Application of Accelerated Solvent Extraction for Simultaneous Isolation and Pre-cleaning Up Procedure During Determination of Polycyclic Aromatic Hydrocarbons in Smoked Meat Products

Food Analytical Methods - A simplified method, following European Commission legislation, for the determination of four polycyclic aromatic hydrocarbons (PAH4)—benzo[a]pyrene (B[a]P),...     

Carcinogenic polycyclic aromatic hydrocarbons (PAH) determined in Nigerian kundi (smoke-dried meat)

Chemical analyses of kundi show that, apart from a high level of carcinogenic benzo (a)pyrene (10·5–66·9 ng g^?1), eight other polycyclic aromatic hydrocarbons (PAH) are present at various concentrations. The high levels of PAH in kundi are due to the high glow and smoking temperatures averaging 926°C and 191·5°C, respectively. Column chromatography was used for PAH extraction with propylene carbonate as the eluting chemical; thin layer chromatography (TLC) on acetylated cellulose layer plates was used for separation, and the determination was performed using spectrophotofluorimetry. The public health implications of PAH as one of the possible carcinogenic factors in the high incidence of primary liver and stomach cancer reported in Nigeria are highlighted.     

Milk and urine excretion of polycyclic aromatic hydrocarbons and their hydroxylated metabolites after a single oral administration in ruminants

The aim of this study was to establish the transfer of phenanthrene, pyrene, and benzo[a]pyrene and their major hydroxylated metabolites to milk and to urine after a single oral administration (100 mg per animal of each compound) in 4 lactating goats. Detection and identification of the analytes (native compounds, 1-OH pyrene, 3-OH phenanthrene, 3-OH benzo[a]pyrene) were achieved using gas chromatography-mass spectrometry. Benzo[a]pyrene, phenanthrene, and pyrene were rapidly detected in the plasma stream, whereas 1-OH pyrene and 3-OH phenanthrene appeared later in plasma. These data suggest that pyrene and phenanthrene are progressively metabolized within the organism. Recovery rates of pyrene and phenanthrene in milk over a 24-h period appeared to be very low (0.014 and 0.006%, respectively), whereas the transfer rates of their corresponding metabolites were significantly higher: 0.44% for 1-OH pyrene and 0.073% for 3-OH phenanthrene. Recovery rates in urine were found to be higher (1 to 10 times) than recovery rates in milk. The 1-OH pyrene was found to be the main metabolite in urine as well as in milk. Thus, as has been established for humans, 1-OH pyrene could be considered as a marker of ruminant exposure to polycyclic aromatic hydrocarbons. Because 1-OH pyrene and 3-OH phenanthrene were measured in milk (unlike their corresponding native molecules), metabolites of polycyclic aromatic hydrocarbons should be taken into consideration when evaluating the safety of milk. Benzo[a]pyrene and 3-OH benzo[a]pyrene were (less than 0.005%) transferred to milk and urine in very slight amounts. This very limited transfer rate of both compounds suggests a low risk of exposure by humans to benzo[a]pyrene or its major metabolite from milk or milk products.     

Rapid determination of benzo(a)pyrene in processed meat and fish samples by second-derivative constant-energy synchronous fluorescence spectrometry

A simple, rapid and cost-effective method has been established for the determination of the quantity of benzo(a)pyrene (BaP), one of the most carcinogenic polycyclic aromatic hydrocarbons (PAHs), in roasted, smoked and charcoal grilled foods. Second-derivative constant-energy synchronous fluorescence spectrometry (DCESFS) improves the spectral resolution and selectivity of the fluorescence method. By using this method, processed meat, fish and some other food samples were analysed without resorting to complex pre-separation and purification procedures. The method was found to have a recovery of 97.7% ± 4.3%. The limit of detection (LOD) for BaP was 0.14 μg kg?1, far below the regulatory limit (1.0 μg kg?1) for BaP in food samples specified by the European Union. A certified reference material (Coconut oil, BCR?-458) was used to confirm the validity of the proposed method. The results suggest that the measurements are in a good agreement with the certified BaP concentrations (5.4% deviation). The results obtained by the proposed method for analysing BaP in food samples correlated well with those obtained by GC/MS.     

江苏地区熏烧烤肉制品质量分析

目的了解熏烧烤肉制品质量状况。方法对江苏省13市418批次熏烧烤肉制品进行抽检,采用最新食品安全国家标准进行检测,并对检测数据进行分析。结果苯甲酸及其钠盐2批次不合格,苯并[a]芘1批次不合格,4种多环芳烃之和[苯并[a]芘、苯并[a]蒽、苯并[b]荧蒽以及1,2-苯并菲总量,简写为PAH4]项目有3批次超过欧盟限量;360批次样品检出多环芳烃,检出率86.1%,分子量相对较低的轻质多环芳烃平均检出率是重质多环芳烃平均检出率的3.2倍;229批次肉制品进行了肉源性成分鉴定,发现21批次与声称成分不符,不符合率为9.2%。结论本次熏烧烤肉制品主要不合格项目为超范围使用食品添加剂、苯并[a]芘超标,PAH4超过欧盟限量标准;由肉种成分分析结果可以看出,存在以低价原料冒充高价原料的情况。     

Occurrence of polycyclic aromatic hydrocarbons in smoked cheese

The presence of polycyclic aromatic hydrocarbons (PAH) in smoked cheeses of different origin was studied. The samples were subjected to an initial extraction of fat and an alkaline treatment, extracted with cyclohexane, cleaned up by means of solid-phase extraction tubes, and analyzed by gas chromatography/mass spectrometry (GC/MS) operating in selective ion-monitoring mode (SIM). The results revealed the presence of numerous polycyclic aromatic hydrocarbons in the exterior zone of the samples, some of them with methyl groups. In all cases, the concentrations of compounds of low molecular weight were much higher than those of high molecular weight. Polycyclic aromatic hydrocarbons with varying degrees of carcinogenicity were identified, including benzo(a)pyrene in concentrations, which, although they did not exceed the limit established for this compound in the rind of ripened cheeses, do exceed the limit of 0.03 microg/kg fixed for other foods smoked with smoke flavorings. Significant differences in the number and concentration of PAH in smoked cheese also were observed from rind to interior, the rind being the most contaminated zone.     

Determination of polycyclic aromatic hydrocarbons in water and water-based alcoholic beverages

This paper proposes a simple HPLC method for the determination of polycyclic aromatic hydrocarbons (PAHs) in water, wine and beer. Samples were purified by PAH collection in solid-phase extraction (SPE) and analysed by reversed-phase HPLC (Supelcosil LC-PAH column from Supelco). For the beer sample, recoveries amounted to 28% for naphthalene and varied from 57% to 103% for the other PAHs; results are quantitative starting from fluoranthene (FI, the seventh component eluted). Almost all the beer and wine samples showed the presence of benzo(b)fluoranthene (BbF), benzo(k)fiuoranthene (BkF), benzo(a)pyrene (BaP), benz(ghi)perylene (BghiP) and indeno(1,2,3-cd)pyrene (IP), and in some cases there were traces of FI, benzo(a)anthracene (BaA) and dibenz(ah) anthracene (DBahA). Total contents of PAHs ranged from trace amounts to 0.72 ppb. Traces of BbF, BkF, BaP, BghiP and IP were also found in the wine samples.     

Rapid determination of benzo(a)pyrene in processed meat and fish samples by second-derivative constant-energy synchronous fluorescence spectrometry

A simple, rapid and cost-effective method has been established for the determination of the quantity of benzo(a)pyrene (BaP), one of the most carcinogenic polycyclic aromatic hydrocarbons (PAHs), in roasted, smoked and charcoal grilled foods. Second-derivative constant-energy synchronous fluorescence spectrometry (DCESFS) improves the spectral resolution and selectivity of the fluorescence method. By using this method, processed meat, fish and some other food samples were analysed without resorting to complex pre-separation and purification procedures. The method was found to have a recovery of 97.7%?±?4.3%. The limit of detection (LOD) for BaP was 0.14?µg?kg^–1, far below the regulatory limit (1.0?µg?kg^–1) for BaP in food samples specified by the European Union. A certified reference material (Coconut oil, BCR®-458) was used to confirm the validity of the proposed method. The results suggest that the measurements are in a good agreement with the certified BaP concentrations (5.4% deviation). The results obtained by the proposed method for analysing BaP in food samples correlated well with those obtained by GC/MS.     

Analysis of polycyclic aromatic hydrocarbons in vegetable oils combining gel permeation chromatography with solid-phase extraction clean-up.

A semi-automatic method for the determination of polycyclic aromatic hydrocarbons (PAHs) in edible oils using a combined gel permeation chromatography/solid-phase extraction (GPC/SPE) clean-up is presented. The method takes advantage of automatic injections using a Gilson ASPEC XL sample handling system equipped with a GPC column (S-X3) and pre-packed silica SPE columns for the subsequent clean-up and finally gas chromatography-mass spectrometry (GC-MS) determination. The method was validated for the determination of PAHs in vegetable oils and it can meet the criteria for the official control of benzo[a]pyrene levels in foods laid down by the Commission of the European Communities. A survey of 69 vegetable oils sampled from the Danish market included olive oil as well as other vegetable oils such as rapeseed oil, sunflower oil, grape seed oil and sesame oil. Levels of benzo[a]pyrene in all the oils were low (<0.2-0.8 microg kg(-1)), except for one sample of sunflower oil containing 11 microg kg(-1) benzo[a]pyrene.     

Multi-Walled Carbon Nanotubes as Effective Sorbents for Rapid Analysis of Polycyclic Aromatic Hydrocarbons in Edible Oils Using Dispersive Solid-Phase Extraction (d-SPE) and Gas Chromatography—Tandem Mass Spectrometry (GC-MS/MS)

A method was developed for the analysis of four polycyclic aromatic hydrocarbons regulated in the European Union, namely, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, and benzo[a]pyrene in edible oils. Multi-walled carbon nanotubes were applied for dispersive solid-phase extraction of analytes from the oils after dilution with n-hexane followed by elution of analytes with toluene under reflux conditions. Gas chromatography coupled to tandem mass spectrometry was used for quantitative determination of the analytes. The efficiency of four nanotube-based sorbents was evaluated. The performance characteristics of the method permitted reliable measurement of four regulated polycyclic aromatic hydrocarbons in oil samples according to the criteria stated in the Commission Regulation No. 836/2011 and considering the maximum levels (MLs) stated in the Commission Regulation (EU) No. 835/2011. The concentrations of the selected analytes in real-world samples determined by our developed method and by previously validated gel permeation chromatography method were found to be in a good agreement.     

Determination of polycyclic aromatic hydrocarbons in Italian milk by HPLC with fluorescence detection

The presence of polycyclic aromatic hydrocarbons (PAHs) in Italian commercial milk samples is reported. The study was carried out on lactating (cow and goat) and plant (rice, soya, oat) milk. The quantitative determination involved liquid–liquid extraction of PAHs, a pre-concentration and determination by HPLC using a fluorescence detector. The recovery of analytes was in the range of 70–115%. The precision of the method was found to be between 6% and 24%. The detection limit ranged from 0.66 to 33.3 µg l^–1 corresponding to 0.03–1.66 µg kg^–1 milk (wet weight), at a signal-to-noise ratio of 3, depending on the compound. By this procedure, the levels of more volatile PAHs (two to three aromatic rings) were confirmed in 34 commercial milk and three plant milk samples, whereas benzo[a]pyrene was found only in five pasteurised milk samples at a mean concentration of 0.17 µg kg^–1 milk. These results provide evidence that PAH levels are influenced by heat treatments and skimming processes of milk production.     

Analysis of polycyclic aromatic hydrocarbons in fish: Optimisation and validation of microwave-assisted extraction

An accurate and sensitive method for determination of 18 polycyclic aromatic hydrocarbons (PAHs) (16 PAHs considered by USEPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) in fish samples was validated. Analysis was performed by microwave-assisted extraction and liquid chromatography with photodiode array and fluorescence detection. Response surface methodology was used to find the optimal extraction parameters. Validation of the overall methodology was performed by spiking assays at four levels and using SRM 2977. Quantification limits ranging from 0.15–27.16 ng/g wet weight were obtained. The established method was applied in edible tissues of three commonly consumed and commercially valuable fish species (sardine, chub mackerel and horse mackerel) originated from Atlantic Ocean. Variable levels of naphthalene (1.03–2.95 ng/g wet weight), fluorene (0.34–1.09 ng/g wet weight) and phenanthrene (0.34–3.54 ng/g wet weight) were detected in the analysed samples. None of the samples contained detectable amounts of benzo[a]pyrene, the marker used for evaluating the occurrence and carcinogenic effects of PAHs in food.     

传统肉制品中多环芳烃来源和检测方法研究进展

详细阐述了目前传统肉制品中多环芳烃的产生途径主要是肉制品烟熏工艺、脂肪的焦化和裂解、蛋白质高温分解和糖的不完全燃烧造成的,指出多环芳烃检测中前处理过程的重要性和困难性,讨论了各种前处理过程和检测方式的优缺点,并将我国食品中多环芳烃限量标准与欧盟限量标准相比较,指出我国在多环芳烃限量保准方面与欧盟的差距,并对多环芳烃的检测和控制技术进行展望.     

Effects of grilling and roasting on the levels of polycyclic aromatic hydrocarbons in beef and pork

The concentrations of seven polycyclic aromatic hydrocarbons (PAHs) viz. chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenzo(a,h)anthracene, benzo(g,h,i)perylene, and indeno(1,2,3-c,d)pyrene in 150 samples of commercial meat products were determined. The PAHs were extracted with hexane, purified with Sep-Pak Florisil cartridges and determined by high-performance liquid chromatography using a fluorescence detector. Levels of PAHs were dependent on the method of cooking and type of heat source used. Relatively high levels of PAHs, 10.2 μg/kg on average, were found in charcoal-grilled pork samples. Average PAH levels in beef did not exceed 0.80 μg/kg. Charcoal grilling of pork samples resulted in extremely high levels of benzo(a)pyrene (3.0 μg/kg), while the average benzo(a)pyrene levels in charcoal-grilled beef samples were 0.15 μg/kg. These data can be used to estimate the dietary exposure of consumers to PAHs and to assess any potential risk associated with the ingestion of these foods.     

Polycyclic aromatic hydrocarbon levels and risk assessment for food from service facilities in Korea

ABSTRACT

In this study, levels of benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene (BaP), dibenzo[a,h]anthracene, benzo[g,h,i]perylene and indeno[1,2,3-c,d]pyrene in 412 food items collected from food service facilities in Korea were analysed. The concentrations of the eight polycyclic aromatic hydrocarbons (PAHs) ranged 0.13–0.48 μg/kg. The concentrations of benzo[a]pyrene in all food samples were <1 μg/kg, which is the lowest maximum limit in foods regulated by European Union legislation. PAH contents were employed to conduct exposure and risk assessment. The chronic daily intake of PAHs from 412 food samples was 5.48 × 10^–6-4.70 ×x 10^–4 µg-TEQ_BaP/kg/day with margins of exposure of 1.04 × 10⁹-1.16 × 10¹¹.     

远红外烤制对烤鱼品质及多环芳烃含量的影响

为了改善烤鱼的质构特性等食用品质,减少多环芳烃的形成,以草鱼为对象,研究传统炭烤和远红外烤制方式对烤鱼质构特性及多环芳烃含量的影响。结果表明：传统炭烤和远红外烤制对烤鱼的食用品质有不同影响,与传统炭烤鱼肉相比,远红外烤制鱼肉硬度显著降低（P＜0.05）,且剪切力均显著低于传统炭烤组（P＜0.05）,能够显著改善烤制鱼肉的嫩度;相对而言,远红外烤制鱼肉具有更优的质构特性;远红外烤制能显著降低烤鱼肉中PAH4（苯并(a)蒽、?、苯并(k)荧蒽、苯并(a)芘）和PAH16（萘、苊烯、苊、芴、菲、蒽、荧蒽、芘、苯并(a)蒽、?、苯并(b)荧蒽、苯并(k)荧蒽、苯并(a)芘、茚苯(1,2,3-c,d)芘、二苯并(a,h)蒽、苯并(g,h,i)芘）的生成量（P＜0.05）,与传统炭烤鱼肉相比,PAH4和PAH16总生成量分别下降39.07%和44.07%。     

凝胶渗透色谱净化-气相色谱-质谱法检测烤鸭鸭皮中16种多环芳烃

建立北京烤鸭鸭皮中16 种多环芳烃（polycyclic aromatic hydrocarbons,PAHs）的凝胶渗透色谱（gel permeation chromatography,GPC）净化-气相色谱-质谱（gas chromatography-mass spectrometry,GC-MS）检 测分析方法。匀浆后的烤鸭鸭皮样品经乙酸乙酯超声提取20 min,采用GPC净化,GC-MS进行检测。结果表 明：16 种PAHs在1～100 μg/L质量浓度范围内线性关系良好（R2＞0.996）,检出限为0.08～0.39 μg/kg,定量 限为0.25～1.29 μg/kg;在1、5、10 μg/kg添加水平下,16 种PAHs的回收率为66.2%～108.3%,相对标准偏差为 0.7%～13.5%（n=6）,满足分析要求;采用该方法对购自超市的北京烤鸭进行检测,烤鸭鸭皮样品中均未检出苯 并（a）芘,苯并（a）芘、苯并（a）蒽、苯并（b）荧蒽和?总含量也未超过欧盟限量标准（12.0 μg/kg）。     

Determination of PAH profiles by GC-MS/MS in salmon processed by four cold-smoking techniques

An analytical method based on gas chromatography/tandem mass spectrometry (GC-MS/MS) (triple quadrupole device) has been developed for quantification of polycyclic aromatic hydrocarbons (PAHs) in smoked salmon. This method was applied to determine PAH concentrations in smoked fish and assess the impact of four industrial smoking processes on their profiles. Two smokehouse temperatures and three smoke-exposure times were applied. All the smoking techniques used lead to acceptable PAH levels: the quantities recovered are 100 times lower than the legal limit (5 µg kg^-1) concerning the principal PAH, i.e. benzo[a]pyrene. To compare different smoking processes, the toxic equivalent quantity (TEQ) approach was chosen. Smouldering leads to the highest TEQ, while liquid smoke leads to the lowest TEQ.     

Evaluation of polycyclic aromatic hydrocarbon contents and risk assessment for fish and meat products in Korea

Contents and human exposure to polycyclic aromatic hydrocarbons (PAHs) in fish and meat products in Korea were analyzed. Liquid-liquid extraction and HPLC with fluorescence detection were used. The average concentrations of total PAHs were 0.21 μg/kg for fish and shellfish, 1.97 μg/kg for meat, and 0.32 μg/kg for smoked products. The benzo[a]pyrene (BaP) content was <5 μg/kg and contents of 4 PAHs (benzo[a]anthracene, chrysene, benzo[b]fluoranthene, and BaP) were lower than 30 μg/kg, which is the maximum tolerable limit. PAHs values were changed to BaP to conduct exposure assessments and risk characterization. Dietary exposure was 0.011-0.544 ng-TEQ_BaP/kg/day. The margin of exposure for all population groups assessed at the mean and 95^th percentile was 13,757–9,090,909, of low concern. PAHs were detected in fish and shellfish, meat, and smoked products, but their contribution to human PAH exposure was small.     

高效液相色谱-荧光法测定油炸型膨化食品中4种多环芳烃

建立了高效液相色谱-荧光法(HPLC-FLD)测定油炸型膨化食品中苯并[a]蒽(BaA)、(CHR)、苯并[b]荧蒽(BbF)、苯并[a]芘(BaP)4种多环芳烃(PAHs)的分析方法。样品经饱和氯化钠分散后,采用正己烷萃取,经BAP-3分子印迹柱净化,Waters PAH C₁₈色谱柱分离,荧光检测器进行测定,外标法定量。在0.5~40 μg/L浓度范围内4种PAHs均有良好的线性(r>0.999),定量限为(LOQ)0.3~0.5 μg/kg。在空白样品中进行1、5、25 μg/kg 3个水平的加标回收实验,方法的平均回收率在90.3%~107.4%之间,精密度在6.5%以下。该方法简单、快速、灵敏、重现性好,可用于油炸型膨化食品中4种PAHs的定量测定。