气相色谱-质谱法测定醇食品模拟物中 16种多环芳烃

目的 建立固相微萃取-气相色谱-质谱联用仪测定醇食品模拟液中16种多环芳烃的分析方法。方法 优化了萃取方式、萃取温度、萃取时间、解吸时间和振荡速率等萃取条件, 样品采用气相色谱-质谱联用仪(gas chromatography-mass spectrometry, GC-MS)总离子流和选择离子模式进行定性定量测定。结果 16种多环芳烃在0.01~10 ?g/L范围内线性良好, R2大于0.99。在0.1、0.5、1.0 μg/L 3个添加水平下, 16种多环芳烃的平均回收率为76.52%?119.8%, 相对标准偏差为0.99%?15.93%。结论 该方法操作简便、灵敏度高、准确度好, 能够满足醇食品模拟物中多环芳烃化合物的检测要求。     

Gas chromatography-mass spectrometry (GC-MS) method for the determination of 16 European priority polycyclic aromatic hydrocarbons in smoked meat products and edible oils

A gas chromatography-mass spectrometry (GC-MS) method was developed for the analysis of 15 polycyclic aromatic hydrocarbons (PAHs) highlighted as carcinogenic by the Scientific Committee on Food (SCF) plus benzo[c]fluorine (recommended to be analysed by the Joint FAO/WHO Expert Committee on Food Additives (JECFA)) in fat-containing foods such as edible oils and smoked meat products. This method includes accelerated solvent extraction (ASE) and the highly automated clean-up steps gel permeation chromatography (GPC) and solid-phase extraction (SPE). Using a VF-17ms GC column, a good separation of benzo[b]fluoranthene, benzo[j]fluoranthene and benzo[k]fluoranthene was achieved. Furthermore, the six methylchrysene isomers and the PAH compounds with a molecular weight of 302 Daltons in fat-containing foods attained a better chromatographic separation in comparison with a 5-ms column. The reliability of the analytical method for edible oils was demonstrated by the results from a proficiency test. Measurements with GC-high-resolution mass spectroscopy (HRMS) and gas chromatography-mass selective detection (GC-MSD) led to comparable results. A survey of the 16 PAHs in 22 smoked meat products showed concentrations in the range <0.01–19 µg kg^?1. The median concentration for benzo[a]pyrene was below 0.15 µg kg^?1.     

Gas chromatography-mass spectrometry (GC-MS) method for the determination of 16 European priority polycyclic aromatic hydrocarbons in smoked meat products and edible oils

A gas chromatography-mass spectrometry (GC-MS) method was developed for the analysis of 15 polycyclic aromatic hydrocarbons (PAHs) highlighted as carcinogenic by the Scientific Committee on Food (SCF) plus benzo[c]fluorine (recommended to be analysed by the Joint FAO/WHO Expert Committee on Food Additives (JECFA) in fat-containing foods such as edible oils and smoked meat products. This method includes accelerated solvent extraction (ASE) and the highly automated clean-up steps gel permeation chromatography (GPC) and solid-phase extraction (SPE). Using a VF-17ms GC column, a good separation of benzo[b]fluoranthene, benzo[j]fluoranthene and benzo[k]fluoranthene was achieved. Futhermore, the six methylchrysene isomers and the PAH compounds with a molecular weight of 302 Daltons in fat-containing foods attained a better chromatographic separation in comparison with a 5-ms column. The reliability of the analytical method for edible oils was demonstrated by the results from a proficiency test. Measurements with GC-high-resolution mass spectroscopy (HRMS) and gas chromatography-mass selective detection (GC-MSD) led to comparable results. A survey of the 16 PAHs in 22 smoked meat products showed concentrations in the range < 0.01-19 microg kg(-1). The median concentration for benzo[a]pyrene was below 0.15 microg kg(-1).     

气相色谱-三重四极杆串联质谱法同时测定茶叶中16种多环芳烃

目的 建立同时测定不同类别茶叶中16种多环芳烃的气相色谱-三重四极杆串联质谱法。方法 茶叶样品粉碎均匀后, 用正己烷超声波萃取, 分子印迹固相萃取柱净化, 氮吹浓缩后, 用气相色谱-三重四极杆串联质谱法检测目标物, 外标法定量。结果 茶叶中16种多环芳烃在5~2500 μg/L范围内线性关系良好, 相关系数(r)在0.9986~0.9999之间, 在绿茶和黑茶样品中添加20、100、500 μg/kg 3个浓度水平的平均加标回收率在80.1%~104.4%之间, 相对标准偏差不大于8.0%, 各目标物的检出限范围为在0.4~4.3 μg/kg之间, 定量限为1.3~14.3 μg/kg。结论 该方法操作简单快捷、灵敏度高、准确度高、选择性良好、线性范围宽, 各目标物分离效果好, 能有效地降低茶叶样品的基质干扰, 能够作为茶叶中的16种多环芳烃含量同时检测的确证方法。     

Demonstration of a method for the direct determination of polycyclic aromatic hydrocarbons in submerged sediments

We describe the development of a novel method for real-time in situ characterization of polycyclic aromatic hydrocarbons (PAHs) in submerged freshwater sediments. Laser-induced fluorescence (LIF) spectroscopy, a mature technique for PAH characterization in terrestrial sediments, was adapted for shipboard use. A cone penetrometer-type apparatus was designed for probe penetration at a constant rate (1 cm/s) to a depth of 3 m. A field-portable LIF system was used for in situ measurements in which the output of a pulsed excimer laser was transmitted by optical fiber to a sapphire window (6.4-mm o.d.) in the probe wall; fluorescent emission was collected by a separate optical fiber for transmission to the spectrometer on deck. Four wavelengths (340, 390, 440, 490 nm) were selected via optical delay lines, and multiple-wavelength waveforms were created. These multiple-wavelength waveforms contain information on the fluorescence frequency, intensity, and emission decay rate. Field testing was conducted at 10 sites in Milwaukee Harbor (total PAH concentrations ranged from approximately 10 to 650 microg/g); conventional sediment core samples were collected concurrently. The core samples were analyzed by EPA methods 3545 (pressurized fluid extraction, PFE) and 8270C (gas chromatography-mass spectrometry, GC-MS) for PAHs. A partial least-squares regression (PLSR) model wasthen created based on laboratory LIF measurements and PFE-GC-MS of the core samples. The PLSR model was applied to the in situ field test data, and 13 of the 16 EPA-regulated PAHs were quantified with a relative error of <30% overall (the remaining three PAHs were found at levels insufficient to quantify). We additionally describe preliminary source apportionment relationships that were revealed by the PLSR model for the in situ LIF measurements.     

分子印迹固相萃取-气相色谱-质谱联用法检测按摩油类化妆品中16种多环芳烃

目的建立分子印迹固相萃取结合气相色谱-质谱联用法(gas chromatography-mass spectrometry,GC-MS)快速测定按摩油类化妆品中16种多环芳烃(polycyclic aromatic hydrocarbons,PAHs)。方法样品用正己烷分散,经多环芳烃分子印迹固相萃取柱(molecularly imprinted solid phase extraction,MIP-PAHs SPE)富集、N-丙基乙二胺(primary secondary amine,PSA)固相萃取柱净化,GC-MS外标法定性定量。结果 16种PAHs在50~500μg/L范围内线性关系良好,相关系数(correlation coefficients,r2)在0.9870~0.9993范围内。样品添加标准品浓度在100~1000μg/kg时,其回收率在75.5%~117.2%之间,相对标准差小于14.9%,方法的测定下限(limit of detection,LOD)介于0.3~4.1μg/kg之间。结论本方法简单、快速、准确,适用于按摩油类化妆品中16种多环芳烃的检测。     

SPE净化-同位素稀释-GC-MS法检测食用油脂中16种多环芳烃

研究建立了乙腈超声提取、硅胶SPE柱净化、DB–5MS毛细管柱分离、同位素稀释法定量检测食用油中16种多环芳烃的气质联用(GC–MS)方法。油脂样品采用乙腈提取、硅胶SPE柱净化,减少了有机溶剂的消耗,再采用16种同位素内标法定量,定量结果更加准确。结果表明:16种多环芳烃在1~100μg/kg范围内线性关系良好,线性相关系数为0.998 9~0.999 9,检出限为0.06~0.17μg/kg,定量限为0.18~0.56μg/kg。16种目标物在2、5、10μg/kg加标水平下的各组分回收率在84.36%~114.35%之间,相对标准偏差在0.12%~10.36%之间(n=6)。21个受测样品中16种多环芳烃的总含量为30.83±0.66~793.13±16.96μg/kg。除全部浓香型油脂及1个花生油外,所有受试油样中Ba P和PAH4含量均达到欧盟限量指标(Ba P≤2μg/kg,PAH4≤10μg/kg),浓香型油脂样中PAHs的污染情况较为严重。从油脂品类来看,低温制油和浸出精炼成品油的多环芳烃的风险低于浓香型油脂。     

Determination of polycyclic aromatic hydrocarbons in edible seafood by QuEChERS-based extraction and gas chromatography-tandem mass spectrometry

A high-throughput analysis of polycyclic aromatic hydrocarbons (PAHs) in edible seafood using QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) based extraction and gas chromatography-tandem mass spectrometry (GC-MS/MS) was developed and validated in 4 seafood matrices--crab, finfish, oyster, and shrimp. The extraction employs QuEChERS with dispersive solid phase extraction (dSPE) using cleanup sorbent that includes C18. The acetonitrile extract is partitioned into hexane and analyzed by GC-MS/MS. The procedure was validated by spike recovery experiments of 15 parent and 5 substituted PAHs at 5ppb and 25 ppb levels in the 4 matrices. Recoveries were 71%-130% with RSDs less than 14%. The limit of quantitation (LOQ) for benzo[a]pyrene are 0.4-2.5 ppb depending on matrix. For all 15 parent PAHs the LOQs are less than 10% of the Levels of Concern established by the U.S. Food and Drug Administration. Good recoveries were also achieved in aged spikes at 5 ppb level in oyster and shrimp. Method accuracy was further evaluated by analyzing NIST Standard Reference Material 1974b. Ten of 14 incurred PAHs corresponding to the parent compounds in the present study fell within the control limits established by the National Oceanic and Atmospheric Administration. Using the present method approximately 20 samples every 24 h can be analyzed with confirmation. PRACTICAL APPLICATION: The presented analytical method could be used for seafood safety assessments to examine petroleum contaminant levels in edible seafood after an oil spill. The method is fast and sensitive.     

两种前处理技术/气相色谱-质谱技术测定食用植物油中16种多环芳烃残留量及其对比研究

目的比较2种前处理技术/气相色谱-质谱技术测定食用植物油中16种多环芳烃残留量。方法本研究利用QuEChERS(quick,easy,cheap,effective,ruggedandsafe)和凝胶渗透色谱(gelpermeation chromatography, GPC)2种前处理技术对样品进行处理,并采用16种多环芳烃全指标同位素内标法定量。比较使用QuEChERS和GPC 2种不同前处理方法的净化效果和方法学参数。结果 16种多环芳烃在10～200 ng/mL范围内线性关系良好,相关系数均大于0.995,定量限为0.3～0.8μg/kg。使用QuEChERS前处理方法的平均回收率和相对标准偏差(relative standard deviation, RSD)分别为88.9%～112.3%和3.6%～12.9%,使用GPC方法的平均回收率和RSD分别为86.2%～107.7%和3.0%～7.3%。对实验室内食用植物油样品进行测定, 2种方法检测结果基本一致。结论 2种前处理方法的精确度和稳定性均较好,均可用于食用植物油中16种多环芳烃残留量的测定。     

Results of an European inter-laboratory comparison study on the determination of the 15 + 1 EU priority polycyclic aromatic hydrocarbons (PAHs) in liquid smoke condensates

A collaborative study on the determination of the 15 + 1 EU priority PAHs in Primary Smoke Condensate (PSC) investigating the performance profile of EU Member States’ laboratories and supporting the work carried out by the European Food Safety Authority on smoke flavourings was organised. Two spiked liquid smoke condensate materials were employed in this study. The results of 25 laboratories from across the European Union, using either high performance liquid chromatography with fluorescence detection or gas chromatography with mass selective detection, were evaluated by application of robust statistics. The assessment of the data indicated broadened Gaussian distributions for all analytes. For benzo[a]pyrene (BaP), benzo[a]anthracene (BaA), chrysene and 5-methylchrysene more than 80% of the respective reported values gave rise to a satisfactory score of |z| ? 2. For benzo[b]fluoranthene, benzo[k]fluoranthene, and dibenzo[a,l]pyrene 70–80%, for the remaining analytes less than 70%, and for dibenzo[a,i]pyrene 52% of the scores were satisfactory. No systematic differences could be detected between values reported by laboratories using methods based on HPLC and the values related to methods based on GC for most of the analytes, except for benzo[k]fluoranthene and benzo[c]fluorene. In both cases laboratories using GC based methods reported about 50% higher values than laboratories using HPLC based methods. The overview on all z-scores sorted by laboratory revealed broad distributions and/or laboratory biases for several laboratories. An assessment of the reported method performance parameters revealed that for the two regulated compounds, BaP and BaA, only two thirds of the reported data were in compliance with Regulation (EC) 627/2006. Overall the methods used in the participating laboratories were – with ample room for improvement – well on the way to comply with European legislation.     

Single-laboratory validation of a saponification method for the determination of four polycyclic aromatic hydrocarbons in edible oils by HPLC-fluorescence detection

An analytical method is reported for the determination of four polycyclic aromatic hydrocarbons (benzo[a]pyrene (BaP), benz[a]anthracene (BaA), benzo[b]fluoranthene (BbF) and chrysene (CHR)) in edible oils (sesame, maize, sunflower and olive oil) by high-performance liquid chromatography. Sample preparation is based on three steps including saponification, liquid–liquid partitioning and, finally, clean-up by solid phase extraction on 2 g of silica. Guidance on single-laboratory validation of the proposed analysis method was taken from the second edition of the Eurachem guide on method validation. The lower level of the working range of the method was determined by the limits of quantification of the individual analytes, and the upper level was equal to 5.0 µg kg^?1. The limits of detection and quantification of the four PAHs ranged from 0.06 to 0.12 µg kg^?1 and from 0.13 to 0.24 µg kg^?1. Recoveries of more than 84.8% were achieved for all four PAHs at two concentration levels (2.5 and 5.0 µg kg^?1), and expanded relative measurement uncertainties were below 20%. The performance of the validated method was in all aspects compliant with provisions set in European Union legislation for the performance of analytical methods employed in the official control of food. The applicability of the method to routine samples was evaluated based on a limited number of commercial edible oil samples.     

Rapid determination of polycyclic aromatic hydrocarbons in natural tocopherols by high-performance liquid chromatography with fluorescence detection

A simple and rapid method has been developed and validated for the determination of seventeen polycyclic aromatic hydrocarbons (PAHs) in natural tocopherol products. Samples were dissolved in n-hexane, cleaned by an alumina column, and separated and determined by reversed-phase high-performance liquid chromatography (HPLC) with fluorescence detection. The recoveries were greater than 77.9%, except for the lowest molecular weight PAHs (Na, 1-Me, 2-Me, AC, F) which were between 15.9% and 75.8%. The limits of quantification were less than 0.38 ng/g for the heavy PAHs and less than 1.50 ng/g for the light PAHs. Good repeatabilities were achieved with RSD less than 10.7% for all the objective compounds. This method has been applied to evaluating PAHs contents in various natural tocopherol products and controlling natural tocopherol product quality.     

Factors affecting elimination of polycyclic aromatic hydrocarbons from smoked meat foods and liquid smoke flavorings

This review deals with effects of environmental and physicochemical factors affecting polyaromatic hydrocarbon (PAH) elimination from smoked meat products and liquid smoke flavoring (LSF). In the introductory part, some essential information are aimed at principles of food smoking and PAH formation during smoke generation as a result of incomplete wood combustion. Also, an application of alternative technology for food aromatization using LSF is briefly mentioned. Similarly, latest European legislation, biological effects, and analytical aspects of PAHs are mentioned concisely. The main part is devoted to physicochemical factors affecting the PAH content in smoked meat products, such as light, additional cooking, and packaging, which are able to decrease considerably PAH content in some meat products. The most important effect on PAH concentration decrease in LSF has low-density polyethylene (LDPE) package due to sorption processes on a surface of the plastic with subsequent diffusion into the plastic bulk. A less effective material is polyethylene terephthalate (PET), when only a surface adsorption process comes into account. Moreover, this process is affected also by other compounds presented in liquid media able to compete for the adsorption center on the PET surface.     

Multiresidue determination of carcinogenic polycyclic aromatic hydrocarbons in honey by solid-phase extraction and high-performance liquid chromatography

An analytical procedure based on solid-phase extraction, using ethyl acetate as the elution solvent, and high-performance liquid chromatography with fluorescence and diode array detection was developed for the identification and quantification of polycyclic aromatic hydrocarbons (PAHs) in honey. The method has been optimized and validated in accordance with Commission Regulation 333/2007 and Commission Decision 2002/657/EC. This method allows the identification of the 15 PAHs that should be monitored in food matrices, as proposed in 2002 by the Scientific Committee on Food and later by the European Union in the Commission Recommendation 2005/108/EC, because of their genotoxic and carcinogenic properties. The results of the validation study were in agreement with quality criteria described in European legislation in terms of sensitivity, accuracy, and ruggedness, and the method was applied to the analysis of 42 honey samples (21 from Spain and 21 from other regions). The honey samples were not contaminated by PAHs at detectable levels and thus could be marketed without health risk.     

同步荧光法测定散装白酒中的多环芳烃

建立了散装白酒中多环芳烃的同步荧光测定方法。通过皂化处理,优化了4种多环芳烃(PΑHs)化合物的测定条件。其多环芳烃(PΑHs)的回收率范围:84.88%～104.60%,相对标准偏差:0.51%～8.17%。该方法具有灵敏度高、准确度好、能同时测定多种PΑHs的优点,适合于散装白酒中多环芳烃的分析测定。     

Environmental tobacco smoke as a source of polycyclic aromatic hydrocarbons in settled household dust

Environmental tobacco smoke is a major contributor to indoor air pollution. Dust and surfaces may remain contaminated long after active smoking has ceased (called 'thirdhand' smoke). Polycyclic aromatic hydrocarbons (PAHs) are known carcinogenic components of tobacco smoke found in settled house dust (SHD). We investigated whether tobacco smoke is a source of PAHs in SHD. House dust was collected from 132 homes in urban areas of Southern California. Total PAHs were significantly higher in smoker homes than nonsmoker homes (by concentration: 990 ng/g vs 756 ng/g, p = 0.025; by loading: 1650 ng/m(2) vs 796 ng/m(2), p = 0.012). We also found significant linear correlations between nicotine and total PAH levels in SHD (concentration, R(2) = 0.105; loading, R(2) = 0.385). Dust collected per square meter (g/m(2)) was significantly greater in smoker homes and might dilute PAH concentration in SHD inconsistently. Therefore, dust PAH loading (ng PAH/m(2)) is a better indicator of PAH content in SHD. House dust PAH loadings in the bedroom and living room in the same home were significantly correlated (R(2) = 0.468, p < 0.001) suggesting PAHs are distributed by tobacco smoke throughout a home. In conclusion, tobacco smoke is a source of PAHs in SHD, and tobacco smoke generated PAHs are a component of thirdhand smoke.     

微孔沸石对卷烟烟气中多环芳烃去除的机理研究

通过多环芳烃（polycyclic aromatic hydrocarbon,PAHs）荧蒽（fluoranthene,Flu）和蒽（anthracene,Ant）在微孔沸石Y、ZSM-5和NaA上的吸附和催化裂解实验,探讨了沸石对卷烟烟气中PAHs选择性去除作用机理。实验结果表明：Y型沸石能吸附和催化裂解Flu和Ant;ZSM-5沸石能吸附和催化裂解Ant而不能吸附Flu;NaA沸石受孔径限制,不能吸附和催化裂解Ant和Flu。然而,将这些沸石添加到卷烟中,它们都不同程度地减少了烟气中B[a]P、Ant和Flu的含量。结合沸石吸附PAHs的红外图谱及量子化学计算结果：微孔沸石对卷烟烟气中PAHs的去除不是直接吸附或催化降解,而是吸附了形成PAHs的中间体/前体从而减少了PAHs的生成。     

气相色谱-质谱法测定白酒中塑化剂残留前处理方法的优化

目的对气相色谱-质谱法(gas chromatography-mass spectrometer,GC-MS)检测白酒中17种塑化剂的前处理方法进行优化。方法对试样中乙醇含量、总酸、总酯及盐添加量4个方面的变化进行了考察。用正己烷提取,离心后取上清液进行分析,根据回收结果筛选出最优的处理参数,并通过对质控样的测定以验证其实际的检测效果。结果当试样中的乙醇含量为10%(V/V)、盐添加量为0.3 g/mL时,17种塑化剂的回收结果较为理想;总酸含量在0～2.0 g/L及总酯含量在0～4.0 g/L范围内,其浓度的变化对测定结果无显著影响。在0.10～1.00μg/mL的浓度范围内,17种塑化剂的检测响应值均具有良好的线性关系,相关系数均大于0.99;方法的检出限范围为0.02～0.06 mg/kg(n=10),定量限范围为0.05～0.19 mg/kg(n=10);当在空白样品中的加标量为0.10、0.50、1.00 mg/kg时,17种塑化剂的平均回收率为80.0%～120.0%,相对标准偏差为2.47%～6.97%(n=6);采用本方法对含有14种塑化剂的质控样进行测定,所有测定结果与指定值间的相对偏差均小于10%,满足实际应用的精密度要求。结论经前处理后的方法,具有操作简易,回收率高,精密度好,检测结果准确等优点,可满足日常监督中对白酒塑化剂检测的需求。     

气相色谱-质谱法测定葡萄中苯醚甲环唑的不确定度评定

目的：评定气相色谱-质谱法测定葡萄中苯醚甲环唑时的不确定度。方法：根据GB 23200.8—2016 《食品安全国家标准 水果和蔬菜中500种农药及相关化学品残留量的测定 气相色谱-质谱法》建立模型,根据JJF 1059.1—2012《测量不确定评定和表示》对不确定度来源进行分析量化。结果：本方法测定苯醚甲环唑的合成不确定度为2.258%,扩展不确定度为0.0451,葡萄中苯醚甲环唑测定结果为（0.06047±0.00273）mg/kg,k=2。结论：本方法不确定度主要来源为标准溶液配制及其曲线拟合,重复性测定对实验结果准确性影响较小。     

油茶籽油中多环芳烃残留检测高效预处理方法的建立

目的建立一种高效的油茶籽油中多环芳烃(PAHs)残留检测预处理方法—凝胶渗透色谱(GPC)净化浓缩法。方法对适量油茶籽油样品添加与不添加PAHs混合标准液处理,经GPC系统净化,并利用系统配置的荧光检测器,比较2个监测样品各组分分离时段图谱,从而获得PAHs的最佳搜集时段,辅以回收率验证。结果对GB/T 24893-2010检测方法进行了优化,并对无PAHs油茶籽油样品进行加标处理,经回收试验,该方法在10~50μg/kg范围内的加标回收率范围为78.21%~95.64%,标准偏差为1.39%~4.55%。结论该方法简化了油茶籽油样品预处理步骤、减少了人工耗时、提高了检测效率,适合实验室批量检测。