A method of gas chromatography-mass spectrometry (GC-MS) was established to determine the migration of dibutyl sebacate, dioctyl sebacate, diisooctyl sebacate, decanedioic acid bis(2,2,6,6-tetramethyl-4-piperidinyl)ester in water-based, acidic and alcoholic food simulants, and olive oil and chemical alternative solvents. The 95% ethanol and isooctane chemical substitution solutions were directly analyzed by GC-MS. The olive oil samples were extracted with acetonitrile followed by QuEChERS purification, and then analyzed by GC-MS. Other simulants (water, 4% acetic acid, 10% ethanol, 20% ethanol, and 50% ethanol) were extracted with n-hexane and then determined by GC-MS. The results showed that the method is well performed under optimized conditions, with the correlation coefficient (r2) greater than 0.995. The limits of detection and the limits of quantitation of the four sebacic acid ester compounds in water, 4% acetic acid, 10% ethanol, 20% ethanol, 50% ethanol, 95% ethanol, isooctane, and olive oil simulants are 0.1-0.2 mg/kg, 0.3-0.5 mg/kg, respectively. Migration experiments on plastic samples were conducted, and spiking experiments at three concentration levels of 0.30, 2.0, 4.0 mg/kg in water, 4% acetic acid, 10% ethanol, 20% ethanol, 50% ethanol, 95% ethanol, and isooctane food simulants, and three concentration levels of 0.50, 2.0, 4.0 mg/kg in olive oil food simulants were carried out. The spiking recoveries range from 92.5% to 108%, and the relative standard deviations (RSDs) are 2.4%-8.8%. The method solves the problem that decanedioic acid bis(2,2,6,6-tetramethyl-4-piperidinyl)ester cannot be extracted into n-hexane in 4% acetic acid by adjusting pH value using ammonium hydroxide, the optimal pH range was determined by comparing the responses of four targets at different pH values. QuEChERS was firstly used for migration experiments of sebacic acid esters in food contact materials to solve the turbidity and partial oil precipitation of olive oil simulants in the concentration process after extraction. By optimizing the QuEChERS filling material, the interference of organic acids, fatty acids, sugar and other impurities on the targets were reduced, producing greater separation effect of the targets. The separation efficiency of four chromatographic columns with different polarity was compared, and the DB-17HT column was selected to detect the four sebacic acid esters simultaneously. Plastics such as polypropylene, polyethylene terephthalic acid terephthalate, polyvinyl chloride, composite membranes, paper cups, recycled PET and recycled PVC were collected and migration experiments were carried out, the migration of sebacic acid esters in these plastics materials was investigated. This method is highly sensitive, precise, and accurate, fully meeting the requirement for determining the migration of the sebacic acid esters in food contact materials and their products.

The method for the determination of migration of lactide in polylactic acid (PLA) food contact material by gas chromatography-mass spectrometry (GC-MS) was established. Olive oil simulants were extracted by acetonitrile, centrifuged and filtered, and then analyzed by GC-MS. Isooctane simulants were directly filtered and analyzed by GC-MS. The method could achieve the determination of lactide migration in PLA. The limit of detection was 0.01 mg/kg and the recoveries at spiked levels were 80.0%~120.0%. The relative standard deviations were 2.6%~6.6% (n=6). Seven PLA samples were analyzed by the method. The detection rate was 85.7% and the range of concentration were 0.033~1.1 mg/kg. The method had the advantages of high sensitivity, high recovery and accuracy. The detection limit can meet the requirements of regulations. The method was suitable for migration of lactide in PLA food contact materials. The results showed that the detection rate of migration of lactide in PLA samples was high and migration of lactide should be paid attention to. Compared with isooctane, the migration of olive oil in the sample was higher than that of isooctane under the substitution condition due to the higher migration temperature of olive oil.

目的 建立并优化氧弹燃烧-离子色谱法测定一次性食品接触用生物基塑料(下文简称生物基塑料)中氟含量的检测方法,分析市售生物基塑料产品中氟含量情况.方法 生物基塑料经氧弹燃烧发生高温氧化分解,氟化物转化为游离态氟离子,被吸收或溶解在吸收液中,以5.0 mmol/L碳酸氢钠和1.0 mmol/L无水碳酸钠溶液作为流动相进行等度洗脱,进样量为20μL,流速为0.8 mL/min;采用Metrosep A Supp 7色谱柱(250 mm×4.0 mm,5.0μm)和Metrosep A Supp 5 Guard保护柱(50 mm×4.0 mm,5.0μm),柱温为45℃;以电导检测器进行测定,外标法定量.结果 氧弹燃烧-离子色谱法测定生物基塑料中氟含量的相关系数R2>0.995,检出限为5.0 mg/kg,定量限为10 mg/kg,线性关系良好,加标回收率为93.8％～98.4％,精密度为2.9％～6.8％(n=6).通过对119款实际样品中氟含量进行定量分析,总体检出率为94.11％,总体不合格率为15.94％;PLA吸管、PLA+PBAT吸管和PLA+PBS吸管的检出率均为100％,不合格率分别为45.16％、30.77％和5.88％.结论 该方法可靠、方便、灵敏,分离效果好,适用于生物基塑料中氟含量的检测.

目的 建立利用燃烧氧化法测试包装用生物降解塑料中TOC含量的方法.方法 对已知含无机碳酸盐填料的样品,分别用盐酸进行酸化处理和不经酸化处理,研究用酸化样品对消除样品中无机碳酸盐干扰的效果;在不同温度下考察薄层纤维素的TOC测定结果,对燃烧温度进行优化;在优化后的条件下,采用碳酸钙作为碳含量的标准物质,对包装用生物降解塑料实际样品进行定量测试.结果 经酸化处理后的塑料样品,TOC检测值与理论值偏差仅为-1.22％～+1.42％,而不经酸化处理的塑料样品,实测值与理论计算值的偏差为+7.40％～+29.36％,可见经过酸化处理所得结果更为准确;在950℃到1250℃区间内,对薄层纤维素样品分别在不同温度下进行燃烧氧化测试,发现最佳燃烧温度为1100℃;利用碳酸钙为标准品绘制标准工作曲线,结果表明在0.6～24 mg碳含量内,标准工作曲线线性关系良好;对7个生物降解塑料实际样品进行检测,TOC实测值与理论计算值的偏差在-4.26％～+3.47％.结论 研究表明,该方法操作简便、线性良好,精密度和准确性高,适用于生物降解塑料中TOC的检测.

为评估食品接触材料及制品中苯系物的迁移风险，建立了同时测定食品接触材料及制品中9种苯系物在4%乙酸、10%乙醇和橄榄油中迁移量的吹扫捕集/气相色谱-质谱联用法（P＆T/GC-MS）。采用HP-INNOWax毛细管色谱柱对迁移实验后的9种苯系物进行分离，选择离子监测（SIM）模式进行检测。结果表明，9种苯系物的分离效果良好，在0.50～5.0μg/kg或0.50～5.0μg/L范围内线性关系良好，相关系数（r2）均不小于0.995，方法检出限为0.15μg/kg，方法定量下限为0.50μg/kg，加标回收率为78.5%～107%，相对标准偏差（n=6）为1.1%～9.2%。该方法具有较高的准确度和较好的重现性，可用于食品接触材料及其制品中9种苯系物迁移量的测定。

采用超高效液相色谱-串联质谱(UPLC-MS/MS)建立了食品接触用纸和纸制品中乙烯亚胺迁移量的测定方法.以0.1％(体积分数)甲酸水溶液和甲醇作为流动相,使用电喷雾离子源对目标物进行电离,采用多反应监测模式进行测定.结果表明,乙烯亚胺在4％乙酸、10％乙醇、95％乙醇与异辛烷模拟物中的线性范围为0.003～0.05 mg/L,检出限为1μg/L;在橄榄油模拟物中的线性范围为0.003～0.05 mg/kg,检出限为1μg/kg.各食品模拟物中,乙烯亚胺的加标回收率为96.0％～102％,相对标准偏差(RSD)为1.6％～5.9％.采用该方法对20批次实际样品进行检测,有2批次检出乙烯亚胺.该方法简单快速,具有较高的准确性、灵敏度,适用于食品接触用纸和纸制品中乙烯亚胺迁移量的检测.

为评估食品接触用塑料中添加剂的迁移风险,采用超高效液相色谱-四极杆飞行时间质谱(UPLC-QTOF MS)建立了同时测定食品接触用塑料中50种添加剂迁移量的方法.以甲醇和0.01％(体积分数)甲酸-5 mmol/L乙酸铵溶液为流动相进行洗脱,采用目标离子采集(Target MS/MS)模式对目标物的一级离子与二级离子进行监测.结果表明,各物质在0.02～5 mg/L质量浓度范围内线性关系良好,方法检出限为0.01～0.1 mg/kg,加标回收率为92.6％～104％,相对标准偏差(RSD)为0.60％～8.4％.在20款实际样品中有12个样品检出塑料添加剂,其中2个样品检出壬基酚,迁移量为0.033～0.071 mg/kg;6个样品检出抗氧化剂1076和抗氧化剂168,迁移量为0.12～3.3 mg/kg;4个样品检出光引发剂369、光引发剂ITX和光引发剂TPO,迁移量为0.054～4.0 mg/kg.该方法简单、灵敏、准确,适用于食品接触用塑料中50种添加剂迁移量的检测.

目的 研究陶瓷制品口缘和器身中多种金属元素的迁移风险,并考察合规判定规则.方法 采用体积分数为4％乙酸模拟物对41种杯类陶瓷口缘和器身进行3次迁移实验,用电感耦合等离子体质谱法对试液中的18种金属元素进行检测.结果 陶瓷制品口缘和器身的金属元素迁移量平均值随迁移次数递减;铝(Al)、钴(Co)、锌(Zn)、铅(Pb)的最大迁移量超过讨论限量10％的样品数,明显高于其他金属元素的样品数,且同样特征的样品中口缘的样品数高于器身的样品数.结论 陶瓷制品具有较高的Al、Co、Zn、Pb迁移风险,而且口缘比器身的迁移风险更高.建议金属元素迁移量以第1次迁移实验结果进行合规判定.

为了评估食品接触材料及制品中抗氧化剂的迁移风险,采用超高效液相色谱一串联质谱法(UPLC-MS/MS)建立了同时测定食品接触材料及制品中9种抗氧化剂迁移量的方法.采用C18色谱柱对迁移实验后的食品模拟物中9种抗氧化剂进行分离,1 mmol/L氟化铵和甲醇为流动相洗脱,采用电喷雾离子源(ESI),多反应监测(MRM)正负离子模式进行扫描.结果表明,9种抗氧化剂的色谱分离效果良好,并在0.3-6mg/L质量浓度范围内与其峰面积均呈良好的线性关系,检出限为0.1 mg/L.加标回收率为93.9％-106％,相对标准偏差(RSD)为0.80％-9.3％.该方法快速高效、线性范围好,适用于塑料食品接触材料及制品中9种抗氧化剂迁移量的检测.

建立了气相色谱-质谱联用法(GC-MS)同时检测食品接触用纸制品中1,3-二氯-2-丙醇(1,3-DCP)、2,3-二氯-1-丙醇(2,3-DCP)、2-氯-1,3-丙二醇(2-MCPD)与3-氯-1,2-丙二醇(3-MCPD)四种氯丙醇迁移量的测定方法,食品模拟物包括4％乙酸、10％乙醇,50％乙醇与橄榄油.通过方法优化,四种氯丙醇的方法检出限与定量限分别为2μg/kg与10μg/kg,加标回收率为87.3％～109％,相对标准偏差(RSD)为1.1％～9.5％(n=6).实验表明,该方法准确度高,重现性好,可满足纸制品中氯丙醇迁移量的检测要求.应用此方法对15批次纸制品进行检测,结果显示,3-MCPD迁移量的检出率与检出水平最高,1,3-DCP与3-MCPD迁移量的检出率分别为33.3％与53.3％,迁移量分别为2.27～12.04μg/kg与2.51～183.32μg/kg,2,3-DCP与2-MCPD迁移量均为未检出;氯丙醇在水基模拟物的迁移水平比橄榄油模拟物的迁移水平高.纸制品中普遍检出1,3-DCP与3-MCPD迁移,其对食品安全的影响需引起关注.

建立了食品接触材料中2-甲基-1,3-丙二醇(MPO)和新戊二醇(NPG)迁移量的气相色谱-质谱(GC-MS)检测方法.食品接触材料经迁移试验后,所得浸泡液经苯硼酸溶液衍生化、正己烷萃取后,GC-MS测定.结果表明,该方法在优化条件下的线性相关性良好,相关系数(r2)大于0.995;MPO和NPG在4％乙酸、10％乙醇、50％乙醇和异辛烷中的检出限均为0.01 mg/L;线性范围均为0.02～0.10 mg/L;在95％乙醇中,MPO的检出限为0.30 mg/L,线性范围为0.50～1.6 mg/L,NPG的检出限为0.03 mg/L,线性范围为0.05～0.16 mg/L.该方法在低、中、高3个浓度水平的平均回收率为85.0％～112％,相对标准偏差(RSD)为0.60％～9.5％.该方法的检测结果准确、灵敏度高,能较好地实现食品接触材料及制品中MPO和NPG迁移量的测定,满足我国法规的限量要求.

对15种餐盘纸中矿物油的含量进行检测,并对其中1种印刷有已知油墨的餐盘纸进行溯源分析.采用离线固相萃取前处理,以混合溶液(正己烷-乙醇(1∶1,V/V)).作为提取溶剂,经0.3％硝酸银硅胶固相萃取柱分离纯化,气相色谱-氢火焰离子化检测法进行定量,气相色谱-质谱法进行定性分析.结果 表明:网店购买的4种餐盘纸的矿物油含量普遍比快餐店中收集到的餐盘纸高,饱和烃矿物油的最高含量为3397.6 mg/kg,芳香烃矿物油的最高含量为374.6 mg/kg,均超过限量值.通过溯源分析发现,有印刷的餐盘纸中一部分矿物油来源于油墨.本方法的检出限和定量限分别为2.73 mg/kg和8.19 mg/kg,加标回收率为92.1％～115.1％,相对标准偏差为3.12％～11.85％,准确性高,实验操作方便,可用于食品接触用纸中矿物油的检测及溯源分析.

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、3h,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.

To determine the occurrence of mineral oil hydrocarbons (MOH) in food contact papers in China, and to investigate the potential sources of MOH contamination, a total of 159 food contact papers and raw materials were analysed by off-line solid-phase extraction-gas chromatography flame ionisation detection (SPE-GC-FID) and a GC-MS method. The migration of MOH from food contact papers into Tenax, olive oil or 50% ethanol under the worst foreseeable conditions of use was determined. The results indicated that the occurrence of MOH in China is of a potential health risk concerning the migration of mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH) which were detected in 82.6% and 50.4% of samples, respectively. Migration of MOSH from 47.9% of samples was higher than 2 mg/kg and migration of MOAH from 32.2% samples exceeded 0.5 mg/kg in case of the worst foreseeable condition of use. The highest mean migration of MOSH and MOAH were found in packaging papers for long-term storage (more than 6 months), with mean migration of 91.2 mg/kg and 1.4 mg/kg, respectively. Migration of MOH from printed paper was considerably higher than that of unprinted paper, validating previous findings that the printing ink is the predominant source of MOH contamination in food contact papers. Migration of MOH from paper bowls used for packing instant noodles was relatively low, suggesting the internal hollow layer may be acting as a functional barrier that could block the transfer of MOH (up to C28) through the gas phrase, even though the outer layer was made from recycled paper. High concentrations of MOSH and MOAH were also detected in de-foamers, adhesives and rosin sizing agents, indicating that the MOH contamination caused by the use of raw materials and additives should also be taken into consideration.

目的 建立微波消解-电感耦合等离子体质谱法(inductively coupled plasma mass spectrometry,ICP-MS)测定食品接触用纸制品中铅、砷、铜等42种无机元素含量的分析方法.方法 纸制品经微波消解后,各元素含量由电感耦合等离子体质谱法进行分析,在动能歧视(kinetic energy discrimination,KED)模式下增加响应值,选择锗、铑、锆、铪、铼元素作为内标校正检测结果.结果 该方法可在约3.5 min内完成42种元素的测定,各元素方法定量限为0.02～0.1 mg/kg,且线性关系良好,r2>0.995,加标回收率为80％～120％,精密度为0.3％～9.9％(n=6).结论 该方法快速、灵敏,适用于纸制餐具的无机元素检测.铬、铜、锰、锶等元素在纸杯、纸碗、纸盒中检出率较高,需引起消费者及监管部门的重视.

为评估食品接触用油墨中光引发剂的迁移风险,采用超高效液相色谱-串联质谱(UPLC-MS/MS)建立了同时测定食品接触用油墨中20种光引发剂迁移量的方法.以0.1％(体积分数)甲酸和甲醇为流动相进行梯度洗脱,采用多反应监测模式对目标物的定量离子和定性离子进行监测,检测迁移实验后食品模拟物中的20种光引发剂.结果表明,该方法对20种光引发剂的色谱分离效果良好,各物质在0.02～0.5 mg/L质量浓度范围内线性关系良好,检出限为0.01 mg/kg,定量下限为0.02 mg/kg.加标回收率为87.1％～104％,相对标准偏差(RSD)为2.1％～8.6％,在10款样品中共检出4类光引发剂.该方法简单、灵敏、准确,适用于食品接触用油墨中20种光引发剂迁移量的检测.

Mineral oil hydrocarbon (MOH) contamination of various foods in the past few decades has raised much concern due to its potential adverse health effects. Since infant formulas (IF) is the major food source for infants, it is necessary to understand MOH contamination level in IF and consequent potential food safety risks. Data on the contamination of IF by mineral oil are lacking in China. On the other hand, the analysis of MOH in food is difficult. There is no harmonised standard analytical method for testing MOHs in IF. GC-FID/MS was chosen as the analytical tool being more convenient for surveys at a national level. Fifty-one IFs comprising dairy milk-based IFs (n = 39) and goat milk-based IFs (n = 12), including different stages (Stage 1, 2 and 3), package type (metal cans and paper boxes) were collected in China market in 2018 for this survey. 17 of 51 IFs were found positive, but trace levels MOAH were found (≤0.7 mg/kg). For the positive samples, all the MOSH and MOAH hump fell into the C16-C25 fraction. MOH humps were found in all the 12 goat milk-based IFs, even 4 samples are reported with quantifiable values which are higher than the method defined LOQ. The highest quantifiable MOH contamination level of goat milk-based IFs were MOSH = 3.5 mg/kg and MOAH = 0.7 mg/kg. Further root cause analysis of contamination is highly recommended to control the MOH contamination for goat milk-based IFs.

目前食品接触材料安全性日益受到关注.食品接触材料产生的挥发性物质,常常具有异常的气味,可能通过气相传质或直接接触迁移至食品中,不但会引发食品感官特性的变化,影响消费者的使用体验,削弱消费者购买欲望,过量摄入后还会危及人体健康.因此,准确识别和检测食品接触材料产生的异味物质,对确保食品接触材料的合规以及保护消费者健康安全显得尤为重要.本文对国内外关于挥发性物质气味评估和检测技术及其在食品接触材料领域的运用进行综述.重点介绍了顶空、顶空-固相微萃取、热脱附、电子鼻等气味分析技术,及其与气相色谱、气相色谱/质谱或气相色谱-嗅闻-质谱仪等结合的联用分析技术,并梳理和展望了食品接触材料中挥发性气味物质分析技术发展前景,为有效管控食品接触材料异味问题提供技术参考.

对胶粘剂中丙烯酸正丁酯在Tenax的迁移行为进行研究,并分析比较了欧盟标准规定的转化条件下不同模拟物中丙烯酸正丁酯的迁移情况和迁移机理.结果 表明,Tenax中丙烯酸正丁酯在不同温度下经过一定时间后迁移达到平衡(175℃除外);20℃下目标物的迁移长期处于“吸附-脱附”的动态平衡中;70℃下随着时间增长迁移量不断上升,72 h后达到平衡;100℃和175℃下Tenax在短时间内快速吸附目标物,之后发生脱附迁移量下降;当模拟物为Tenax,70℃,72h时,胶粘剂中丙烯酸正丁酯达到迁移平衡时的迁移量最大,为65.16 μg/kg.转化条件下95％乙醇、异辛烷和Tenax中目标物的迁移量均大于橄榄油的结果,且结果差异较大,其中Tenax的结果与橄榄油最接近,在低温条件下(20℃,70℃)差距较小,相对偏差在0.6％～5.1％之间.结果 证明,丙烯酸正丁酯在Tenax中的迁移行为受多种因素的影响,迁移量并非随着温度和时间呈正相关的关系;使用替代模拟物进行迁移试验所获得的结果“高估”了实际情况下的迁移量,因此需依据食品接触材料的实际情况科学地选择模拟物,才能对材料进行准确有效的安全风险评估.

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(solid phase 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(mineral oil saturated hydrocarbons,MOSH)和芳香烃类矿物油(mineral oil aromatic hydrocarbons,MOAH)的在线分离,仪器分析时间仅为34 min.MOSH和MOAH的检出限为0.5 mg/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.