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。     

2种方法检测食品模拟物中矿物油含量的比较研究

目的 考察离线固相萃取-气相色谱-氢火焰离子化检测器法(off-line solid phase extraction-gas chromatography-flame ionization detector method, off-line SPE-GC-FID)与高效液相色谱-气相色谱-氢火焰离子化检测器在线联用法(on-line high performance liquid chromatography-gas chromatography-flame ionization detectorion method, on-line HPLC-GC-FID)测定食品模拟物中矿物油含量的异同。方法 分别以4种食品模拟物为样品,从前处理程序、仪器方法、方法学考察与样品测定等几个方面对两种检测方法进行了比较。结果 off-line 离线SPE-GC-FID和on-line HPLC-GC-FID 在线联用2种方法的挥发损失均能满足实验需求,off-line 离线SPE-GC-FID的定量限为水基模拟物1.25 mg/L,油基模拟物5.00 mg/L,on-line HPLC-GC-FID的定量限为水基模拟物0.10 mg/L,油基模拟物0.40 mg/L,回收率和相对标准偏差均可以满足矿物油检测要求;两种方法分析不同食品模拟物中的饱和烃矿物油和芳香烃矿物油没有显著性差异。结论 off-line 离线SPE-GC-FID和on-line HPLC-GC-FID测定食品模拟物中的矿物油含量不存在显著性差异,二者均可应用于食品模拟物中的矿物油含量检测,其中on-line HPLC-GC-FID灵敏度更高,适合低含量矿物油污染物的分析。     

植物油基鱼罐头中矿物油污染物高灵敏检测方法的建立

本文建立了植物油基鱼罐头中矿物油（MOH）的高灵敏测定方法并调查了部分市售商品的MOH含量。方法采用皂化反应、环氧化反应进行提取和净化，以高效液相色谱-气相色谱联用法（HPLC-GC）分级、富集和定量检测。结果表明:所建立的植物油基鱼罐头中饱和烃矿物油（MOSH）和芳香烃矿物油（MOAH）测定方法的定量限（LOQ）为0.5 mg/kg，加标回收率为90.0%~106.0%，精密度（RSD）为1.6%~12.7%，满足欧洲联合研究中心（JRC）关于高油脂食品中矿物油的分析要求。应用该方法检测了北京地区10个市售鱼罐头产品，发现所有样品均含有MOSH，含量为2.6~53.7 mg/kg，其中5个检出MOAH，含量为0.7~5.5 mg/kg；谱图分析表明这些罐头的MOH污染与其植物油和鱼肉来源密切相关。     

全二维气相色谱-飞行时间质谱测定婴幼儿配方奶粉中的矿物油

目的建立全二维气相色谱-飞行时间质谱(two-dimensional gas chromatography with time of flight mass spectrometry, GC×GC-TOFMS)/氢火焰离子化检测器(flame ionization detector, FID)法测定婴幼儿配方奶粉中矿物油的分析方法。方法样品经过提取皂化、0.3%(质量分数)硝酸银硅胶-分子筛硅藻土混合固相萃取(solidphase extraction,SPE)柱净化处理后,采用全二维气相色谱-飞行时间质谱联用进行检测和分析。结果该法实现了饱和烃类矿物油(mineraloilsaturatedhydrocarbons,MOSH)和芳香烃类矿物油(mineraloilaromatichydrocarbons,MOAH)的在线分离,仪器分析时间仅为34min。MOSH和MOAH的检出限为0.5mg/kg,加标回收率为88.0%～97.2%,相对标准偏差为5.0%～8.3%(n=6)。运用该法对20款配方奶粉进行测定,均未检出MOAH,其中11款检出MOSH,含量为0.5～8.2 mg/kg;奶粉中普遍含有奇数碳的正构烷烃和植物甾醇烯类物质,推断矿物油污染可能来源于油墨和润滑油。结论方法灵敏,进一步提高了定量的准确性,可同时进行定性和定量分析,适合于奶粉中矿物油的检测。样品检测结果表明,婴幼儿配方奶粉中矿物油的污染情况需引起关注。     

果蔬中复硝酚盐残留量检测方法的建立

建立了固相萃取-气相色谱-电子捕获检测水果蔬菜中复硝酚盐残留量的方法,样品经甲醇-水-磷酸体系提取,HLB固相萃取柱净化,乙酸酐衍生,气相色谱-电子捕获检测器测定,外标法定量,液相色谱-质谱定性。结果表明,在0.01～1.0mg/L范围内线性良好,方法定量限为0.01mg/kg。对草莓、苹果、番茄、马铃薯、菠菜、茄子6种水果蔬菜进行3个水平(0.01、0.02、0.05mg/kg)的添加回收,回收率在81.0%～106.6%之间,相对标准偏差3.9%～8.1%,该方法可靠、稳定,可满足水果蔬菜中复硝酚盐残留检测与确证的需要。     

定量分析食品中的矿物油污染物

矿物油是碳数为10~50的直链、支链和烷基取代的环状饱和烷烃与芳香烃的混合物,其化学组成非常复杂。近年来,食品中的矿油油污染问题受到持续关注,主要原因是食品包装涉及使用回收纸和再生纸,其残留印刷油墨中的大量工业级矿物油造成与其接触食品的污染。调查显示:几乎所有食品中都或多或少含有矿物油。目前,国内对于食品中矿物油的分析方法还仅局限于定性鉴别。欧洲对矿物油的定量研究较多,陆续开发出在线联用的高效液相色谱-气相色谱-氢火焰离子化器检测法(HPLC-GC-FID)、离线固相萃取法(SPE-GC-FID)以及二维气相色谱法(GC×GC)等定量分析方法。本文综述了食品中矿物油污染物的最新分析技术、操作步骤以及定量结果的数据处理方法,目的是通过借鉴,研发出适用于我国食品中矿物油的定量分析方法,开展市售食品调查,保障食品安全。     

固相萃取柱净化-气相色谱法定量测定食用植物油中饱和烃类矿物油

目的以自制硫酸硅胶和10%硝酸银硅胶填料分层装填的复合固相萃取柱为净化手段,建立一种测定食用植物油中饱和烃类矿物油的分析方法。方法样品经正己烷提取,固相萃取柱净化,氮吹浓缩,然后经DB-1石英毛细管色谱柱分离,采用气相色谱-火焰离子化检测器检测,外标法定量。结果考察了填料类型、填料用量、洗脱体积等因素对提取效率的影响。在优化的条件下,饱和烃类矿物油检测的线性范围为5.0~500.0mg/L,相关系数r~2=0.9991,方法检出限为3.0 mg/kg,定量限为10.0 mg/kg。样品在10.0、20.0、50.0 mg/kg 3个水平下的加标回收率为93.2%~103.7%,相对标准偏差为3.97%~5.33%(n=6)。结论该法操作简单、快速、准确度高,检出限能满足对食用植物油中饱和烃类矿物油残留的检测要求,且使用常规分析仪器、分析成本低,值得推广应用。     

气相色谱-质谱法测定食品基质中四聚乙醛残留量

建立气相色谱-质谱法测定食品基质中四聚乙醛残留量。采用二氯甲烷-丙酮混合溶剂提取,石墨化炭黑/氨基复合固相萃取柱净化,气相色谱-质谱法检测大米、大豆、菠菜、番茄、洋葱、茶叶、苹果、板栗等多种植物源食品基质中四聚乙醛残留的方法。结果表明,该方法定量限为0.01mg/kg,在添加0.01～0.5mg/kg范围内,加标回收率为70.5%～111.7%,相对标准偏差为4.4%～11%。     

固相萃取结合气相色谱-火焰离子化检测器分析面包中饱和烃类矿物油

为分析面包中饱和烃类矿物油(mineral oil saturated hydrocarbons,MOSH),建立了一种硝酸银硅胶固相萃取GC-FID方法。在优化的前处理及色谱条件下,面包中的MOSH最低检出限为1.0 mg/kg,定量限为3.0mg/kg,一定范围内线性良好(R2=0.999 1),回收率(90.4%~105.1%)和相对标准偏差(3.29%~5.77%)(n=6)均满足方法性能要求。实际样品的分析表明,面包中的MOSH的含量较高,其中MOSH(n-C_(16)-C_(24))最高为101.4mg/kg,MOSH(n-C24-C35)最高为71.3mg/kg。     

固相萃取－气相色谱法同时检测茶叶中多种农药和多氯联苯残留

建立茶叶中21种有机氯、拟除虫菊酯类农药和多氯联苯(polychlorinated biphenyls,PCBs)残留固相萃取(solid-phase extraction,SPE)-气相色谱分析方法。用正己烷-丙酮(1:1,V/V)提取,经Envi-Carb/NH2复合固相萃取柱净化,采用RTX-5毛细管柱分离,气相色谱-电子捕获检测器(gas chromatography-electron caputure detector,GC-ECD)检测。在0.02、0.05、0.3mg/kg三个添加水平,平均回收率为68.64%～125.62%,相对标准偏差(relative standard deviation,RSD)为1.05%～12.78%,该方法的检测限(detection of limit,LOD)在0.0022～0.0129mg/kg之间,适用于茶叶试样中痕量残留的分析。     

速食食品纸桶包装冲泡过程的矿物油迁移试验研究

目的 建立速食食品纸桶在冲泡过程中产生矿物油迁移的化学溶剂替代试验,并且以此考察市售纸桶包装的矿物油迁移情况。方法 首先将100 ℃的玉米油倒入空纸桶,自然放置30 min以模拟冲泡过程;然后以该植物油为参考,分别考察换作正己烷和95%乙醇的迁移数据,寻找纸桶在食品冲泡过程中矿物油迁移试验的替代化学溶剂。结果 冲泡过程中纸桶及其外层印刷油墨均会迁移矿物油至玉米油中,其中饱和烃（mineral oil saturated hydrocarbons, MOSH）的迁移量为2.26~22.73 mg/kg;纸桶迁移矿物油至正己烷的数据与其迁移到植物油的具有较好的可比性,因而确定正己烷为纸桶的矿物油迁移的化学替代溶剂,从而建立了纸桶冲泡过程的迁移试验,即100 mL正己烷在常温下置于空纸桶30 min,然后测定迁移液中MOSH和芳香烃（mineral oil aromatic hydrocarbons, MOAH）。结论 纸桶包装在冲泡过程会不同程度地迁移出矿物油,其中白桶的迁移量普遍高于牛皮纸桶,部分白桶的MOAH迁移量超出欧盟限量（0.05 mg/kg）。考虑到MOAH有致癌和遗传毒性,建议予以重视。     

Comparability of mineral oil testing for dry food and cardboard samples – Perspectives from different PT rounds

Mineral oil hydrocarbons (MOH) can be found in detectable levels in a multitude of foodstuffs. Therefore, chemical analysis of food for MOH gains importance. Different proficiency testing (PT) rounds on mineral oil testing have been performed in different matrices: cereals and rice as well as cardboard samples were examined. The laboratories participating in the PT rounds had to follow specific requirements for examination. The sample materials used contained different concentrations of mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH). The PT results were statistically evaluated according to ISO 13528:2005 and additionally the HorRat(R) value was calculated to gain information on the comparability of the mineral oil testing. It could be shown that for the examined sample materials and under the chosen specifications for testing a comparable determination of the mineral oil content is possible within the required relative standard deviations. A useful analytical determination can be achieved with an acceptable relative standard deviation of <50% from a concentration of defined mineral oil fractions at ≥1 mg/kg in food. In the concentration range for MOH in food of between 1 mg/kg and 2 mg/kg, relative standard deviations of 20–40% were achieved. MOH concentrations of ≥ 2 mg/kg food were determined with good relative standard deviations of around 20%. Moreover, due to the results gained within this work a statement concerning the comparability for MOSH and MOAH contents below concentrations of 1 mg/kg food is possible: under the chosen conditions for examination as part of this work, mineral oil determination below 1 mg/kg food showed high variability. To gain reliable information with regard to consumer protection on the risk of mineral oil contents in this low concentration range further standardisation of the test method is indicated.     

Potential for short-term migration of mineral oil hydrocarbons from coated and uncoated food contact paper and board into a fatty food simulant

ABSTRACT

Mineral oil hydrocarbons (MOH) are widely used in the food industry for applications such as printing inks, additives, adhesives, and processing aids for food additives. Recently, the migration of MOH from food contact paper and board into foods has raised public health concerns. In this study, a total of 110 food contact paper and board samples, including baking and cooking paper (23), baking cups (28), food packaging bags (22), lunch boxes (8), party plates (26), and straws (3) were evaluated to quantify the content and short-term migration levels of MOH. The MOH were separated into mineral oil saturated hydrocarbons (MOSH)/polyolefin oligomeric saturated hydrocarbons (POSH) and mineral oil aromatic hydrocarbons (MOAH) via a validated on-line liquid chromatography?gas chromatography?flame ionisation detection (LC–GC–FID) technique. The coating materials of the sample products comprised polyethylene, polypropylene, polyethylene terephthalate, and silicone. The effects of the coating materials on the content and migration of MOH/POSH were evaluated. Quantitative analysis of the MOH in the samples showed that the MOSH/POSH and MOAH content varied widely, ranging from 16 to 5626 mg kg^?1 for MOH, regardless of the coating materials. Short-term migration of MOSH/POSH was observed only in samples with polyolefinic coatings, such as polyethylene and polypropylene, in experiments conducted at 25 °C for 10 min, although the extent of MOAH migration for all samples was at the trace level. The migration of MOSH/POSH was detected within the range of 0.93 to 62.3 μg L^?1 in 22 samples, and the migration of MOAH was detected within the range of 0.80 to 2.6 μg L^?1 in only 4 samples. These results demonstrate that although the short-term migration potential of MOH is generally negligible, the migration of MOSH/POSH into wet fatty foods can be accelerated by polyolefinic coatings, even within a very short time.     

Migration of mineral oil from printed paperboard into dry foods: survey of the German market

From the German market, 119 samples of dry food were analyzed for the migration of mineral oil. The products selected were packed in paperboard boxes and intended for storage for extended periods of time at ambient temperature. The 0.6 mg/kg limit for mineral oil saturated hydrocarbons (MOSH) derived from the WHO/JECFA evaluation was frequently exceeded by a factor of 10–100. Typically, 10–20% of the migrating mineral oil consisted of aromatic hydrocarbons (MOAH). Most samples were merely 2–3 months old and far from the end of their shelf life (usually 1–3 years). From the assumption that about 70% of the MOSH and MOAH which are eluted from GC up to the C₂₄ n-alkane (<C24) end up in the food (potential of migration), it was estimated that migration might almost triple before the products reach the end of their shelf life, reaching 31 mg/kg on average, with several samples exceeding 100 mg/kg. At the time of the analysis, products without an internal bag and with a bag of paper or polyethylene reached up to about 80% of the potential of migration (average, 30–50%). Bags of polypropylene, acrylate-coated polypropylene, PET or with an aluminum layer seemed to block migration (with one possible exception), but it was premature to reach conclusions on long-term functional barrier properties. From the comparison with <C₂₄ MOSH concentrations in unprinted recycled paperboards, it was estimated than on average about a quarter of the migrating mineral oil was from printing ink used for decorating the box.     

The analysis of saturated and aromatic mineral oil hydrocarbons in dry foods and from recycled paperboard packages by online HPLC–GC–FID

ABSTRACT

The purpose of this study was to determine the concentrations of mineral oil hydrocarbons in dry foodstuffs packed in recycled paperboard, which were imported from different foreign countries to Germany. After collection, mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH) in dry foodstuffs and recycled paperboard were analysed using online coupled high-performance liquid chromatography–gas chromatography–flame ionisation detection (online HPLC–GC–FID) far before the end of the shelf life of the samples. Our results showed that recycled paperboard has MOAH content higher than that of dry foodstuffs. The proportion of MOAH within total mineral oil hydrocarbons was determined to be 7–45% in dry foodstuffs and 4–48% in paperboard. In addition, 29% of the products were found to contain over 1.00 mg/kg MOAH, with a maximum of 2.72 mg/kg in oatmeal. White colour recycled paperboard contained lower amounts of MOSH and MOAH than that of brown and grey colour recycled paperboard. The MOSH concentration in dry foodstuffs ranged from 0.11 to 21.92 mg/kg (?C25 hydrocarbons), which may be an indication of rapid migration. The lowest determined MOSH concentrations (?C25 hydrocarbons) were found in sea salt and soda samples, even when their paperboard contained high mineral oil hydrocarbons. Our three samples in packages containing internal bags (for complete barriers) were found to have low mineral oil concentration due to reduced migration through plastic (acrylate-coated polypropylene). However, one sample, a ‘crispy’ product with an internal bag, contained the extreme amount of 21.92 mg/kg. Differences in contaminants observed in both dry foodstuffs and recycled paperboard may have been due to the different packaging and production techniques of the different countries. In addition, 8 of 24 dry foodstuff samples contained MOSH concentrations frequently exceeding the 2.0 mg/kg limit for MOSH C₂₀–C₃₅.     

基于液相色谱-气相色谱联用测定巧克力中的饱和烃与芳香烃矿物油

建立基于液相色谱-气相色谱（on-line liquid chromatography-gas chromatography,LC-GC）联用测定巧克力中饱和烃（mineral oil saturated hydrocarbons,MOSH）和芳香烃矿物油（mineral oil aromatic hydrocarbons,MOAH）的方法。该方法以正己烷于60 ℃超声提取20 min,取上清液以硅胶除去脂肪,以间氯过氧苯甲酸与烯烃进行环氧化反应,最后以LC-GC联用技术分离测定,其中LC用于保留油脂和烯烃环氧化物,同时分离得到MOSH和MOAH,通过由阀切换、保留间隙与溶剂排空阀组成的LC-GC接口分别将MOSH和MOAH导入2 个平行的GC通道并以氢火焰离子化检测器测定。该方法的定量限为0.5 mg/kg,矿物油在0.5～85.5 mg/L内线性关系良好（R2=0.998）,加标回收率为80.3%～93.8%,相对标准偏差为1.58%～8.22%。测定了28 个巧克力产品中的矿物油含量,其中有20 个产品检出MOSH,含量为1.83～22.23 mg/kg,1 个检出1.57 mg/kg MOAH。谱图分析表明,一些产品中含有塑料迁移出的聚烯烃低聚饱和烃（polyolefin oligomeric saturated hydrocarbons,POSH）,LC-GC无法分离POSH与MOSH,因此测得结果实际上是MOSH和POSH的总量。     

Enrichment for reducing the detection limits for the analysis of mineral oil in fatty foods

A German draft for a regulation requires that there must be no migration of mineral oil aromatic hydrocarbons (MOAH) from recycled paperboard into food. The Federal Institute for Risk Assessment (BfR) is requested to establish the detection limit. It was previously shown that the detection limit of the commonly used methods is below 0.1 mg/kg for the majority of the foods, but substantially higher in fatty products because of limited capacity of the liquid chromatographic preseparation to retain fat, interference by olefins and, if also the mineral oil saturated hydrocarbons (MOSH) should be analyzed, the natural paraffins primarily consisting of odd-numbered n-alkanes. A method is described for the enrichment of the MOSH and MOAH conceived as an auxiliary tool for fatty foods analyzed by the conventional methods, such as on-line HPLC–GC. In a double bed liquid chromatographic column, the lower packing consists of a mixture of activated aluminum oxide, silica gel with silver nitrate and activated silica gel, the upper of activated silica gel. The technical detection limit in edible oils is below 0.3 mg/kg, which translates to less than 0.1 mg/kg in the dry foods packed in recycled paperboard. The distinction between migrated mineral oil and that present before packaging often presupposes the availability of the food prior to packaging.     

Analysis of mineral oil in food: results of a Belgian market survey

ABSTRACT

Recently, migration of mineral oil components from food contact materials into various foods has been reported. The analysis of mineral oil in food is complicated since it consists of mineral oil saturated hydrocarbons (MOSH) comprising a complex mixture of linear, branched and cyclic compounds and variable amounts of mineral oil aromatic hydrocarbons (MOAH), mainly alkylated. Both MOSH and MOAH form ‘humps’ of unresolved peaks in the chromatograms with the same range of volatility. Since these two fractions have a different toxicological relevance, it is important to quantify them separately. Occurrence data on mineral oil are available only for a limited number of food groups and only from few countries. In Belgium, data on the contamination of food by mineral oil are lacking. In this contribution, an in-house validated online combination of liquid chromatography with gas chromatography (LC–GC) with flame ionisation detection (FID) was used for the quantification of MOSH and MOAH. Totally, 217 packed food samples were selected using a well-defined sampling strategy that targeted food categories which are highly consumed and categories suspected to contain mineral oil. For 19 samples, the method was not applicable. For the 198 remaining samples, MOSH was detected in 142 samples with concentrations up to 84.82 mg kg^?1. For the MOAH fraction, there are 175 samples with a concentration below the limits of quantification (LOQ), while 23 samples had a higher concentration ranging from 0.6 to 2.24 mg kg^?1. Finally, these results were compared with the action thresholds as proposed by the Scientific Committee (SciCom) of the Belgian Food Safety Agency (FAVV-AFSCA). Only one sample exceeded the threshold for MOSH, while the threshold for MOAH was exceeded in 23 samples. For the samples exceeding the action threshold, further investigation is needed to identify the contamination source.