Occurrence of polycyclic aromatic hydrocarbons in artisanal Palmero cheese smoked with two types of vegetable matter

Palmero cheese is a fresh smoked cheese from the Isle of Palma (Canary Islands), manufactured with goat's milk. To guarantee its safety, the occurrence of polycyclic aromatic hydrocarbons (PAH) in artisanal Palmero cheese smoked with 2 types of vegetable matter (almond shells and dry prickly pear) was studied. The determination of PAH includes extraction and clean-up steps, followed by separation, identification, and quantification of PAH by gas chromatography-mass spectrometry in selected ion-monitoring mode. The most abundant PAH are those with 2 and 3 aromatic rings. Although the highest total PAH concentrations corresponded to the cheeses smoked with almond shells, the degree of PAH contamination of the cheeses studied was lower than that found in other cheeses smoked in the traditional way. The nature of the vegetable material used for smoking seemed to have an influence on the type of PAH formed, especially on alkylderivatives and some light PAH. However, despite the artisanal, and consequently variable, production process of these cheeses, many similarities have been found among their PAH profiles. In fact, relatively constant relationships are observed between the concentrations of certain pairs of PAH. Benzo(a)pyrene was only present in 2 samples, and in much lower concentrations than the maximum allowed legal limits. Therefore, according to the results obtained, it appears that it is possible to obtain a safe product without renouncing the artisanal character or the sensory properties of this type of cheese.     

Contamination of cheese by polycyclic aromatic hydrocarbons in traditional smoking. Influence of the position in the smokehouse on the contamination level of smoked cheese

This paper sets out to determine the polycyclic aromatic hydrocarbon (PAH) contamination degree of a traditionally smoked cheese: Herreño cheese, which comes from one of the Canary Islands. Its PAH profile is thoroughly studied by means of gas chromatography-mass spectrometry in SIM mode, and compared with that of an unsmoked cheese. Furthermore, a parameter not previously studied is evaluated, namely the influence of the position of the individual cheeses in the smokehouse on their PAH contamination level. Heavy PAH, among which are included most of the carcinogens, are very scarce and their concentrations low. In fact, benz[a]anthracene, together with chrysene+triphenylene, are the only heavy PAH detected in all of the smoked samples studied. The concentration of benzo[a]pyrene, detected only in 1 of the samples, is below the limit established in Spain for the rind of smoked cheese. In contrast, high concentrations of light PAH have been found, especially of naphthalene and its alkyl derivatives, whose effect on human health is not yet well established. The results derived from the analysis of the PAH profile suggest the potential usefulness of certain ratios between some pairs of PAH (phenanthrene/anthracene, naphthalene/acenaphthylene) to provide information on the PAH contamination source. Furthermore, differences have been found, depending on the position of the cheeses in the smokehouse, those placed in the path followed by the smoke being more contaminated. Therefore, the findings of this study could help in improving the design of smokehouses, to decrease the PAH contamination degree of smoked cheese.     

Polycyclic aromatic hydrocarbons in smoked cheese

BACKGROUND: Polycyclic aromatic hydrocarbons (PAHs) represent a group of organic compounds containing two or more aromatic rings. Their control in the human food chain is required due to the mutagenic and carcinogenic potential, exhibited in vertebrates. In the present study, the occurrence of PAHs in 36 cheeses smoked by various processes was investigated. RESULTS: PAH concentrations (sum of 15 US EPA PAHs) found in samples smoked under controlled industrial conditions were at level 0.11 µg kg^?1, whereas in ‘home‐made’ cheeses, the PAH content was up to 10 times higher. A similar trend was observed for B[a]P, a marker compound representing carcinogenic PAHs. While its levels in commercial products prepared by controlled smoking technologies were close to the limit of quantification (0.03 µg kg^?1); in household samples, the B[a]P content ranged from 0.6 to 0.9 µg kg^?1. Significantly higher amounts of PAHs (up to three to six times) were found in surface layers as compared to internal parts of cheese. CONCLUSION: Although smoked cheese is a popular food, only several papers have focused on PAH levels in these products. This paper evaluates the contribution of different smoking technologies to PAH contamination of several cheeses and thus can help in a risk assessment associated with their consumption. Moreover, the study shows the concentration ratios of selected PAHs, from which the type of smoking technology can be indicated. The results obtained in this study also supported the suggestion of the EU Scientific Committee on Food to use benzo[a]pyrene as an indicator of the occurrence of higher‐molecular mass PAHs. Copyright © 2008 Society of Chemical Industry     

高分子印迹固相萃取法测定熏烤肉制品中16 种欧盟优控多环芳烃

目的 建立高分子印记固相萃取-气相色谱质谱联用(MIPSPE-GC/MS)测定熏烤肉中 16 种欧盟优控多 环芳烃的检测方法。方法 样品经均质、超声波提取、高分子印记固相萃取柱净化后, 采用气相色谱质谱联用 仪在选择离子(SIM)扫描模式下进行测定, 内标法定量。 结果 本方法检出限为 0.07~0.24 μg/kg, 在 1~500 μg/L 范围内目标化合物具有很好的相关性, 相关系数均大于 0.999。日内及日间精密度小于 10%, 在 1、5 μg/kg 两 个加标水平下, 16 种 PAHs 回收率为 66.27 % ~ 111.61%, 相对标准偏差均小于 10%。 结论 本方法灵敏、 快速、 简便, 能满足熏烤肉制品中欧盟多环芳烃的检测要求。     

Headspace solid-phase microextraction as a tool to estimate the contamination of smoked cheeses by polycyclic aromatic hydrocarbons

Headspace solid-phase microextraction (HS-SPME) was used to study polycyclic aromatic hydrocarbons (PAH) in smoked cheeses. Two types of fiber coatings and different extraction conditions were tested. The results reveal that the use of an 85-microm polyacrylate fiber immersed in the headspace of the samples at 70 degrees C for 60 min is suitable for the detection of PAH with no more than 4 aromatic rings. To determine if a relationship can be established between the results obtained using a solvent extraction technique and HS-SPME, 6 samples of smoked cheese previously studied by a solvent extraction method were analyzed by HS-SPME, and the results obtained by both methodologies were compared. Polycyclic aromatic hydrocarbons were identified and quantified by gas chromatography-mass spectrometry operating in selective ion monitoring mode. Among the PAH determined by the solvent extraction method, only those with 4 aromatic rings or less were detected by HS-SPME and, consequently, this technique does not allow one to determine the PAH content of smoked cheese samples under the conditions of the study. Nevertheless, the relationship between the results obtained by both techniques for some PAH revealed that HS-SPME could be useful as a screening method to distinguish among samples with different degrees of PAH contamination.     

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。     

烟熏肉制品中多环芳烃测定的不确定度评定

目的评定用气相色谱-质谱法测定烟熏肉制品中多环芳烃残留量的不确定度。方法采用微波萃取法提取烟熏肉制品中的多环芳烃,经凝胶渗透色谱仪净化处理,用气相色谱-质谱法对烟熏肉制品中多环芳烃的残留量进行分析,建立数学模型,对测量结果的各不确定度来源进行分析和量化。结果本方法的不确定度主要来自于标准溶液的配制及标准曲线的建立。当烟熏肉制品中多环芳烃的含量为4.92~8.76μg/kg时,其扩展不确定度为0.37~0.78μg/kg(k=2)。结论该评定方法可用于气相色谱-质谱法对烟熏肉制品中多环芳烃残留量测定的不确定度评定。     

Determination of four priority polycyclic aromatic hydrocarbons (4PAHs) by GC-MS in traditional Turkish yoghurts

ABSTRACT

Polycyclic aromatic hydrocarbons (PAHs) are ingested with foods and cause toxicities for humans. Yoghurt is one of the main foods that mediate PAH ingestion. Yan?k yoghurt, a traditional strained yoghurt, can contain PAHs due to its production process. Therefore, the concentration and types of four polycyclic aromatic hydrocarbons were determined by gas chromatography-mass spectrometry (GC-MS). Yan?k yoghurt samples were collected from different shops in Denizli, Turkey. For the method validation, the Eurachem guide (second edition) was adopted. Accordingly, linearity, working range, limits of detection (LOD), quantification (LOQ), precision and trueness values were set. Due to the selected validation parameters, the limit for detection was between 0.03 ng g^?1and 0.05 ng g^?1while the limit for quantification was between 0.10 ng g^?1 and 0.16 ng g^?1. Recovery rates higher than 83.80 % were obtained for four PAHs at two spiked concentrations (2.0 and 5.0 ng g^?1). Five Yan?k yoghurt samples and one commercial concentrated yoghurt sample were successfully analysed using the validated method.     

食品中多环芳烃及卤代多环芳烃的研究进展

综述了多环芳烃及卤代多环芳烃的性质、毒性及国内外食品中的污染情况和研究现状,并对目前的分析测定方法进行了介绍,希望为我国开展食品领域内多环芳烃和卤代多环芳烃的研究提供参考。     

Survey of polycyclic aromatic hydrocarbons of vegetable oils and oilseeds by GC-MS in China

There is a lack of information regarding the occurrence and content of contamination of polycyclic aromatic hydrocarbon (PAH) in edible vegetable oils and oilseeds used for oil production in China. By combining the advantages of ultrasound-assisted extraction, low temperature separation and silica SPE purification, a method for the determination of the USEPA, 16 PAHs was developed based on GC-MS to fill this gap. The method recoveries for oils and oilseeds were 84.4–113.8% and 84.3–115.3%, respectively. The LODs and LOQs for 16 PAHs were ranged from 0.06–0.17 and 0.19–0.56 μg kg^–1, respectively. Based on the established method, PAH concentrations in 21 edible oils and 17 oilseeds were determined. Almost all the PAHs were found in all the samples tested, especially the light PAHs (LPAHs). Three oil samples exceeded the maximum level of 10 μg kg^–1 for BaP set by China. However, five and six oil samples, respectively, exceeded the maximum limits of 2 and 10 μg kg^–1 set for BaP and PAH4 by the European Union. The concentrations of PAH16 in oilseed samples were 1.5 times higher than corresponding oil samples. The relationships between PAH4 and PAH8, PAH4 and PAH16 as well as PAH8 and PAH16 indicates that PAH4 is a sufficient surrogate for the contamination level of PAHs in edible oils when compared with PAH8.     

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.     

Influence of smoking parameters on the concentration of polycyclic aromatic hydrocarbons (PAHs) in Danish smoked fish

A new method for the analysis of 25 polycyclic aromatic hydrocarbon (PAH) compounds in fish was developed, validated, and used for the quantification of PAHs in 180 industrially smoked fish products. The method included pressurized liquid extraction, gel-permeation chromatography (Bio-beads S-X3), solid-phase extraction (silica gel), and gas chromatography-mass spectrometry analysis. The sum concentration of 25 PAHs (∑PAH₂₅) was highest in smoked herring (n = 3) and mackerel fillets (n = 13), with an average concentration of 320 and 235 µg kg^?1, respectively. Lowest average ∑PAH₂₅ concentrations were obtained for indirectly smoked trout (26 µg kg^?1). Principal component analysis was used to correlate processing parameters to PAH concentrations and to identify the effects of these parameters. The analysis showed that for salmon hot-smoking conditions lead to higher ΣPAH₂₅ than cold smoking, and for other fish species direct smoking leads to higher ΣPAH₂₅ than indirect smoking. Also, the usage of common alder increases the PAH contamination compared with beech. The effects of smoking time, combustion temperatures, and two types of smoke-generating material on the ∑PAH₂₅ were also tested in a pilot plant study with smoked trout as a model fish. In addition to confirming that increased combustion temperatures and usage of common alder in comparison with beech increased ∑PAH₂₅, it was also revealed that the PAH concentration decreased in the order fish skin ? outer layer of the fish muscle > inner part of the fish muscle.     

加速溶剂萃取-气相色谱质谱法测定土壤中多环芳烃的含量

目的 建立土壤中7种多环芳烃(PAHs)的气相色谱质谱测定方法。方法 采用加速溶剂萃取法(ASE), 以二氯甲烷和丙酮(1∶1, v/v)为溶剂, 萃取液通过弗罗里硅土固相萃取柱净化后, 用GC/MS检测, 检测模式为选择离子监测(SIM)模式, 利用保留时间和特征离子进行定性, 外标法定量。结果 7种多环芳烃线性关系良好, 相关系数均大于0.995, 加标回收率均在87.2%~129%范围内, 最低检出限在0.096~1.48 μg/kg之间。结论 该方法操作方便、灵敏度高、重现性好, 可用于土壤中痕量多环芳烃的测定。     

食品中多环芳烃的研究进展

简述了近年来关于食品中多环芳烃的形成机理、分析方法及控制措施的研究进展,以期为解决食品中多环芳烃的污染问题提供依据。     

Selected polycyclic aromatic hydrocarbons in smoked tuna, swordfish and Atlantic salmon fillets

The presence of polycyclic aromatic hydrocarbons (PAHs) in commercial smoked fillets of tuna, swordfish and Atlantic salmon was studied. In Europe, the smoking technique is widely used in fish processing and these species are the most representative of the taste of consumers for smoked products. Samples were purchased on the Italian market and analysed by HPLC. Mean concentrations (ng g⁻¹) of acenaphthene (4.4, 6.2, 11.2), phenanthrene (11.5, 18.5, 8.9), anthracene (2.4, 5.2, 1.8), fluoranthene (17.0, 9.4, 4.7), benzo( k )fluoranthene (0.3, 0.1, 0.2) and benzo( a )pyrene (1.3, 0.1, 0.4) were found in Atlantic salmon, tuna and swordfish respectively. Benzo( b )fluoranthene (1.2 ng g⁻¹) was detected only in Atlantic salmon whereas dibenz( a,h )anthracene was never detected in this species, but only in tuna (0.5 ng g⁻¹) and swordfish (1.1 ng g⁻¹). Atlantic salmon contained the highest level of benzo( a )pyrene (2.8 ng g⁻¹) which is below the European regulatory level of 5 ng g⁻¹.     

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。     

食用油中多环芳烃的研究进展

多环芳烃(PAHs)是指2个或2个以上苯环以稠环形式相连的一类化合物,具有基因毒性和致癌性.对食用油中PAHs的来源、检测方法及控制和脱除方法进行了详尽的阐述,并指出PAHs前处理方法和控制、脱除方法是未来的研究方向.     

HPLC-FLD快速测定大豆中的多环芳烃

建立了大豆中多环芳烃的快速检测方法.采用乙腈-四氢呋喃(1+1)提取大豆中的多环芳烃,并用高效液相色谱-荧光光谱(HPLC-FLD)法测定多环芳烃含量.方法检出限和定量限分别为0.07～0.61 μg/kg和0.27 ～ 2.04 μg/kg,线性范围为2～ 200 μg/kg,回收率在81.7％ ～96.5％之间,相对标准偏差在2.10％ ～ 10.44％之间.     

天然生育酚中痕量多环芳烃脱除工艺的研究

采用活性炭吸附法脱除天然生育酚中的多环芳烃（PAHs）,考察了脱除溶剂、活性炭种类、搅拌时间、温度、活性炭用量、脱除次数对多环芳烃脱除率的影响。结果表明,用乙醇（分析纯）溶剂溶解生育酚（液固比为5：1）,加入10％的HC-2型活性炭,在20℃下搅拌45min,对PAHs可以达到较好的脱除效果（对轻PAHs的脱除率达到48％以上,对重PAHs的脱除率达到98％以上,对总PAHs的脱除率达到88％以上）,重PAHs的残留量为5．22ng／g,轻PAHs的残留量为86．22ng／g。