食品接触用塑料产品中19种邻苯二甲酸酯类增塑剂GC-MS检测研究

研究建立了食品接触用塑料产品中19种邻苯二甲酸酯类增塑剂的气相色谱-质谱联用仪(GC-MS)法快速检测方法。塑料产品以正己烷为萃取溶剂,采用超声萃取法对产品中邻苯二甲酸酯类增塑剂进行萃取,萃取液浓缩过滤后进行测定。19种邻苯二甲酸酯类增塑剂在0.05~1mg/L、0.5~10mg/L范围内线性良好,方法检出限(MDL)为0.1238mg/kg~0.9714mg/kg,加标回收率为89.6%~112.9%,相对标准偏差(RSDs)为2.61%~6.36%。该方法重现性好,检出限低,检测结果准确,可用于食品接触用塑料产品中19种邻苯二甲酸酯类增塑剂含量的检测,为食品接触材料中邻苯二甲酸酯质量控制提供相应的技术支撑。     

HPLC-MS/MS法测定食品接触材料中6种邻苯二甲酸酯的含量

建立了测定食品接触材料中6种邻苯二甲酸酯的含量的高效液相色谱-串联质谱法(HPLC-MS/MS)。实验以Agilent ZORBAX SB-C18色谱柱为分析柱,以甲醇-0.1%的甲酸水为流动相,采用梯度模式洗脱。质谱离子源的工作模式为正离子电离模式(ESI+),流速为0.35 mL/min,采用多反应监测离子模式(MRM)进行检测定量。实验样品前处理采用了加速溶剂萃取法,明显提高了食品接触材料中邻苯二甲酸酯的提取效率。结果表明:6种邻苯二甲酸酯在其线性范围内线性关系良好(R2>0.999),DPRP和BBP的定量限为1.0 ng/mL,DCHP,DNHP,DHP,DBEP的定量限为0.2 ng/mL,DPRP和BBP的检测限为0.2 ng/mL,DCHP,DNHP,DHP,DBEP的检测限为0.05 ng/mL。该方法的加标回收率为89.2%～107.5%,相对标准偏差均小于5.0%。实验表明,所建立的方法简单、灵敏度高,适用于食品接触材料中的6种邻苯二甲酸酯类增塑剂的分析检测。     

欧盟指令限制的与食品接触塑料中邻苯二甲酸酯类增塑剂迁移量的测定

建立了欧盟2007/19/EC指令中限制的对与食品接触的塑料材料中七种邻苯二甲酸酯迁移量的检测方法。样品采用食品模拟物浸泡后,取浸泡液用正乙烷进行液-液萃取,气相色谱仪/质谱联用仪（GC/MS）采用选择离子方式（SIM）检测,内标法定量。DBP、BBP、DEHP、nDnOP、DIDP、DINP、DAP检出限各为0.20...     

UPLC-LTQ/Orbitrap MS法测定塑料袋中35种致敏致癌染料

建立了用超高效液相色谱-线性离子阱/静电场轨道阱组合高分辨质谱(UPLC-LTQ/Orbitrap MS)快速检测日用塑料袋中的35种致敏致癌染料的检测方法。样品经二氯甲烷超声提取后,用ACQUITY UPLC BEH C18色谱柱分离目标物,在m/z为150~1000范围内进行一级质谱全扫描。以准分子离子峰的精确质量数和提取的色谱图峰面积进行筛查分析和定量,以保留时间和数据依赖扫描(data-dependent scan)模式获得的子离子质谱图进行定性确证。35种致敏致癌染料的质量偏差不大于5×10~(-6)(5ppm),方法检出限为0.02 mg/kg~0.3 mg/kg,精密度(RSD)为3.5%-9.2%。     

气相色谱-质谱法同时测定人体尿液中16种邻苯二甲酸酯

建立人尿中16种邻苯二甲酸酯的离子阱气相色谱-质谱方法。该方法采用正己烷萃取,经HP-5MS色谱柱(30 m×0.25 mm×0.25μm)分离,使用GC-MS选择离子扫描模式进行分析测试。结果表明:16种邻苯二甲酸酯在0.05～4 mg/L范围内线性良好,r20.99,方法检出限为0.001～0.017 mg/L,定量下限(LOQ)为0.002～0.056 mg/L,加标回收率在80%～120%之间;RSD(n=8)小于10%。并采用该方法测定了90份人尿中的16种邻苯二甲酸酯,检出10种邻苯二甲酸酯,其中DIBP检出率高达50%,DEHP检出率也达到22%。     

超声波提取-气相色谱-质谱法测定塑料食品接触材料中的乙二醇醚及其酯类

本文建立了采用超声波提取-气相色谱-质谱联用检测塑料食品接触材料中的乙二醇醚及其酯类的方法。通过以甲醇为溶剂,超声波萃取乙二醇醚及其酯类,固相硅胶小柱净化,气相色谱-质谱联用仪测定,外标法定量,该方法检测低限在20mg/kg,加标回收率在80%~95%之间,相对标准偏差(RSD)不大于6%,线性范围在10mg/L~1000mg/L,相关系数(r)大于0.999。实验结果表明方法简便、可靠,能满足塑料食品包装材料中的乙二醇醚及其酯类的检测要求。     

气相色谱-质谱法测定食品接触耐高温材料中氯苯和对二氯苯迁移量

目的利用气相色谱-质谱联用法测定食品接触耐高温材料中氯苯类物质(氯苯、对二氯苯等)的迁移量。方法从水基、酸性、醇类、油基等食品模拟物的迁移试验中得到的样品,通过正己烷或甲醇等有机溶剂萃取后,提取液中的氯苯类物质经由键合聚乙二醇的毛细管柱分离,最终在质谱中进行检测分析。结果在优化萃取溶剂、色谱柱等检测条件下,该方法可有效测定食品模拟物中氯苯、对二氯苯等物质的迁移量,在0.05~50 mg/kg(水性模拟物)或0.2~50 mg/kg(油性模拟物)的范围内线性良好,检出限可达到0.02 mg/kg(水性模拟物)或0.1 mg/kg(油性模拟物),回收率在87.6%~113.2%之间,相对标准偏差小于10%(n=6)。结论建立了食品接触材料中氯苯和对二氯苯迁移量的气相色谱-质谱联用方法,该方法简单、快捷、准确,满足了食品接触材料中氯苯类物质日常检验的要求。     

气相色谱串接质谱快速检测不同类别食品中的邻苯二甲酸酯

目的建立食品中16种塑化剂的快速检测方法。方法采用简化净化步骤,不同试样采用不同的萃取溶剂,然后用固相萃取柱净化、洗脱,洗脱液浓缩后,用气相色谱-串接质谱仪测定,内标法定量测定不同食品中16种邻苯二甲酸酯。结果 16种邻苯二甲酸酯的线性关系较好,方法检测限范围为0.01~0.03 mg/kg。在高中低3个水平下进行加标实验,得到的平均回收率为65.7%~115.3%,相对标准偏差小于15%(n=6)。结论该方法简便快速,溶剂消耗量小,且应用串接质谱更好地消除了基质效应的干扰,灵敏度高,定性更准确。     

含油脂食品中邻苯二甲酸酯的前处理及其GC-MS测定方法

建立了15种邻苯二甲酸酯的提取-固相萃取净化-气相色谱/质谱检测分析方法。讨论了含油脂食品中邻苯二甲酸酯的提取、净化方法,优化了色谱分离条件。研究表明,该前处理方法具有较高的净化效率,且缩短了整个检验所需时间;15种邻苯二甲酸酯的方法线性范围为50～2000μg/L,相关系数均大于0.999,加标样品在200μg/L和2000μg/L两个浓度水平下,相对标准偏差在1.1%～11.2%范围,除邻苯二甲酸二甲酯较低外,样品加标回收率均在70%～120%之间。检测限在0.07～1.2μg/L范围(S/N=3)。     

不同材质食品接触材料及制品中PAEs合规情况调查及评价

目的 了解不同材质食品接触材料及制品中邻苯二甲酸酯类物质(Phthalate Esters,PAEs)的含量及分布情况,为食品接触材料及制品中邻苯二甲酸酯安全合规管理提供科学依据。方法 采用GC/MS对来自不同省市的781批不同材质食品接触材料测定其PAEs含量,从PAEs检出情况、量值分布、材质分布等维度对食品接触材料的PAEs安全合规情况进行了分析,并给出相关管控建议。结果 研究中测试的781批食品接触材料样品中,PAEs的总体检出率为12.8%(检出限为0.3 mg/kg),共检出6种PAEs。其中,邻苯二甲酸二(2–乙基)己酯(DEHP)检出率最高,为10.5%,其次为邻苯二甲酸二正丁酯(DBP)和邻苯二甲酸二异丁酯(DIBP),检出率分别为2.9%和1.7%。邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二异壬酯(DINP)和邻苯二甲酸二环己酯(DCHP)检出率均低于0.5%。从检出量值来看,86.7%的检出数据小于10 mg/kg。不同材质食品接触材料中,橡胶制品的PAEs检出率最高,为50.0%,且检出物质多达5种;塑料制品的检出率为14.5%,仅3批PVC塑料中DEHP和1批橡胶制品中DINP检出数据大于100 mg/kg。结论 邻苯二甲酸酯在食品接触材料及制品中整体检出率较高,但检出数值高的占比较低,在橡胶和PVC塑料制品中检出率和检出数值相对较高,因此应高度关注其迁移风险。     

加速溶剂萃取-GC-MS法检测食品接触材料——纸、纸板、木材和木制品中的6种氯酚类物质残留

建立了检测食品接触材料——纸、纸板、木材和木制品中含氯酚(CPs)残留量的气相色谱-质谱(GC-MS)分析方法。采用加速溶剂萃取(ASE)法为样品前处理手段,优化了萃取溶剂、萃取温度、静态萃取时间、冲洗体积和萃取循环次数等实验参数。优化结果为:以二氯甲烷为萃取溶剂,萃取温度为150℃,静态萃取时间为10 min,冲洗体积为(占萃取罐体积的)60%,萃取循环次数为1次。结果表明:6种CPs在0.05～2.0μg/mL质量浓度范围内具有良好的线性关系(R>0.99);平均回收率在86.8%～108.8%之间(n=6);相对标准偏差(RSD)为1.8%～14.2%(n=6);方法的检测限为0.01 mg/kg。研究表明该方法高效、简便、快捷、灵敏、准确可靠,可用于实际样品的CPs残留量的监测。     

加速溶剂萃取-GC-MS/MS法测定食品接触材料中双酚A、双酚F及其衍生物的残留量

建立了加速溶剂萃取-气相相色谱-串联质谱法测定食品接触材料(婴儿奶瓶)中双酚A、双酚F及其衍生物残留量的分析方法。样品用二氯甲烷作提取剂,用加速溶剂萃取仪进行了提取,经乙酸酐衍生化,用气相色谱-串联质谱仪进行了定性、定量分析。结果表明:BPA,BPF,BADGE,BFDG 4种化合物的回收率范围在78.9%～101.1%之间,相对标准偏差小于10%,线性关系良好,方法的检出限分别为0.2,0.1,5,5 ng/g,该方法简便、快速、灵敏度高、重复性好。     

Development of a solid-phase microextraction gas chromatography/tandem mass spectrometry method for polybrominated diphenyl ethers and polybrominated biphenyls in water samples

Solid-phase microextraction has been applied for the first time to the determination of trace concentrations of some brominated flame-retardant compounds (BFRs) in water samples. For the development of the method, six polybrominated diphenyl ethers and two polybrominated biphenyls were considered as target analytes. The factors expected to influence the extraction process are fully discussed. Quantification has been performed by gas chromatography/tandem mass spectrometry using an ion trap mass analyzer. This is also the first time that tandem mass spectrometry is applied with these analytes. Unlike conventional methods for BFR analysis, which involve solvent extraction and several cleanup steps before gas chromatography, the proposed method uses headspace extraction and hard contamination of the chromatographic system is prevented. In addition, tandem mass spectrometry provides selectivity and sensitivity in the detection process. The method performs well achieving good linearity (R(2) > 0.997), precision, and detection limits (S/N = 3) ranging from 7.5 to 190 pg/L. The method has been applied to a variety of water samples.     

纸质包装材料中挥发性有机物迁移量的测定

目的研究纸质包装材料中挥发性有机物向食品模拟物中的迁移量。方法选取改性聚苯醚作为食品模拟物,首次建立模拟物MPPO直接顶空进样-气相色谱/质谱联用法测定包装用纸中23种有机挥发物质迁移量的方法。结果该法测定23种挥发性物质的相关系数R均大于0.998,相对标准偏差为1.4%~4.6%(n=7),检出限为0.03~0.60 mg/m2,加标回收率为81.2%~110.2%。结论该法无需前处理,简单快速,灵敏度高,重现性好,能满足包装用纸中23种有机挥发性物质迁移量的测定要求。     

GC-MS法测定食品包装材料印刷油墨中光引发剂二苯甲酮和4-甲基二苯甲酮

建立了气相色谱-质谱(GC-MS)检测食品包装材料表面印刷油墨中光引发剂二苯甲酮(BP)和4-甲基二苯甲酮(MBP)迁移量的方法。样品以正己烷为提取溶剂进行振荡提取和超声波辅助萃取,提取液用GC-MS分析检测。结果表明:该方法线性范围为0.02～0.1mg/mL,检测限为0.004～0.005mg/mL,在0.01,0.02,0.10mg/mL 3个添加水平下,2种光引发剂的平均回收率为88.2%～114.5%,相对标准偏差(n=6)为5.13%～7.95%。该方法简单快速,适用于食品包装材料的日常检测需要。     

Screening for Chemicals in Paper and Board Packaging for Food Use: Chemometric Approach and Estimation of Migration

An analytical survey of 20 paper and board (P&B) materials intended for food use was carried out with the aim to identify chemicals with a potential to migrate into foods. Representative materials covering a range of uses (primary and secondary packaging and article for take away foods) were obtained from distributors. A screening approach was applied by means of solvent extraction with subsequent analysis by gas chromatography/mass spectrometry. A large number of analytes were detected, and a chemometric approach was used to explore the data. Principal component analysis was used to identify and select some compounds as markers for sample classification. In the corrugated and printed packaging, it is worth emphasizing the presence of residual solvents, probably coming from printing inks, as well as hydrocarbons and aromatic compounds, mainly toluene and plasticizers linked also to the recycled pulp content such as diisobutyl phthalate or diisopropylnaphthalenes, whereas in the plastic‐laminated samples, triacetin was identified as the prevailing compound. A literature search for safety data or legislative restrictions of the identified substances was performed. Additionally, the semi‐quantification of the compounds in the packaging allowed a worst case estimation of food contamination by means of the infinite total migration model; occasionally, migration estimations overcame the specific migration limits. The chosen analytical methods coupled with a chemometric approach proved to be an effective way to describe the data; it may be concluded that only the simultaneous consideration of several chemicals with a multivariate approach allowed the investigated packaging materials to be distinguished. Copyright © 2014 John Wiley & Sons, Ltd.     

分散固相萃取-高效液相色谱-串联质谱快速测定鸡肉中盐霉素残留

建立了分散固相萃取-超高效色谱-电喷雾串联质谱快速测定鸡肉中盐霉素残留的方法。样品经乙腈提取后,采用QuEChERS方法净化,氮吹转换溶剂后,采用Acquity BEH C18柱进行分离,0.3%甲酸水溶液-甲醇体系为流动相,梯度洗脱,电喷雾质谱正离子多反应监测模式测定,外标法定量。结果表明,在优化的条件下对样品进行分析检测,盐霉素的检出限为0.03μg·kg-1,添加水平为5.5~31.4μg·kg-1时,加标回收率为78.2-97.8%,RSD<2.0%(n=6),在0.630~25.2μg·L-1质量浓度范围内呈良好线性,相关系数R2>0.9989。该方法前处理步骤简单,具有较高灵敏度,可用于大批量样品的快速筛查检测。     

Hollow fiber-protected liquid-phase microextraction of triazine herbicides

A new microextraction technique termed hollow fiber-protected liquid-phase microextraction (LPME) was developed. Triazines were employed as model compounds to assess the extraction procedure and were determined by gas chromatography/mass spectrometry. Toluene functioned as both the extraction solvent and the impregnation solvent. Some important extraction parameters, such as effect of salt, agitation, pH, and exposure time were optimized. The new method provided good average enrichment factors of > 150 for eight analytes, good repeatability (RSDs <3.50%, n = 7), and good linearity (r2 > or = 0.9995) for spiked deionized water samples. The limits of detection (LODs) were in the range of 0.007-0.063 microg/L (S/N = 3) under selected ion monitoring mode. In addition to enrichment, hollow fiber-protected LPME also served as a technique for sample cleanup because of the selectivity of the membrane, which prevented large molecules and extraneous materials, such as humic acids in solution, from being extracted. The utilization of this procedure in the extraction of a slurry sample (mixture of soil and water) also gave good precision (RSDs <5.00%, n = 3) and LODs (0.04-0.18 microg/L, S/N = 3). Finally, the comparison of the new method with the static solvent drop LPME and solid-phase microextraction was performed. The results demonstrated that hollow fiber-protected LPME was a fast, accurate, and stable sample pretreatment method that gave very good enrichment factors for the extraction of triazine herbicides from aqueous or slurry samples.