气相色谱-质谱法测定纸质食品包装材料中富马酸二甲酯

建立了微波辅助萃取气相色谱-质谱测定纸质食品包装材料中富马酸二甲酯的分析方法。以乙酸乙酯为萃取溶剂,采用微波辅助萃取法提取纸质食品包装材料中的富马酸二甲酯,萃取液浓缩后,经过中性氧化铝小柱脱脂净化、无水硫酸钠脱水后,用气相色谱-质谱仪分析。结果表明:方法检出限为0.1mg/kg,加标回收率为82.5%~98.2%,重复测量结果之间的相对标准偏差为3.4%。该方法具有快速、方便、准确度高等优点。     

液相色谱串联质谱法测定纸制食品接触材料中芳香族伯胺迁移量

目的 建立纸制食品接触材料中24种芳香族伯胺迁移量的液相色谱串联质谱检测方法。方法 以不同种类食品模拟物进行模拟迁移实验, 模拟迁移液过0.22 μm滤膜测定。液相色谱使用ZORBAX-C18反相色谱柱, 以乙腈和0.1%甲酸为流动相, 在梯度条件下分析。在正离子模式下多反应监测(MRM) 采集质谱信号, 进行定性和定量分析。结果 24种初级芳香胺在50%乙醇溶液(v/v)模拟物中标准曲线的线性相关系数为0.9876~0.9999, 加标回收率为72.98%~97.88%, 相对标准偏差均在0.30%~9.90%, 定量限均小于或等于3.0 μg/kg。结论 该方法快速简便、灵敏度高、准确性好, 满足了相关法规的限量测定要求。     

顶空-气相色谱-质谱联用法检测食品纸包装材料中13种烯烃类化合物

目的建立顶空-气相色谱-质谱联用法(headspace-gas chromatography-mass spectrometry,HS-GC-MS)测定食品纸包装材料中13种烯烃化合物(四氟乙烯、六氟丙烯、异戊二烯、1,1-二氯乙烯,4-甲基-1-戊烯、己烯、二环[2,2,1]庚-2-烯、辛烯、3,4-二羟基-1-丁烯、苯乙烯、苯丙烯、2-苯丙烯、3,4-二乙酰氧基-1-丁烯)的含量。方法样品在平衡温度为115℃,平衡时间为10 min的条件下自动顶空进样,经DB-624(60 m×0.25 mm,1.4μm)色谱柱分离,采用电子轰击离子源和选择离子扫描模式,用GC-MS进行检测。结果该方法检出限为6~60μg/kg,方法定量限为20~200μg/kg;13种烯烃类化合物在5~1000μg/kg范围内线性良好,相关系数均大于0.99;方法回收率为93.9%~99.9%,相对标准偏差为2.0%~7.9%。结论该方法操作简便,灵敏度高,可适用于食品纸包装材料中13种烯烃化合物的检测。     

自动顶空-气相色谱-质谱联用法检测食品纸包装材料中9种烯烃类化合物

目的建立自动顶空-气相色谱-质谱联用法(head space-gas chromatography-mass spectrometry,HS-GC-MS)检测食品纸包装材料中9种烯烃化合物(2-苯丙烯、苯丙烯、2-苯乙烯、二环[2,2,1]庚-2-烯、己烯、辛烯、异戊二烯、1,1-二氯乙烯和4-甲基-1-戊烯)的定性定量确证方法。方法样品在平衡温度为120℃,平衡时间为10 min的条件下自动顶空进样,经DB-624色谱柱分离,采用GC-MS选择离子扫描方式进行检测,以内标法定量。结果在优化的条件下,9种烯烃化合物在5~1000μg/kg范围内线性良好,相关系数(R~2)均大于0.999;方法定量限为20~40μg/kg;方法的回收率在93.5%~103.0%之间,相对标准偏差为2.3%~5.1%(n=6)。结论该方法简便准确,灵敏度高,重现性好,可满足食品纸包装材料中9种烯烃化合物检测的要求。     

Comparing different gas chromatographic methods for the quantification of bisphenol A (BPA) trace levels in paper and cardboard products from the market

Bisphenol A (BPA; 4,4?-(propane-2,2-diyl)diphenol), a suspected endocrine disruptor with weak estrogenic activity, is used in a variety of consumer products, including paper and cardboard products used as food contact materials. The present study compared four different gas chromatographic methods for the analysis of BPA in paper and cardboard food packages. Eighteen different food packages were extracted and BPA was determined using two different derivatisation reactions – trimethylsilylation with N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) and halide alkylation with pentafluorobenzoyl chloride (PFBOCl) – and four different separation and detection techniques. The BSTFA derivatives were quantified with (1) GC-MS in single-ion monitoring (SIM) mode with electron ionisation (EI-GC-MS) and (2) GC-MS/MS in multiple reaction monitoring (MRM) mode using electron ionisation (EI-GC-MS/MS); while the PFBOCl derivatives were quantified with (3) GC-MS using electron ionisation (EI-GC-MS) as well as (4) GC-MS with negative chemical ionisation (NCI-GC-MS). All developed methods showed good linearity (R² > 0.9938), precision (CV < 4.5% for reproducibility; CV < 2.2% for repeatability) and sensitivity, with limits of detection (LODs) between 0.02 µg kg^?1 for the pentafluorobenzoyl derivatives measured with the NCI-GC-MS method and 6 µg kg^?1 for the pentafluorobenzoyl derivatives determined with EI-GC-MS. Levels of BPA in the samples were in agreement for all methods, ranging from values below the limit of quantitation (LOQ) to 11.9 mg kg^?1 paper. In a last step, the maximum potential migration into food products was calculated for all tested paper and cardboard samples, assuming a ‘worst case’ scenario of 100% migration.     

Determination of furan in jarred baby food purchased from the Spanish market by headspace gas chromatography-mass spectrometry (HS-GC-MS)

The aim of this paper is to offer a method based on headspace gas chromatography-mass (HS-GC-MS) spectrometry technique in-house validated and use to estimate furan concentrations in jarred baby-food samples purchased from the Spanish market. The validation was performed according to ISO 17025 and European Food Safety Authority (EFSA) requirements and the results obtained (limit of detection (LOD) = 0.05 µg kg^?1; limit of quantification (LOQ) = 4 µg kg^?1, lowest validated level; relative standard deviation (RSD) = 3.1–10.5%; recoveries = 85.4–101.5%) confirm that this method is fit for the routine analysis of furan in jarred baby food control. Furan was analysed in 39 different baby-food samples and the mean levels varied between 64.6 µg kg^?1 (rice and chicken samples) and less than or equal to the LOQ (fruit-based samples). The mean concentrations found for the different matrices were 5.0, 37.8, 25.2, 33.8 and 30.5 µg kg^?1 for fruit, vegetables, meat/vegetables, fish/vegetables and dairy-containing baby foods, respectively. According to the statistical analyses, fruit-based baby-food samples had significantly lower concentrations of furan. Mean values for the other matrices were at least five times higher, and this is in accordance with the levels reported in other studies.     

气相色谱-质谱法测定食品用纸制品中五氯酚含量

目的 建立气相色谱-质谱法测定食品用纸制品中五氯酚含量的分析方法,了解食品用纸制品中五氯酚的残留状况.方法 纸制品试样加入2,4,6-三溴酚内标后,经液-液萃取,SLC柱净化,乙酸酐-吡啶溶液衍生后,采用气相色谱-质谱法测定,内标法定量.结果 在50～1000 ng范围内,相关系数均>0.9995.方法 的检出限为0....     

Analytical determination of bisphenol A (BPA) and bisphenol analogues in paper products by GC-MS/MS

ABSTRACT

Bisphenol A (BPA; 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol), a suspected endocrine disruptor with a weak estrogenic activity, is used in a variety of consumer products, including food-contact materials made of paper and cardboard products. Due to restrictions on the use of BPA because of its potential health risks, BPA is gradually being replaced by other bisphenols because no limitations exist for these substances. This study presents a method for the simultaneous analysis of BPA, bisphenol AF (BPAF), bisphenol B (BPB), bisphenol E (BPE), bisphenol F (BPF) and bisphenol S (BPS) in paper and board products using gas chromatography-tandem mass spectrometry (GC-MS/MS). Paper samples were extracted by liquid extraction, as well as by Folch extraction, derivatised with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) and the results compared. The developed method showed good linearity (R² > 0.9965) and precision, yielding relative standard deviations (RSDs) of less than 16.6% for reproducibility and 19.8% for repeatability. The limits of detection and limits of quantification for the different bisphenols ranged from 0.23 to 2.70 µg kg^–1 paper and from 0.78 to 9.10 µg kg^–1 paper, respectively. Analysis of different paper products (recycled, virgin fibre) showed that all the analysed bisphenols were present in the samples, except for BPAF and BPB. A calculation of the ‘worst-case’ scenario assuming a maximum potential migration of 100% of the analytes into food showed that the analysed products can be assumed to be safe regarding the migration of bisphenols.     

食品用纸杯中光引发剂特定迁移量的气相色谱- 串联质谱测定方法

目的建立11种光引发剂类化合物食品用纸杯特定迁移量的气相色谱-串联质谱(gas chromatographytandem mass spectrometry,GC-MS/MS)检测方法。方法食品模拟物中的光引发剂类化合物经反相固相萃取柱富集净化后,采用中等级性的DM-17MS气相色谱柱进行分离;采用三重四极质谱的多反应监测模式(multiple reaction monitoring,MRM)对化合物进行定量测定。结果本方法可在17 min内完成11种目标化合物的色谱分离。11种光引发剂在低、中、高3个添加水平的回收率在65.0%~119.8%范围内,相对标准偏差为1.2%~10.6%(n=6),方法检出限为1~7μg/L,定量限为2~20μg/L。结论该方法灵敏度高,定量准确,适用于食品模拟物中光引发剂类物质特定迁移量的测定。     

塑料包装材料中邻苯二甲酸酯的LC/MS/MS测定方法研究

建立了LC/MS/MS测定塑料包装材料中邻苯二甲酸酯含量的分析方法.将塑料包装材料粉碎后索氏提取,经LC/MS/MS分析在50μg/L～400μg/L范围内呈现良好的线性关系(R2＞0.9985),方法检测限小于35μg,/kg;在50μg/kg、200μ g/kg、400μg/kg三个样品加标水平,PAEs的回收率在91.42％～99.90％之间;方法精密度实验的相对准偏差在5％之内.结果表明该方法准确可靠,精密度较高.     

高效液相色谱法测定纸质食品包装材料中的荧光增白剂

目的使用高效液相色谱法检测云南省纸质食品包装材料11种荧光增白剂的添加情况。方法样品采集自云南省16个州市118份纸质包装材料,粉碎后经用40%乙腈-水超声提取3次,合并提取液,离心,上清液经正己烷脱脂。脱脂后的溶液在C_(18)色谱柱上,用带有离子对试剂的流动相梯度洗脱分离后,采用紫外检测,外标法定量。结果本方法在22 min内完成11种目标化合物的分离分析,线性关系良好,相关系数(R~2)均大于0.99。在低、中和高3个添加水平的回收率为85.1%～104.6%,相对标准偏差(relative standard deviations,RSDs)小于8.2%(n=6),方法定量限(limits of quantitation,LOQ)为3.2～6.0 mg/kg,阳性样品检出率达到7.62%,含量最高达38.6 mg/kg。结论云南省纸制品存在添加荧光增白剂,部分样品中检测出多种荧光增白剂非法添加,相关部门应该予以重视,加强对纸质食品包装材料的监督管理。     

Analytical determination of bisphenol A (BPA) and bisphenol analogues in paper products by LC-MS/MS

ABSTRACT

In this study a sensitive analytical method based on liquid chromatography-electrospray tandem mass spectrometry (LC-MS/MS) was developed for the simultaneous analysis of bisphenol A (BPA), bisphenol AF (BPAF), bisphenol B (BPB), bisphenol E (BPE), bisphenol F (BPF) and bisphenol S in different paper and board products, including virgin fibre samples and recycled samples. Analytes were extracted from the paper matrix using a simple solvent extraction and chromatographic separation was performed on a C18 core-shell (100 mm x 2.1 mm i.d.; 1.7 µm particle size) column. The developed method showed good linearity (R² > 0.9921) for all analytes. Absolute recoveries ranged from 71 to 115% and precision in terms of reproducibility and repeatability (intra- and inter-day) yielded in relative standard deviations (RSDs) of less than 15.0% and 17.4%, respectively. The limit of detection (LOD) and limit of quantification (LOQ) for the different analytes ranged from 0.29 to 0.40 µg kg^?1 paper and from 1.09 to 1.32 µg kg^?1 paper, being in the same range for all analytes. Quantitation of the analytes was performed using the internal standard procedure, with concentrations of < LOQ to 9599 µg kg^?1 for the different analytes. Furthermore, a calculation of the maximum migration, assuming the ‘worst case’ scenario of 100% migration was performed.     

液相色谱-串联质谱法快速测定食品中的可乐定

目的 采用超高压液相色谱-电喷雾串连四极杆质谱分析食品基质中的可乐定, 为可乐定中毒事件的 样本分析提供依据。方法 食物样本粉碎后经甲醇水溶液超声提取, 低温离心后, 上清液用 Waters ACQUITY UPLCTM BEH C18 色谱柱分离, 以 0.1%甲酸和甲醇溶液为流动相梯度洗脱, 最后用串联四极杆质谱在正离子 MRM 模式下进行测定。结果 以淀粉和炸鸡为加标基质, 三个加标水平下可乐定的平均回收率为 91.5%~127.8%, 相对标准偏差小于 16%, 定量限为 0.02 mg/kg。结论 该方法操作快速简单、重现性好, 成功 用于 2010 年 4 月怀柔水岸山吧可乐定中毒事件的食品检测。     

超高效液相色谱-串联质谱法测定食品包装材料中全氟辛酸及其盐类物质

建立了超高效液相色谱-串联质谱(UPLC-MS/MS)结合加速溶剂萃取测定食品包装材料中全氟辛酸及其盐类物质(PFOA)的方法.采用甲醇作为溶剂,加速溶剂提取法提取食品包装材料中的PFOA,提取液经0.2 μm有机滤膜过滤后,以甲醇、水为流动相,梯度洗脱,经UPLC分离后用多级反应监测(MRM)方式测定.用两个子离子的...     

液相色谱-串联质谱法测定食品包装PE材料中荧光增白剂残留量

目的建立同时测定食品包装PE材料中荧光增白剂WS、PF、OB、EBF、EGM、KCB、KSN、OB-1等8种荧光增白剂含量的检测方法。方法采用液相色谱-串联质谱法建立食品包装PE材料中8种荧光增白剂同时测定方法。食品包装PE材料中的荧光增白剂经四氢呋喃和N,N-二甲基甲酰胺提取后,采用Discovery C_(18)柱(150 mm×4.6 mm, 5μm)色谱柱,以乙腈和5 mmol/L乙酸铵-甲酸溶液作为流动相,梯度洗脱,液相色谱-串联质谱法(liquid chromatography-tandem mass spectrometry, LC-MS/MS)电喷雾电离源,正离子多反应监测模式测定,外标法定量。结果本文建立的食品包装PE材料中8种荧光增白剂检测低限均可达到0.01 mg/kg;在0.01～6.25 mg/L浓度范围内相关系数均大于0.995,线性关系良好;在0.05、0.25、1.25 mg/kg 3个浓度水平加标回收,回收率在70.8%～99.6%之间;相对标准偏差在1.56%～9.66%之间。结论该方法净化效果好、灵敏度高,且快速简便,可应用于食品包装PE材料中荧光增白剂残留量的检测分析。     

稳定性同位素稀释气相色谱-质谱法测定白酒中DBP、DEHP含量及不确定度评定

采用稳定性同位素稀释气相色谱-质谱法对白酒中DBP、DEHP的含量进行测定,并对整个测试过程的不确定度来源进行系统分析。样品提取、离心后取上层有机相进行测定,利用选择离子监测模式,以氘代同位素标记物作内标,以m/z 149和m/z153为定量离子对,对其定性定量测定,并对测试过程中引入的各个分量进行评定与合成。结果表明,DBP、DEHP在0.2~2.0 mg/L浓度范围内线性关系良好,r≥0.999,定量限为0.05 mg/kg,不同加标水平中的平均回收率为DBP:91.2%~100.4%,RSD为2.24%~2.79%(n=5);DEHP:99.0%~110.6%,RSD为4.98%~5.44%(n=5)。当DBP测定结果为0.572 mg/kg时,扩展不确定度为0.040 mg/kg,DEHP测定结果为0.251 mg/kg时,扩展不确定度为0.025 mg/kg,k=2,p=95%。该方法准确可靠,可用于白酒中DBP、DEHP的含量测定。并且建立的不确定度评定方法可用于气相色谱-质谱法测定白酒中DBP、DEHP浓度的不确定度评估。标准溶液配制和标准曲线拟合、样品前处理以及分析仪器是主要的不确定度来源。     

高效液相色谱-串联质谱法测定食品用纸制品中氯酚类化合物残留量

目的建立高效液相色谱-串联质谱(HPLC-MS/MS)同时测定食品用纸制品中2,4-二氯酚、2,4,6-三氯酚、2,3,4,6-四氯酚、五氯酚4种氯酚类化合物残留量的检测方法。方法样品经0.5%甲酸甲醇超声提取后,混合型阴离子交换固相萃取柱净化,以HSS T3色谱柱(2.1 mm×100 mm,1.8μm)分离待测物,采用电喷雾离子化,负离子扫描和多反应监测模式(MRM)检测,以保留时间和特征离子对定性,内标法定量。结果 4种待测物在5～100μg/L浓度范围内线性关系良好,相关系数(r)均大于0.99;方法检出限为0.01～0.02 mg/kg,定量限为0.03～0.06 mg/kg;4种物质的添加水平为0.03～0.14 mg/kg时,平均回收率为80.1%～110.4%,相对标准偏差为3.2%～9.9%(n=6)。结论该方法样品前处理简单,准确性、精密度和灵敏度均较好,适用于食品用纸制品中4种氯酚类化合物残留量的检测。     

索氏提取-气相色谱/质谱法测定食品包装材料中羟基苯醚

目的 建立一种适用于食品包装材料中羟基苯醚的气相色谱/质谱检测方法。方法 采用索氏提取法, 以二丙醚萃取提取样品中二苯醚类物质, 经色谱分离后采用质谱检测器, 保留时间、分子碎片峰定性, 外标法定量。结果 对于二苯醚类物质检测回收率范围88%~109%, 相对标准偏差<3.9, 检测限0.032 ~0.067mg/L。结论 本方法便捷、重现性好, 适用于各种类型食品包装材料中二苯醚类物质检测。     

Determination of ethylenethiourea (ETU) and propylenethiourea (PTU) in foods by high performance liquid chromatography-atmospheric pressure chemical ionisation-medium-resolution mass spectrometry

A robust and sensitive method for the determination of ethylenethiourea (ETU) and iso-propylenethiourea (i-PTU) in foods is reported. ETU and i-PTU were extracted by blending with dichloromethane (DCM) in the presence of sodium sulphate, sodium carbonate, thiourea and ascorbic acid. ²H₄-ETU and n-PTU were used as internal standards. After filtration the DCM was removed by rotary evaporation and the extract re-dissolved in water before analysis by reversed-phase liquid chromatography with detection by atmospheric pressure chemical ionization-mass spectrometry using a double focusing mass spectrometer at a resolution of 5000. Mean recoveries of ETU and i-PTU from fruit-based, cereal-based and meat-based infant foods, potato chips and tinned potatos at 0.01 mg kg^-1 and from pizza and yoghurt at 0.02-0.1 mg kg^-1 were 95% and 97% respectively. Precision, including both repeatability and internal reproducibility, was in the range of 3.1-13.1%.     

热脱附-气相色谱/质谱法检测食品接触材料中有机残留物

目的 建立适用于食品接触材料中有机残留物的气相色谱/质谱检测方法。方法 采用热脱附仪结合气相色谱/质谱法对食品接触材料中的多种类型有机残留物进行检测, 采用质谱检测器、保留时间定性, 外标法定量。结果 对于醇、酯、苯系物等残留有机物检测回收率达到92.7%~112.5%, 相对标准偏差<3.2%, R2>0.9890, 检测限为0.06~0.11 mg/L。结论 本方法便捷、重现性好, 适用于各种材料中有机残留物的检测。