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.     

Polycyclic aromatic hydrocarbons (PAHs) in two Spanish traditional smoked sausage varieties: “Androlla” and “Botillo”

The polycyclic aromatic hydrocarbon (PAH) content in two traditional smoked sausages from Spain was determined. Determination and quantification of PAHs in smoked sausages were performed by HPLC with fluorescence detection. Results showed, that total mean levels of PAHs found were higher in “Androlla” (36.45 µg/kg) than in “Botillo” (29.39 µg/kg) although no significant differences (P < 0.05) were observed. In all examined samples content of phenanthrene was the highest in the two traditional sausage varieties. The maximum level for benzo[a]pyrene (BaP) of 5 µg/kg in smoked meat products was not exceeded in any samples. BaP represented 1.3% and 1.2% in “Androlla” and “Botillo” samples, respectively of the total sum of the 15 PAHs investigated in both sausages. Correlation statistic analysis (P < 0.01) showed that BaP was a good marker for 6 IARC possible and probable carcinogenic PAHs in “Androlla” samples (R_BaP/6IARC = 0.63) and in “Botillo” samples (R_BaP/6IARC = 0.96).     

Determination of polycyclic aromatic hydrocarbons (PAHs) in commonly consumed Nigerian smoked/grilled fish and meat

Smoking and/or grilling, when carried out with traditional methods involving direct contact with wood combustion fumes, is responsible for high contamination levels with carcinogenic polycyclic aromatic hydrocarbons (PAHs). The aim of this work was to investigate the PAH content of different smoked or grilled meat and fish products commonly consumed in Nigeria. A rapid method involving microwave-assisted saponification and simultaneous extraction followed by solid-phase extraction (SPE), high-performance liquid chromatography (HPLC) separation and spectrofluorometric detection was employed. Samples that were smoked or grilled using traditional systems, which use a wood fire, were heavily contaminated with benzo[a]pyrene (BaP) at levels ranging from 2.4 to 31.2 µg kg^?1 wet weight. Considerably lower contamination levels were found in samples smoked or grilled in the laboratory using a charcoal fire (BaP from 0.7 to 2.8 µg kg^?1 wet weight). The health risk associated with a daily consumption of 100 g of these products was also evaluated using the margin of exposure (MOE) approach. MOE values lower than 10,000 were obtained for all smoked/grilled commercial samples, indicating a potential concern for consumer health.     

Content of carcinogenic hydrocarbons in smoked foods in the German Democratic Republic and the Hungarian People's Republic

In the GDR, industrially smoked foods contain on an average 0.43 microgram Benzo(a)pyrene (BaP)/kg; products smoked according to trade rules, 0.76 microgram/kg; home-smoked products, 0.74 microgram/kg. The mean BaP content of smoked meat and sausage products in the GDR is 0.55 microgram/kg. Smoked fishes (without skin) contained on an average 1.39 microgram BaP/kg. The following average values were found in the Hungarian People's Republic: 0.6 microgram/kg (industrially smoked), 0.74 microgram/kg (home-smoked), 0.7 microgram/kg (total mean). Smoked cheese contained on an average 0.85 microgram/kg. The average BaP value of home-smoked (softwood) products of a Slovene ethnic group in the Hungarian People's Republic is 4.16 microgram/kg; the population of this region shows a considerably increased rate of stomach cancer. Apart from this particular case, the techniques used in both countries permit to obtain smoked meat and sausage products and smoked cheese with BaP contents less than 1 microgram/kg.     

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.     

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.     

Determination of PAHs in various smoked meat products and different samples by enzyme immunoassay

An enzyme immunoassay was used to determine benzo[a ]pyrene (BaP) in smoked meat products and other samples of food and environmental origin. The method used has a detection limit (3 σ) of 0.1 μg kg⁻¹ and a coefficient of variation less than 10%. The main aim of the study was to compare the possible influence of different smoking processes and packaging material on the amount of BaP deposited on smoked meat product, mainly different sausages. The lowest amount of BaP was found when smoke produced by steam in the indirect method smoking‐chamber was used. A slightly protective effect of polyamide casing was noted. © 1999 Society of Chemical Industry     

Levels of benzo[a]pyrene and benzo[a]anthracene in smoked “Provola” cheese from Calabria (Italy)

Levels of benzo[a]pyrene (BaP) and benzo[a]anthracene (BaA) in “Provola” cheese samples from Calabria, smoked naturally and using commercial smoke-flavouring, have been determined. A comparative study of BaP and BaA concentrations was carried out on rind, exterior zone, core and slice of these samples. Quantitative determination of BaP and BaA was ascertained by HPLC using fluorescence detection. Levels of BaP and BaA were found in all smoked “Provola” cheese samples, but higher in cheese smoked with natural methods (0.46–1.13 µg kg^?1 for BaP and 1.38–9.29 µg kg^?1 for BaA) compared to samples smoked using commercial flavouring (0.085–0.32 µg kg^?1 for BaP and 1.20–2.98 µg kg^?1 for BaA). The smoking process contributes to polycyclic aromatic hydrocarbons contamination; however, for improved food safety, the use of commercial buffered smoke is preferable to traditional smoking procedures.     

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.     

气相色谱-质谱法测定肉及肉制品中的2,4-D-丁酯

建立肉及肉制品中2,4-D-丁酯的气相色谱-质谱联用仪检测方法。样品采用乙腈提取,弗罗里硅土柱固相萃取柱净化,外标法定量。结果表明：方法添加量为5～100μg/kg时,回收率均大于70%,相对标准偏差为1.0%～3.6%,线性相关系数为0.99996,方法的检出限为5μg/kg。本方法适用于肉及肉制品中2,4- D-丁酯的测定。     

Changes of benzo(a)pyrene contents in smoked fish during storage

The paper refers to the determination of benzo(a)pyrene (BaP) contents in smoked fish by an HPLC method. Samples were analyzed after saponification and purification on Florisil and Separon SGX C-18, using selective fluorescence detection for the determination of BaP in smoked fish as well as in the model system, which was kept at the same conditions.

In the model system, the BaP degradation was found to be directly proportional to the duration of influence of environmental physicochemical factors with a clearly linear BaP decay line.

On the other hand, in the case of smoked fish the BaP contents were changed in dependence on diffusion into the internal product layers where their amount was relatively stabilized due to the absence of both light and oxygen.

Measurements have shown that BaP contents cannot be considered as a constant but that a gradual decrease is taking place as a result of various factors influencing the degradation process, which in itself can attain different velocities depending on the changing properties of the meat products as well as on environmental conditions.     

Polycyclic aromatic hydrocarbons in smoked fish

Summary The levels of polycyclic aromatic hydrocarbons (PAH) were determined in 70 samples of smoked fish and fish products. By application of capillary gas chromatography with flame ionization detection 13 PAH components were determined simultaneously.In 19 of 46 samples of commercially smoked fish, mainly from traditional kilns, the concentration of benzo[a]pyrene (BaP) exceeded 1 g/kg. The BaP levels in the samples from kilns with external smoke generation were without exception lower than 1 g/kg.Four of 16 canned smoked fish samples contained more than 1 g/kg of BaP. A sample of home-smoked herring from a home-made bricked kiln showed the highest level of BaP and total PAH in this study, 11.3 and 1,100 g/kg, respectively.

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Polycyclische aromatische Kohlenwasserstoffe in geräuchertem Fisch

Zusammenfassung Die Gehalte an polycyclischen aromatischen Kohlenwasserstoffen (PAH) wurden in 70 Räucherfischproben bestimmt. Bei Anwendung von Capillargaschromatographie mit Flammenionisationsnachweis wurden gleichzeitig 13 PAH bestimmt.In 19 von 46 Proben von kommerziell geräucherten Fischen, hauptsächlich aus herkömmlichen Öfen, überstieg der Gehalt an Benz(a)pyren (BaP) 1 g/kg. Die BaP-Gehalte in den Proben aus Rauchanlagen mit externer Raucherzeugung lagen ausnahmlos unter 1 g/kg.Von 16 untersuchten Räucherfisch-Konserven enthielten 4 Proben mehr als 1 g BaP/kg. Eine Probe eines hausgeräucherten Herings aus einem selbstge mauerten Räucherofen wies den höchsten Gehalt an BaP und totalen PAH dieser Untersuchung mit 11,3 und 1 100 g/kg auf.

     

Polycyclic aromatic hydrocarbons in smoked fish – a critical review

Among hundreds of components, wood smoke also contains at least 100 polycyclic aromatic hydrocarbons (PAH) and their alkylated derivatives. Many of them are carcinogenic. Benzo[α]pyrene (BaP) is regarded as a marker of the carcinogenic PAH in smoke and smoked fish, although in olive residual oil the maximum level of 2 μg/kg for each of the eight most carcinogenic PAHs, including BaP, has been set. Contemporary analytical procedures based on extraction of the hydrocarbons from the matrix, clean-up procedure, separation by gas chromatography (GC) or high performance liquid chromatography (HPLC), followed by detection and quantification by mass spectrometry (MS) or fluorescence detectors (FLD), respectively, make it possible to determine individual PAH in smoked foods at concentrations of the order of 0.1 μg/kg or even 0.01 μg/kg. Heavily smoked fish from traditional kilns, especially their outer parts, may contain up to about 50 μg BaP/kg wet weight, while the meat of mild hot-smoked fish, from smokehouses supplied with conditioned wood smoke from external generators, contains only about 0.1 μg/kg, or even less. Some older data on the contents of BaP in smoked fish should be treated with caution, if the analytical procedures used did not guarantee unequivocal separation and identification of the individual PAH.     

Polycyclic aromatic hydrocarbons (PAHs) in two Spanish traditional smoked sausage varieties: "Chorizo gallego" and "Chorizo de cebolla"

The polycyclic aromatic hydrocarbon (PAH) content in two traditional smoked sausages from Spain was determined. Results showed, that total average levels of PAHs found were higher in "Chorizo de cebolla" (101.81 vs. 98.48 μgkg(-1)). Most contents of PAHs found in both sausages were phenanthrene, naphthalene and anthracene. The maximum level for benzo[a]pyrene (BaP) of 5 μgkg(-1) in smoked meat products was not exceeded in any samples. BaP represented a 0.73% and 1.15% with respect to the total sum of the 15 PAHs that were investigated in this study for "Chorizo gallego" and "Chorizo de cebolla", respectively. Correlation statistic analysis (P < 0.01) of the contents from samples analysed, showed that BaP was a good marker for Σ15 PAHs in "Chorizo gallego" samples (R(BaP/Σ15PAHs) = 0.77; P < 0.01) and it was a good marker for 7 U.S. EPA probably carcinogenic PAHs in "Chorizo de cebolla" samples (R(BaP/7EPA) = 0.95) and in "Chorizo gallego" samples (R(BaP/7EPA) = 0.81).     

Polycyclic aromatic hydrocarbons in German smoked meat products

The contents of the 15+1 EU priority PAH were analysed from 113 representative commercial smoked German meat products collected in the year 2006 with a Fast-GC/HRMS method. The median of benzo[a]pyrene content was 0.03 μg/kg and therefore greater than a factor of 100 below the maximum level of 5 μg/kg. The highest content of benzo[a]pyrene was detected in a Frankfurter-type sausage (0.43 μg/kg). The sum content of benzo[a]pyrene, benzo[a]anthracene, chrysene and benzo[b]fluoranthene (“PAH4”), as proposed by the European Food Safety Authority to be a good marker for PAH in food, was 0.28 μg/kg in median, and the sum content of the 15+1 EU priority PAH was 0.64 μg/kg in median. The analysed smoked meat products showed an increasing presence of PAH in the following order: cooked ham (n = 17) < raw sausages (n = 25) < liver sausages (n = 25) < raw ham (n = 23) < Frankfurter-type sausages (n = 23). The correlation coefficient (R) between BaP and the sum of the 15+1 EU priority PAH was 0.90. To increase the safety of the consumer, a lowering of the BaP maximum level to 1 μg/kg is proposed and critical aspects using “PAH4” as a marker for PAH in food surveillance are discussed.     

烟熏肉制品中甲醛含量的测定

为测定烟熏肉制品中的甲醛含量,比较室温浸泡法和水蒸气蒸馏法预处理方法,并对不同产地和种类烟熏腊肉中的甲醛含量进行测定。结果表明,综合考虑加标回收率、相对标准偏差以及方法检出限,采用水蒸气蒸馏预处理方法要优于采用室温浸泡法。而对烟熏肉制品甲醛含量的测定结果表明,传统烟熏肉制品中甲醛含量较高,其中表层的甲醛含量21～124mg/kg,内部的甲醛含量8～22mg/kg。     

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.     

Influence of cooking on benzo(a)pyrene content in smoked sausages

The changes in benzo(a)pyrene (BaP) content of smoked sausages were monitored during 1 h cooking. During this time, the BaP content decreased from 4·80 to 1·87 μg/kg. The maximum drop in BaP content was reached in the first 20 min of cooking. Two factors affected the course of BaP changes, viz. water-holding capacity and the fat content. After excluding these factors, there was a high correlation coefficient of 0·996 between time of cooking and BaP content, which confirmed an inverse relationship between the decrease in BaP content and time of cooking.

The BaP decrease was directly proportional to the decrease of fat content during cooking, when the relatively high BaP content of 7·71 μg/kg was found in the cooked-out fat.     

Determination of polycyclic aromatic hydrocarbons in commercial roasted coffee beans

This study was conducted to investigate the presence of 7 polycyclic aromatic hydrocarbons (PAHs) [benzo[a]anthracene (BaA), chrysene (CRY), benzo[b] fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[a] pyrene (BaP), dibenzo[a,h]anthracene (DahA), benzo [g,h,i]perylene (BghiP)] in roasted coffee beans from Korean market. In this study, the method for sample preparation involved liquid-liquid extraction after saponification with potassium hydroxide (KOH), followed by solid-phase extraction (SPE). The external standard method was used for measurement, and regression coefficients ranged from 0.9938 to 0.9995. To determine how much of the analyte remained in the samples after sample preparation, 3-methylcholanthrene was spiked into the samples for a recovery study. The limits of detection and quantification of the 7 PAHs ranged from 0.016 to 0.497 and 0.054 to 1.656 μg/kg, respectively. The concentrations of PAHs in the 10 coffee samples ranged from 0.62±0.08 to 53.25±9.38 μg/kg. According to the results, the critically harmful PAH, BaP, was presented at levels harmless to humans.     

Benzo(a)pyrene penetration on a smoked meat product during smoking time

The Codex Alimentarius gives recommendations to prevent carcinogenic polycyclic aromatic hydrocarbons (PAH) (represented by benzo(a)pyrene (BaP)) contamination during processing of meat products, including the control of smoking time. The influence of direct smoking time (0, 1, 3, 5 and 7 days) on the relationship between the BaP and moisture content of a typical Spanish smoked meat product called chorizo and the mechanism of BaP penetration and water release from four different depths in the product was studied. Chorizo was studied from the Principality of Asturias, a location never before tested. An analytical method was developed for this purpose consisting of PAH extraction assisted by sonication followed by solid-phase extraction (SPE) sample clean-up and analytical determination using GC-MS. Results show that an increase in smoking time produced contradictory and independent effects on the moisture and BaP content (µg kg^–1) of chorizos. The moisture content decreased from 49.9% to 31.3%. On the other hand, the BaP content increased from less than 0.24 µg kg^–1 to 0.75 µg kg^–1, finally stabilising after 5 days of smoking. After this time, the natural pores of the casing could be blocked by the large size tar particles from smoke, preventing the continued penetration of PAHs. The BaP content decreased and the moisture content increased progressively from the casing to the centre of the meat product. BaP mainly accumulated in the smoked casing, being four times in excess of the legal limit. This paper analyses the mechanism for preventing PAHs contamination during the process of smoking meat products.