超高效液相色谱-串联质谱法同时测定食品接触材料及制品中9种抗氧化剂迁移量

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-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0.3~6 mg/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。     

在线净化液相色谱-高分辨质谱法快速测定动物源性食品中均三嗪类药物及其代谢产物的残留量

基于在线净化液相色谱-四极杆/静电场轨道阱高分辨质谱技术建立了快速测定动物源食品中地克珠利、妥曲珠利、妥曲珠利砜和妥曲珠利亚砜残留的分析方法。样品采用乙腈提取,经Cyclone在线净化柱净化后,将富集的目标物洗脱转至C_(18)分析柱,经色谱分离后,采用四极杆/静电场轨道阱高分辨质谱以Full Scan/dd MS2模式进行检测。4种化合物在0.5~50 ng/m L范围内呈良好线性,相关系数均大于0.999 4,方法的定量下限(LOQ)为2μg/kg。待测物在4种基质中的加标回收率为80.2%~110.5%,相对标准偏差为2.8%~9.7%。该方法简化了前处理过程,消除了基质干扰。利用精确质量数、保留时间、同位素峰比、二级碎片多个定性信息能够实现快速确证测定。     

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。     

通过型固相萃取-液相色谱-高分辨质谱法快速测定粮谷中17种酰胺类农药残留量

应用PRiME HLB固相萃取柱通过式净化技术,采用液相色谱-四极杆静电场轨道阱高分辨质谱(LC-Q Orbitrap),建立了粮谷中17种酰胺类农药的检测方法。样品经乙腈提取,PRiME HLB固相萃取柱净化,在GL Intersil ODS-3色谱柱上以0.5%甲酸水和乙腈为流动相进行梯度洗脱,四极杆静电场轨道阱高分辨质谱以Full Scan/ddMS^2模式进行检测。结果表明,各组分在各自浓度范围内线性关系良好,相关系数均大于0.996。方法定量限在0.5~5μg/kg之间。待测物在5.0,10.0,50.0μg/kg 3个浓度水平下加标回收率在70.4%~101.6%之间,相对标准偏差在2.7%~10.8%之间。该方法可用于粮谷中酰胺类农药的测定。     

超高效液相色谱-四极杆飞行时间质谱法同时测定食品接触用塑料中50种添加剂的迁移量

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。     

四极杆/静电场轨道阱高分辨质谱在青椒中农药多残留快速筛查的应用

建立了分散固相萃取法(d-SPE)萃取,高效液相色谱-四极杆/静电场轨道阱高分辨质谱快速筛查青椒中农药多残留的分析方法。样品采用乙腈提取,经N-丙基乙二胺(PSA)和C18分散固相萃取净化,以BEH C18色谱柱为分析柱,0.1%甲酸乙腈及含0.1%甲酸和4 mmol/L甲酸铵水溶液作为流动相进行梯度洗脱分离。采用正、负离子切换,同时对欧盟青椒定性和定量考核样品进行快速筛查,并对定量考核样品筛查到的16种农药进行定量测定。16种农药在一定浓度范围内呈良好的线性关系,相关系数(r2)大于0.995,该方法的定量下限为0.4~2.0μg/kg。在不同加标水平下的平均回收率为81.6%~116.5%,相对标准偏差为0.4%~7.5%。以欧盟青椒定量考核样品为研究对象,对其分别进行四极杆/静电场轨道阱高分辨质谱和三重四极杆质谱测定,结果表明,四极杆/静电场轨道阱高分辨质谱定量结果可与三重四极杆质谱结果相媲美。本方法简单、灵敏、准确,适用于农产品中农药多残留的快速筛查和分析测定,具有很好的实际应用价值。     

UPLC-MS/MS法同时测定食品接触用油墨中20种光引发剂的迁移量

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。     

磁性分散固相微萃取/UHPLC-Q-Orbitrap HRMS测定运动营养食品中27种氨基酸

基于磁性分散固相微萃取净化,建立了测定运动营养食品中27种氨基酸含量的超高效液相色谱-四极杆-静电场轨道阱高分辨质谱法。通过优化液相色谱条件、质谱条件和样品前处理过程,在20 min内实现了对27种目标物的测定。样品经涡旋振荡,超声提取,磁性氧化石墨烯分散固相微萃取净化,采用Thermo Accucore HILIC色谱柱分离,以0.1%甲酸水溶液（含5.0 mmol/L甲酸铵）和0.1%甲酸乙腈（含5.0 mmol/L甲酸铵）为流动相进行梯度洗脱,静电场轨道阱高分辨质谱检测,外标法定量。结果表明,27种目标化合物在一定质量浓度范围内线性良好,相关系数（r2）均大于0.99,方法的定量下限为0.10～0.25 mg/kg,平均回收率为70.0%～93.0%,日内相对标准偏差（RSD,n=6）为1.6%～10%,日间RSD(n=5)为1.4%～5.2%。该方法高效灵敏,准确可靠,适用于运动营养食品中27种氨基酸的测定。     

亲水相互作用色谱-四极杆/静电场轨道阱高分辨质谱检测奶粉中的氟乙酸钠

基于亲水相互作用色谱-四极杆/静电场轨道阱高分辨质谱系统,建立了奶粉中氟乙酸钠的快速筛查和定量检测方法。奶粉样品用水溶解后经正己烷脱脂,用6 mol/L硫酸调节pH值,经乙腈提取后用亲水相互作用色谱-四极杆/静电场轨道阱高分辨质谱进行分析。结果表明,该方法在1~50 μg/kg范围内线性关系良好,定量限为1 μg/kg,平均回收率为85.5%~106%,相对标准偏差为5.20%~13.6%。该方法可用于配方奶粉、脱脂奶粉和乳清粉等奶粉产品中氟乙酸钠的快速筛查和定量分析。     

液相色谱-四极杆/静电场轨道阱高分辨质谱快速分析动物源性食品中多肽类药物残留

建立了液相色谱-四极杆/静电场轨道阱高分辨质谱(Q/Exactive)分析鸡肉、鸡肝、鸡肾、猪肉、猪肝、猪肾、牛奶和鸡蛋中粘杆菌素A、粘杆菌素B、多粘菌素B、杆菌肽A和维吉尼霉素M的方法。动物源性食品采用1%(体积分数)乙酸乙腈-水(体积比为8∶2)超声提取,提取液直接经C18液相色谱柱分离。在电喷雾正离子模式下,四极杆质谱在m/z 1.2隔离窗口下过滤一级带电离子,高分辨静电场轨道阱质谱在35 000分辨率下进行目标物子离子全扫描(targeted-MS2)。根据5种多肽类药物的高分辨分子离子峰、同位素分布、特征子离子信息建立数据库,采用Trace Finder 3.0软件实现定性检索。为解决多肽类药物残留测定结果重复性差的难题,系统地评价了5种多肽类药物的关键操作技术条件,发现导致该类药物降解的主要因素包括:提取时间、玻璃器皿、存放时间。该方法测定5种多肽类药物时,测定结果的质量精度均小于5×10-6,维吉尼霉素M的定量限(LOQ)为0.5μg/kg,另外4种多肽类药物的LOQ均为10μg/kg。在0.25~500μg/kg范围内,5种多肽类药物的峰面积与质量浓度呈良好的线性关系,相关系数R2≥0.993 1,方法回收率为67.4%~108.9%,相对标准偏差为4.5%~17.2%。该方法操作简单,测定结果准确,可用于动物源性食品中多肽类药物残留的高通量测定。     

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。     

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。     

Interactions between poly(vinyl chloride) stabilised with epoxidised sunflower oil and food simulants

Commercial sunflower oil was epoxidised and used as organic co-stabiliser for rigid and plasticised poly(vinyl chloride) (PVC) containing Zn and Ca stearates as primary stabilisers and stearic acid as lubricant. For applications in the packaging of foodstuffs, migration testing must be performed. The detection and the quantification of contaminants migrating from the polymer into the food simulants are essential for the safety assessment of food contact plastic packaging materials. For that purpose, two food simulants were used: olive oil and 15% (v/v) aqueous ethanol. These represent fatty and moist food and beverages, respectively. The test conditions were 12 days at 40 °C. Circular samples of rigid PVC and PVC plasticised with dioctyl phthalate were immersed in a known volume of food simulant. A circular sample and 10 ml of food simulant were taken off every day to be analysed. Each sample was wiped and weighed. The rate of variation of the mass was determined as a function of time. The evolution of the peroxide index of olive oil with time was analysed. The specific migrations of the present additives were investigated by using two analytical methods (atomic absorption spectrometry and Fourier transform infrared spectroscopy). The influence of various parameters such as the nature of food simulant, the presence or the absence of the plasticiser, the agitation and time of contact was considered.     

Application of capillary electrophoresis in migration studies of food contact materials – part 1: Substituted phenolic additives

A method has been developed to determine 11 phenolic antioxidants in the food simulants distilled water, 3% acetie acid, and 15% ethanol, using; micellar capillary electrophoresis (MCE). All the phenols could he analyzed within 35 min. The analytical recovery from spiked simulants was 80 to 119% except for 2,6-di-tert-butyl-4hydroxytoluenc (BHT) and octyl gallate, which could not be recovered from 3% acetic acid simulant. Calibration graph correlation coefficients for the 11 phenols were 0.982 to 0.999. Limits of detection (LoDs) were from 2.8 to 8.6 mg/L. These LoDs are well below European Union migration limits for these substances. It is concluded therefore that MCE offers a rapid and reliable analysis for the control of migration from plastics intended for food contact which employ these phenols as antioxidants.     

超高效液相色谱法测定聚乙烯类食品接触材料中8种添加剂

食品接触材料中添加剂残留量的测定为食品接触材料从源头进行安全监管具有重要意义。然而目前的大多数研究只针对食品接触材料中有害物迁移量的测定,对于食品接触材料中有害物含量的测定方法仅局限于残留单体、低聚体、重金属,以及邻苯二甲酸酯类、双酚类化合物等环境污染物,对食品接触材料中添加剂残留量的测定较少。该研究系统地优化了样品前处理过程及仪器分析中影响8种添加剂分析准确度与响应灵敏度的各主要因素,建立了超高效液相色谱同时测定聚乙烯材料中8种添加剂的定量分析方法。聚乙烯样品冷冻研磨后,取2.0 g样品采用甲苯作为萃取溶剂,80 ℃, 10.34~11.72 MPa (1500~1700 psi)下对其进行加速溶剂萃取,取10 mL上清液,氮气吹干后用10 mL初始流动相(甲醇-水,7∶3, v/v)定容。采用ACQUITY UPLC BEH C₈色谱柱(100 mm×2.1 mm, 1.7 μm)进行分离,柱温30 ℃,进样量5 μL,以乙腈和水作为流动相进行梯度洗脱,流速0.3 mL/min,二极管阵列检测器(DAD)在210~400 nm范围内扫描,230、250、280、330 nm监测,外标法定量。8种目标物在0.2~10 μg/mL质量浓度范围内线性关系良好,相关系数(R ²)>0.999。空白聚乙烯样品添加含量为0.05%时,加标回收率在83.8%~103.4%之间,RSD在0.14%~7.86%之间。对于含量为0.2%~0.9%之间的质控样品,8种目标物的平均回收率在63.5%~118.5%之间,RSD在4.61%~15.6%之间。8种目标物的定量限为0.02%。应用该方法测定10份市售聚乙烯食品包装袋和手套,其中6份样品均检测出含有亚磷酸三(2,4-二叔丁苯基)酯(抗氧剂168),含量为0.02%~0.07%,均小于GB 9685-2016规定的聚乙烯类食品接触材料中抗氧剂168的最大使用量(0.2%)。该方法能够满足聚乙烯类产品中8种添加剂的分析要求,可用于食品接触材料风险监测。     

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     

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.     

Ultra‐high pressure LC for astaxanthin determination in shrimp by‐products and active food packaging

Nowadays, there is increasing interest in natural antioxidants from food by‐products. Astaxanthin is a potent antioxidant and one of the major carotenoids in crustaceans and salmonids. An ultra‐high pressure liquid chromatographic method was developed and validated for the determination of astaxanthin in shrimp by‐products, and its migration from new packaging materials to food simulants was also studied. The method uses an UPLC® BEH guard‐column (2.1 × 5 mm, 1.7 µm particle size) and an UPLC® BEH analytical column (2.1 × 50 mm, 1.7 µm particle size). Chromatographic separation was achieved using a programmed gradient mobile phase consisting of (A) acetonitrile–methanol (containing 0.05 m ammonium acetate)–dichloromethane (75:20:5, v/v/v) and (B) ultrapure water. This method was evaluated with respect to validation parameters such as linearity, precision, limit of detection, limit of quantification and recovery. Low‐density polyethylene films were prepared with different amounts of the lipid fraction of fermented shrimp waste by extrusion, and migration was evaluated into food simulants (isooctane and ethanol 95%, v/v). Migration was not detected under the tested conditions. Copyright © 2012 John Wiley & Sons, Ltd.