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.     

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.     

Load of polycyclic aromatic hydrocarbons in edible vegetable oils: importance of alkylated derivatives

The presence of polycyclic aromatic hydrocarbons (PAHs) has been studied in different samples of olive oil, extra virgin olive oil, and refined seed oils. A high number of PAHs have been found, with a wide range of molecular weights and in concentrations that are high or even very high compared with the data obtained by other authors, especially in the seed oils. Among the PAHs identified, more than half are alkylated compounds, which account for the major part of the total PAH concentration in some of the samples. The total PAH concentrations in olive oils and extra virgin olive oils are similar, but the former present a higher proportion of heavy PAHs than the latter. The seed oils, in general, have much higher concentrations than the different types of olive oil and their PAH profiles are different. One of the olive oil samples exhibited a PAH distribution similar to that observed in olive pomace oil, suggesting possible adulteration. These data reveal that, in some cases, PAH profile provides useful information in relation to the possible origin of the contamination. We also observed large differences in PAH distribution between oils with the same label but from different batches. PAHs with varying degrees of carcinogenicity have been identified in all the samples, including benzo[a]pyrene, although this PAH was identified neither in the extra virgin olive oils nor in two of the seed oil samples.     

Determination of polycyclic aromatic hydrocarbons (PAH) in edible vegetable oils by liquid chromatography and programmed fluorescence detection. Comparison of caffeine complexation and XAD-2 chromatography sample clean-up

Two clean-up procedures were compared for the analysis for polycyclic aromatic hydrocarbons (PAHs) in edible vegetable oils. One method comprises a liquid-liquid extraction followed by XAD-2 chromatography and the other a caffeine-formic acid complexation. The clean-up step is followed by gradient reversed-phase HPLC in combination with wavelength-programmed fluorescence detection. Due to better repeatability and simplicity, the XAD-2 method was selected for the determination of PAHs in 14 different vegetable oils. Between the different oil samples large differences were observed in PAH concentrations. PAH concentrations in vegetable oils sampled from the Dutch market appear to be comparable with those found in other countries.     

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).     

部分食品煎炸用油的反式脂肪酸比较

为探究不同品种食用油和煎炸食品对反式脂肪酸形成的影响,本文使用5种食用油(葵花油、大豆油、菜籽油、棕榈油、花生油),在一定温度下炸制14批次油条,又依次使用大豆油炸制豆腐、油条和鸡腿,对2种情况下产生的煎炸油进行气相色谱分析,比较反式脂肪酸含量.结果表明:炸油条过程中,食用油中反式脂肪酸的含量均随着煎炸时间的延长而增加...     

Bioaccumulation and toxic potencies of polychlorinated biphenyls and polycyclic aromatic hydrocarbons in tidal flat and coastal ecosystems of the Ariake Sea,Japan

Sediment and marine biota comprising several species of tidal flat and coastal organisms were analyzed for polychlorinated biphenyls (PCBs) including non- and mono-ortho coplanar congeners and polycyclic aromatic hydrocarbons (PAHs) to examine bioaccumulation profiles and toxic potencies of these contaminants. Concentrations of PCBs in tidal flat organisms ranged from 3.6 ng/g (wet wt) in clams to 68 ng/g (wet wt) in omnivore tidal flatfishes, a discernible trend reflecting concentrations and trophic levels. In contrast, PAHs concentrations were the highest in lower trophic organisms, such as crabs and lugworms from tidal flat, whereas those in coastal fishes, squid, and finless porpoises were less than detection limit. Greater bioaccumulation of PAHs was found in lugworms and crabs, which might be due to their direct ingestion of sediment particulates absorbed with PAHs. TCDD toxic equivalents (TEQs) were calculated for PCBs and PAHs in sediments and biota. PCBs accounted for a greater proportion of total TEQs (sum(TEQs): sum of TEQ(PCB) and TEQ(PAH)) in coastal and tidal flatfishes (>95%), while PAHs occupied a considerable portion of sum(TEQs) in sediment (>97%). Interestingly, TEQ(PAH) accounted for 37% and 81% of the sum(TEQs) in crabs and clams, respectively. Benzo[b]fluoranthene was the dominant contributor to TEQ(PAH) in both the species. Considering these observations, the environmental risks of PAHs may not be ignored in benthic tidal flat organisms due to their greater bioaccumulation through sediments.     

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.     

Comparison of donor–acceptor and alumina columns for the clean-up of polycyclic aromatic hydrocarbons from edible oils

Two methods for clean-up and sample enrichment for the analysis of polycyclic aromatic hydrocarbons (PAHs) in edible oils are compared; a clean-up based on a donor–acceptor complex chromatography (DACC) column and a standardized method widely used in the food industry consisting in a low pressure column chromatography with alumina as stationary phase. Both methods are followed by a reversed-phase high-performance liquid chromatography with fluorescence detection for the separation and quantitation of each PAH. Certified materials were used in order to validate the methods. The limits of detection were lower than 1 ng/g and good selectivity was achieved in both cases. The DACC column clean-up is faster and better accuracies were obtained. The advantages and disadvantages of both methods are discussed.     

Polycyclic aromatic hydrocarbons in traditionally smoked meat products from the Baltic states

A total of 77 traditionally smoked meat samples produced in Latvia, Lithuania, and Estonia were tested for the occurrence of four EU regulated polycyclic aromatic hydrocarbons (PAHs). Levels of PAHs exceeding the EU maximum levels for benzo[a]pyrene and for the sum of four PAHs (PAH4) were detected in 46% and 48% of the samples originating from Latvia. The detected BaP levels in smoked meats ranged from 0.05 to 166 μg kg^?1, while the PAH4 content ranged from 0.42 to 628 μg kg^?1. The mean dietary exposure to PAHs was estimated at the levels of 5.4 ng BaP/kg bw/day and 36 ng PAH4/kg bw/day. The margin of exposure (MOE) approach was utilised to assess the risks to Latvian consumers due to PAHs and the obtained MOEs were in a range of 7205–24,434, thus indicating a potential concern for consumer health for specific population groups.     

不同植物油制取工艺对毛油中多环芳烃含量的影响

以花生仁、芝麻、油菜籽为原料,采用不同工艺分别制取毛油,并对毛油中多环芳烃(PAHs)含量进行检测分析,探究制油工艺对毛油中PAHs含量的影响。结果表明:6个浸出毛油样品中Ba P、PAH4、PAH16平均含量分别是6个压榨毛油样品的1.53、1.45、1.08倍,说明PAHs在浸出溶剂正己烷中有很好的溶解度,因此油籽无论脱皮与否所制取浸出毛油中PAHs含量均高于压榨毛油;6个脱皮油籽所制取毛油中Ba P、PAH4、PAH16平均含量分别是未脱皮油籽毛油的1.51、1.61、1.53倍,即无论是压榨法还是浸出法,脱皮油籽所制取毛油中PAHs含量均高于未脱皮油籽毛油。这可能是因为种皮主要成分为粗纤维,而PAHs的亲脂性使其更容易富集在种仁中。     

Polycyclic aromatic hydrocarbons (PAHs) in different types of smoked meat products from Serbia

The contents of the16 EU priority PAHs in six different meat products from Serbia (beef ham, pork ham, bacon without skin, bacon with skin, cajna sausage and sremska sausage) were examined during the process of smoking. All these meat products from meat industry Zlatiborac, Mačkat, Serbia presented in this study, have not previously been analysed concerning to their contents of PAH compounds. Determination and quantification of PAHs in meat products were performed by a Fast GC/HRMS method. The maximum level for benzo[a]pyrene (BaP) of 5 μg/kg in smoked meat products was not exceeded in any samples. BaP comprises in general 4.6% of the total sum of the 16 EU priority PAHs and 15.2% of the total sum of the 12 IARC PAH compounds. The suitability of BaP as a marker both for 16 EU priority PAHs and 12 IARC probably and possibly carcinogenic PAHs was checked by applying correlation analysis.     

Assessment of contamination source and quality control approach for polycyclic aromatic hydrocarbons in wood-pressed rapeseed oil

Contamination sources of polycyclic aromatic hydrocarbons (PAHs) in the raw material, oil production and storage processes of wood-pressed rapeseed oil were investigated in this study. The results showed that benzo[a]pyrene (BaP) and PAH4 (sum of BaP, benzo[a]fluoranthene, benzo[b]fluoranthene and chrysene) were unevenly distributed in the kernel (0.56–0.98 and 2.84–8.64 μg/kg, respectively) and hull (1.53–3.17 and 13.49–22.31 μg/kg, respectively) of the rapeseed raw materials. The contents of BaP and PAH4 continuously increased during the process of wood-pressed rapeseed oil, ranging from 2.21 to 10.93 and 9.36 to 40.03 μg/kg, thus demonstrating that a wide range of pollution sources of PAHs existed for the test wood-pressed rapeseed oils. The initial temperature and time of roasting should be controlled at <210°C and <60 min, due to the generation of PAHs in rapeseed by over-roasting. In addition, contact tools and substance such as lubricating oil (from the mill), heat-transfer oil (from roasting machine), rubber gaskets and straws should be properly screened. The BaP and PAH4 of rapeseed placed in the roasting area increased from 0.5 to 2.24 and from 2.08 to 9.03 μg/kg, respectively. Therefore, roasting fume control and treatment systems are necessary and the roasting section should be strictly isolated from the other stages. Storage can slightly lower the PAHs amounts in the rapeseed oil, which made the contents of BaP and PAH4 decrease from 27.00 to 24.70 and from 138.63 to 117.58 μg/kg, respectively. Quality control measures of PAHs in wood-pressed rapeseed oil were proposed and implemented, and the final oil products’ BaP and PAH4 were kept below 2 and 10 μg/kg, respectively, which meets the European Commission Regulation No. 835/2011.     

食用油中多环芳烃检测的前处理方法研究进展

近年来，食用油中多环芳烃的检出多有报道，其安全问题备受社会关注。多环芳烃作为一类复杂的高亲脂性有机污染物，具有致畸致癌性，易在食用油的生产加工贮存过程中残留，对人体健康造成危害。因此，开发快速准确的分析方法检测食用油中的多环芳烃对于认识和应对食用油中多环芳烃的危害有着重要的理论和实践价值，其中分析检测过程的关键环节是选择合适的前处理方法。本文首先对食用油脂中多环芳烃进行概述，同时重点综述了近年来检测食用油中多环芳烃的常用样品前处理方法，并比较了不同前处理方法的优缺点，最后对未来多环芳烃检测方法的发展方向进行了展望，以期为开发更高效的油脂中多环芳烃检测的前处理方法提供参考。     

Effects of a chemical company fire on the occurrence of polycyclic aromatic hydrocarbons in plant foods

On Friday, September 1, 2006, the facilities of a chemicals distributor in the Spanish town of Caldas de Reis, were almost completely destroyed as a result of a fire. Comprehensive liquid chromatography-fluorescence detection (LC-FD) analyses were performed on plant foods to determine the toxic impact of this kind of accident on population. PAHs from a polluted atmosphere are generally transferred to plants by particle-phase deposition on the waxy leaf cuticle or by uptake in the gas phase through stomata. PAH levels in all samples were not alarming (total PAHs were below 4.240 ng/g) and the PAH profiles were similar, with the exception of peppers, in all vegetal materials (5-to-4 rings ratio of 1–2), suggesting the similarity in source type (the fire). PAH concentrations in plants were related to their surface exposed to air, indicating that the contribution of soil/water PAHs to plants (aerial part) accumulation was insignificant.     

选择离子流动管质谱法测定油脂中的呋喃

目的测定食用油等油中的呋喃含量。方法将5 g油样密封于(540±5)mL瓶中,加入一定量呋喃(X),于65℃水浴加热1 h后测定其呋喃(Y)含量。选择离子流动管质谱(selected ion flow tube mass spectrometry,SIFT/MS)方法,以NO+为初始离子,测定油样密封瓶顶空中呋喃浓度,再据呋喃标准曲线定量密封瓶中油样的呋喃含量。结果所得标准曲线为:Y=29.55X+1.11(r~2=0.9867,n=6),其检测限和定量限分别为0.052 ng/g和0.063 ng/g。利用该标准曲线测定多种油,其中废弃餐用油(即各种类型的地沟油、煎炸老油等)呋喃含量为4.37~17.83 ng/g;大豆油、花生油、两种菜籽油、茶油、葵花油的呋喃含量均小于1 ng/g;两种冷榨橄榄油的呋喃含量分别为1.19和4.39 ng/g。结论该法可方便、快速、准确地测定油样中呋喃的含量,呋喃可以作为鉴伪食用油和废弃餐用油的特征性指标。     

Historical records of airborne polycyclic aromatic hydrocarbons by analyzing dated corks of the bark pocket in a Longpetiole Beech tree

Historical monitoring of airborne polycyclic aromatic hydrocarbons (PAHs) pollution levels was novelly demonstrated by analyzing the dated corks of a bark pocket formed from 1873 to 2003 in a Longpetiole Beech (Fagus longipetiolata) tree trunk sampled from southeastern China. The fundamental studies indicated that the PAHs of log K(oa) < 8.5 are primarily accumulated through interactions with lipid substances in cork and log K(oa) dependent, while the PAHs of log K(oa) > 8.5 existing as particle-phase dependent on log Vp are accumulated through stochastic entrapment by the lenticels on the surface of the cork. The translocation of PAHs by xylem flow and phloem stream as well as radial diffusion from the cork to the inner tissues was not significant, and the cork is most effective for accumulating airborne PAHs. The total concentrations of 16 EPA PAHs (sumPAHs) in the dated corks progressively increased from 43.5 ng/g recorded in the earliest available cork in 1873-1875 to the maximum 345.7 ng/g in 1956-1961, and then gradually decreased to 267.0 ng/g in 2003, while the concentration of perylene (PER) was slightly fluctuating at 0.178 +/- 0.033 ng/g. Moreover, the concentration ratio of sumPAHs to PER increased from 193 to 2431 from 1873 to 2003, indicating a progressive increase in PAH pollution in southeastern China.     

Distribution of polycyclic aromatic hydrocarbons in the coastal region off Macao, China: assessment of input sources and transport pathways using compositional analysis

The coastal region off Macao is a known depositional zone for persistent organic pollutants (POPs) in the Pearl River Delta and Estuary of southern China and an important gateway for the regional contributions of contamination to the globe. This paper presents a comprehensive assessment of the input sources and transport pathways of polycyclic aromatic hydrocarbons (PAHs) found in the coastal sediments of Macao, based on measurements of 48 2-7 ring PAHs and 7 sulfur/oxygenated (S/O) PAH derivatives in 45 sediment, 13 street dust, and 68 aerosol samples. Total sediment PAHs concentrations ranged from 294 to 12741 ng/g, categorized as moderate contamination compared to other regions of Asia and the world. In addition, the PAH compounds appeared to be bound more strongly to aromatics-rich soot particles than to natural organic matter, implying a prevailing atmospheric transport route for PAHs to Macao's coast. Compositional analysis and principal component analysis (PCA) suggested that different classes of PAHs in the coastal sediments of Macao may have been derived from different input sources via various transport pathways. For example, alkylated and S/O PAHs were likely derived from fossil fuel leakage and transported to sediments by both aerosols particles and street runoff. High-molecular-weight parent PAHs were predominantly originated from automobile exhausts and distributed by direct and indirect atmospheric deposition. Low-molecular-weight parent PAHs, on the other hand, may have stemmed from lower temperature combustion and fossil fuel (such as diesel) spillage from ships and boats and were transported to sediments by river runoff or direct discharge as well as by air-water exchange.     

Effects of toasting procedures on the levels of polycyclic aromatic hydrocarbons in toasted bread

Some polycyclic aromatic hydrocarbons (PAHs), particularly those with a high molecular weight, have been classified as probably carcinogens to humans by the International Agency for Research on Cancer (IARC). The significance of the determination of PAHs is reflected by the special attention of the European Union, which is paying to regulate the maximum allowed levels of PAHs in foodstuffs such as smoked foods. Like other thermally processed foodstuffs, toasted bread can contain these carcinogenic chemicals, not only due to a contamination at source but also during toasting. In order to check PAHs generated from toasting in sandwich bread, several treatment conditions were evaluated: direct toasting (flame-toasting, coal-grilling or gas oven-toasting) or indirect toasting (electric oven-toasting). PAHs were extracted by solid–liquid extraction (SLE) and determined by liquid chromatography with fluorescence detection (LC-FD). Based on the results, the used toasted technique would strongly affect in PAH levels in the final product. No samples obtained by electric oven and toaster were polluted; otherwise the samples toasted by charcoal and flame grilling presented very important levels. Up to 350 μg/kg of total PAHs were detected in toasted samples by wood flame. Differences between different ways of toasting could be ascribed to deposition of PAHs from smoke. Finally, several commercial toasted samples of bread were tested to determine PAHs. Overall, the PAH levels were very low. Benzo[a]pyrene ranged from no detectable to 0.23 μg/kg.     

Exposure to polycyclic aromatic hydrocarbons through consumption of edible marine species in Catalonia, Spain

The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs; naphthalene, acenaphtylene, acenaphtene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-c,d]pyrene, dibenzo[a,h]anthracene, and benzo[g,h,i]perylene) were determined by gas chromatography-mass spectrometry in samples of 14 edible marine species (sardine, tuna, anchovy, mackerel, swordfish, salmon, hake, red mullet, sole, cuttlefish, squid, clam, mussel, and shrimp) collected in March and April 2005. These species are widely consumed by the population of Catalonia, Spain. PAH intake was also estimated for eight age and sex groups of this population. Mussel, clam, and shrimp had the highest PAH concentrations (22.4, 21.5, and 15.9 ng/g of fresh weight, respectively). In contrast, sole (2.5 ng/g of fresh weight) and cuttlefish and squid (both 3.0 ng/g of fresh weight) had the lowest mean concentrations. The highest PAH intake was found in women and girls (5.3 and 5.2 ng/kg/day, respectively), but female adolescents and female seniors had the lowest PAH intakes (3.3 ng/kg/day in both groups). The intake of benzo[a]pyrene and six other PAHs that are probably human carcinogens through consumption of these marine species would be associated with 0.27/10(6) increase in the risk of development of cancer over a 70-year life span.