定聚对苯二甲酸乙二醇酯瓶中乙醛和丙酸乙烯酯迁移量

建立了顶空-气相色谱法同时测定聚对苯二甲酸乙二醇酯(PET)瓶中乙醛和丙酸乙烯酯迁移量的方法.将食品模拟液水、4％(体积分数,下同)乙酸溶液或橄榄油灌入PET瓶中,在迁移温度为40,60℃下迁移1,10,20,30 d.取10 mL模拟液于22 mL顶空进样瓶中,设置顶空平衡温度为80℃,顶空平衡时间为60 min.气...     

高效液相色谱-串联质谱法同时测定食品接触材料中间苯二酚-o,o’-二乙酸、2-羟基-6-萘甲酸、间苯二甲酸二甲酯-5-磺酸钠的特定迁移量

建立了高效液相色谱-串联质谱(HPLC-MS/MS)法同时测定食品模拟物(10%乙醇、3%乙酸、20%乙醇、50%乙醇和橄榄油)中间苯二酚-o,o’-二乙酸、2-羟基-6-萘甲酸、间苯二甲酸二甲酯-5-磺酸钠的特定迁移量(SM)。水基食品模拟物样品经亲水性聚四氟乙烯针式过滤器过滤后进样;橄榄油食品模拟物样品用0.1%乙酸铵溶液震荡提取12 min后,静置15 min,下清液用亲水性聚四氟乙烯针式过滤器过滤后进样。用C8柱梯度洗脱分离;Qtrap4500质谱在电喷雾离子源负离子及多反应监测(M RM)模式下进行检测。方法在5种食品模拟物中的定量限为0.3~1.2μg/kg;水基食品模拟物在10~200μg/L、橄榄油食品模拟物在10~200μg/kg范围内线性关系良好(r0.99904);加标回收率为86.0%~116%,相对标准偏差为0.5%~7.2%。方法满足欧盟(EU)NO 10/2011法规附表1中间苯二酚-o,o’-二乙酸、2-羟基-6-萘甲酸、间苯二甲酸二甲酯-5-磺酸钠的SM限量要求。方法已应用于实际样品的检测。     

顶空-气相色谱法快速测定蜜胺餐具中甲醛单体迁移量

建立了顶空-气相色谱法快速测定蜜胺制品中甲醛迁移量的方法。采用水、质量分数3%乙酸、50%乙醇、橄榄油作为食品模拟物对样品浸泡后,对浸泡液中的甲醛进行顶空提取后进色谱分析,采用HP-INNOWAX毛细管柱分离,以氢火焰离子化检测器进行检测,以保留时间定性,外标法定量。结果表明,4种食品模拟物中甲醛的平均回收率为88.3%~97.6%;RSD为2.3%~4.1%。甲醛在水、3%乙酸中的检出限均为0.8 mg/L,在50%乙醇中检出限为2.0 mg/L,在橄榄油中检出限为0.8 mg/kg。方法适用于蜜胺制品中甲醛单体迁移量的快速测定。应用建立的方法研究了同等浸泡条件下不同食品模拟物对甲醛迁移的影响,结果表明蜜胺制品中甲醛在3%乙酸中迁移量最大。     

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.     

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。     

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).     

Migration Study of Polypropylene (PP) Oil Blends in Food Simulants

Migration study in aqueous and olive oil food simulants was carried out on PP and its blend with oil mixture. It was found that after 10 days at 44 °C PP with oil content up to 0.83% had overall migration into olive oil less than 10 mg/dm². However, under high temperature migration test (at 110–138 C for 4 hours), the overall migration into olive oil was large for both the virgin PP and all its blends. The overall migration in water, 10% ethanol, and 3% acetic acid was smaller than those in olive oil under both migration test conditions. DSC and density measurement showed that addition of oil in PP led to smaller spherulite size and increased degree of crystallinity in the pure PP part. Small decrease in tensile strength in the oil blends was also observed but there was no significant change in tensile strength after migration test.     

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.     

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。