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).     

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 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.     

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.     

Benzo(a)pyrene contents of meat products

The Benzo(a)pyrene contents of 386 smoked and 18 grilled meat products were determined by application of capillary gas-chromatography-mass fragmentography using inner standards. 82 per cent of 183 black smoked hams contained appreciably more than the legal maximum amount of 1 ppb. The quantities of BaP increased very much with increase of soot accumulation on the surface. Only 15 per cent of 95 hams and only 9 per cent of 87 sausages smoked by normal methods had excessive BaP content. The amounts in excess of 1 ppb were much lower in these hams. Bratwurst grilled by use of pine-cones, spruce-cones and hard wood contained on average 28 ppb BaP. The BaP amounts of Bratwurst grilled over charcoal were without exception lower than 1 ppb.     

大豆油精炼过程中多环芳烃的迁移规律

明确大豆油精炼过程多环芳烃（polycyclic aromatic hydrocarbons,PAHs）风险成分的迁移规律,以便于食品中PAHs的风险防范和控制。通过对大豆油精炼生产中脱胶油、脱酸油、脱色油、脱臭油和对应加工助剂磷酸、烧碱、活性白土以及精炼副产物油脚、皂脚、废白土、脱臭馏出物样品中PAHs组分含量的检测,分析PAHs在大豆油精炼生产中的迁移规律。结果显示：大豆油精炼用加工助剂中均含有PAHs,磷酸、烧碱和活性白土中苯并[a]芘（benzo[a]pyrene,BaP）含量分别为0.95、1.84?μg/kg和0.71?μg/kg,欧盟限量控制的4?种PAHs（PAH4）（苯并[a]蒽、?、苯并[b]荧蒽和BaP）含量为2.81、16.81?μg/kg和8.85?μg/kg,美国优先控制的16?种PAHs（PAH16）含量为26.18、112.61?μg/kg和111.85?μg/kg;在大豆油水化脱胶、碱炼脱酸、蒸馏脱臭过程BaP的脱除率分别为7.57%、23.57%、91.65%,水化脱胶、碱炼脱酸、吸附脱色、蒸馏脱臭过程PAH4的脱除率分别为15.93%、10.41%、19.31%、50.91%,PAH16的脱除率分别为15.45%、11.59%、6.66%、52.99%;大豆油精炼副产物油脚、皂脚、废白土、脱臭馏出物中BaP含量分别为0.45、0.90、0.52、12.49?μg/kg,PAH4含量分别为10.14、7.39、9.69、300.50?μg/kg,PAH16含量分别为261.60、434.49、156.29、2?775.15?μg/kg。     

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     

Polycyclic aromatic hydrocarbons (PAHs) in traditional and industrial smoked beef and pork ham from Serbia

Smoked beef and pork ham samples were analysed during process of smoking (after packing and storing) for the presence of the 16 EU priority PAHs via Fast GC/HRMS method. This study showed that there are differences in PAH contents between final smoked beef ham samples from traditional smokehouse (TS) (3.9 μg kg⁻¹) and industrial smokehouse (IS), (1.9 μg kg⁻¹). Also there is a difference in PAH contents in final smoked pork ham samples (4.9 μg kg⁻¹, TS; 4.2 μg kg⁻¹, IS). In beef and pork ham samples from the same smokehouse different PAH contents were observed during smoking. The highest content of examined PAHs in all beef and pork ham samples during smoking showed benzo[c]fluorene (BcL) (beef ham: from 0.3 μg kg⁻¹ to 1.5 μg kg⁻¹; pork ham: from 0.2 μg kg⁻¹ to 2.1 μg kg⁻¹).The maximum level for benzo[a]pyrene (BaP) of 5 μg kg⁻¹ in smoked meat products was not exceeded in any samples. Correlation statistic analysis (P < 0.05) of obtained contents from samples both from TS and IS showed that BaP is a good marker both for 16 EU priority PAHs and 12 IARC probably and possibly carcinogenic PAHs (IS: R _BaP/Σ16PAHs = 0.95, R _BaP/Σ12PAHs = 0.96; TS: R _BaP/Σ16PAHs = 0.71, R _BaP/Σ12PAHs = 0.88).     

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.     

Benz(a)pyren in Fleischerzeugnissen

Zusammenfassung Im Rahmen der Lebensmittelüberwachung wurden 386 geräucherte und 18 gegrillte Fleischerzeugnisse auf ihre Gehalte an Benz(a)pyren untersucht. Die Bestimmungen erfolgten massenfragmentographisch mit einer Capillar-GC-MS-Kombination unter Verwendung innerer Standards.Von 183 schwarzgeräucherten Schinken enthielten 82% z. T. erheblich mehr als die zulässige Höchstmenge von 1 g BaP/kg. Die Mengen an BaP erhöhten sich dabei stark mit zunehmender äußerer Berußung.Bei 95 normal geräucherten Schinken wiesen nur 15% und bei 87 normal geräucherten Würsten nur 9% überhöhte BaP-Gehalte auf. Die Überschreitungen waren dabei von wesentlich geringerer Natur.Mit Kiefern- und Fichtenzapfen sowie mit Hartholz gegrillte Rostbratwürste enthielten durchschnittlich 28 g BaP/kg. Bei mit Holzkohle gegrillten Erzeugnissen lagen die BaP-Gehalte dagegen ausnahmslos unter 1 g/kg.

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Benzo(a)pyrene contents of meat products

Summary The Benzo(a)pyrene contents of 386 smoked and 18 grilled meat products were determined by application of capillary gas-chromatography-mass fragmentography using inner standards.82 per cent of 183 black smoked hams contained appreciably more than the legal maximum amount of 1 ppb. The quantities of BaP increased very much with increase of soot accumulation on the surface.Only 15 per cent of 95 hams and only 9 per cent of 87 sausages smoked by normal methods had excessive BaP content. The amounts in excess of 1 ppb were much lower in these hams.Bratwurst grilled by use of pine-cones, spruce-cones and hard wood contained on average 28 ppb BaP. The BaP amounts of Bratwurst grilled over charcoal were without exception lower than 1 ppb.

     

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.     

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.     

Effect of replacing pork backfat with pre-emulsified olive oil on lipid fraction and sensory quality of Chorizo de Pamplona - a traditional Spanish fermented sausage

Six treatments of Chorizo de Pamplona, traditional Spanish fermented sausage, were manufactured under usual commercial conditions by replacing 0, 10, 15, 20, 25 and 30% of pork backfat by pre-emulsified olive oil with soy protein isolate. Sausages with 20-30% replacing level had higher (P<0.05) protein content than control as a result of the addition of soy protein isolate. The oleic acid increased (P<0.05) in sausages with 15-30% replacing level, and linoleic acid increased in sausages with 10-25%. Sausages with 10-25% of substitution had lower total SFA-stearic and higher (P<0.05) total MUFA, total PUFA, (MUFA+PUFA)/(SFA-stearic), and PUFA/(SFA-stearic). Cholesterol content showed reduction about 12-13% in sausages with 20-25% replacing level, and up to 22% in sausages with 30% replacing level. Sausages with 10-25% of substitution were acceptable from the sensorial point of view. The texture and colour instrumental measures were comparable with that of commercial products. No increments in hexanal content were observed. It is concluded that up to 25% of pork backfat can be replaced with pre-emulsified olive oil in the production of Chorizo de Pamplona fermented sausages. Higher replacing levels of pork backfat did not show nutritional advantages in relation to the fatty acid profile and were unacceptable due to considerable dripping of fat during ripening.     

Class separation of mutagenic polycyclic organic material in grilled and smoked foods

A method for class separation of mutagenic polycyclic organic material in grilled and smoked foods is described. The procedure involves an initial extraction with acetone, removal of fat and proteins by precipitation at -55 degrees C, and an acid-base extraction. Further fractionation was carried out by gel filtration and silica gel chromatography. In four samples of grilled sausages, 80%-90% of the extracted mutagenicity (TA98 + S9) was contained in the basic fractions. Flame-grilled sausages showed higher mutagenicity than charcoal-grilled ones. In a smoked fish sample, the mutagenicity was low and evenly distributed between the basic and the neutral/acidic fractions. A few samples showed a weak direct-acting mutagenicity in the neutral/acidic fractions. The presence of nitrite in grilled sausages did not influence the mutagenicity markedly. Gas chromatography-selected ion monitoring was used to successfully identify a number of polycyclic aromatic hydrocarbons (PAHs) and tentatively identify several nitro-PAHs and oxygenated compounds. However, the identification of mutagens in the basic fractions was complicated by peak tailing and the presence of co-eluting material.     

Identification and occurrence of 1,2,3,4-tetrahydro-β-carboline-3-carboxylic acid: the main β-carboline alkaloid in smoked foods

Tetrahydro-β-carboline alkaloids are biologically active compounds that occur in foodstuffs. 1,2,3,4-Tetrahydro-β-carboline-3-carboxylic acid, a tetrahydro-β-carboline derived from a Pictet–Spengler condensation reaction among l-tryptophan and formaldehyde, was identified by GC–MS as its N-methoxycarbonyl methyl ester derivative in smoked fish, sausage and cheese. The occurrence of this β-carboline was determined by RP-HPLC-fluorescence in numerous commercially available samples of these products and the concentrations ranges were 0.03–12.2 μg/g, 0.07–6.06 μg/g and 0.01–14.8 μg/g in smoked fish, smoked cheeses and smoked sausages and meats, respectively. These results showed that 1,2,3,4-tetrahydro-β-carboline-3-carboxylic acid is the main β-carboline in such products. Smoked foods contained a higher relative amount (2–7 fold) of this compound in their exterior part exposed to the smoke than in their interior counterpart suggesting a reaction involving formaldehyde from smoke and tryptophan. Smoked products appear to be one of the food stuffs with the highest amount of this particular tetrahydro-β-carboline.     

Analytical Method Validation and Rapid Determination of Polycyclic Aromatic Hydrocarbons (PAHs) in Cocoa Butter Using HPLC-FLD

A simple, fast and ecological analytical method using a semi-automatic fat extractor and HPLC-FLD (fluorescence detection) for determination of polycyclic aromatic hydrocarbon markers i.e. benzo(a)anthracene (BaA), chrysene (Chr), benzo(a)pyrene (BaP) and benzo(b)fluoranthene (BbF) in cocoa butter has been validated. Validation’s procedure performed out in concordance with French standard NF V03-110 (2010) was based on existing polycyclic aromatic hydrocarbon (PAH) determination methods in various smoked foodstuffs and edible vegetable oils. Determination of correlation coefficients for specific PAHs ranged from 0.9992 to 0.9998. Respective values of limits of detection were 0.010, 0.011, 0.033 and 0.029 μg kg^?1 and those of quantification were 0.035, 0.038, 0.111 and 0.098 μg kg^?1 for BaA, Chr, BbF and BaP. Both values of repeatability and intermediary precision tests coefficients of variation were less than 5%. Recovery scores of four PAH markers matched EU standard 836/2011 recommendations. Sum of four PAH markers (BaA, Chr, BbF, BaP) contents varied from 5.42?±?0.58 to 11.37?±?0.01 μg kg^?1 whereas those of BaP was comprised between 0.26?±?0.00 and 1.75?±?0.13 μg kg^?1 in 20 cocoa butter samples extracted from raw cocoa bean stored at Ivorian cocoa farmer levels.     

Polycyclic aromatic hydrocarbons in milk powders marketed in Argentina and Brazil

The aim of this study was to quantify polycyclic aromatic hydrocarbon (PAH) levels in milk powder samples commercialised in Argentina and Brazil during 2012. Thirty-one samples were available from the retail market. An HPLC method for the determination of PAHs was applied involving a clean-up step with silica cartridges. Recoveries were greater than 79% for all PAHs analysed. Reproducible determination with adequate detection and quantification limits (LOD and LOQ) were attained by HPLC with fluorescence detection for 14 PAHs. Acenaphthylene was determined with a UV–VIS detector. There is no significant difference in any PAHs or in the sum of them between the Argentinean and Brazilian samples. Therefore, the samples were evaluated together. The highest concentration of benzo(a)pyrene (BaP) detected was 0.57 µg kg^?1 in milk powder. Contamination of samples expressed as the sum of 15 analysed PAHs varied between 11.8 and 78.4 µg kg^?1 and as PAH4 (BaP, chrysene, benzo(a)anthracene and benzo(b)fluoranthene) was between 0.02 and 10.16 µg kg^?1. The correlation coefficient for PAH2 (BaP and chrysene) and PAH4 groups was 0.95, for PAH2 and PAH8 it was 0.71, and for PAH4 and PAH8 it was 0.83. All the samples were below the regulatory limit for BaP, but 65% of commercial milk powders do not comply with the European Union limit for PAH4. This is the first report of PAH contamination in powder milk from Argentina and Brazil.     

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     

Analysis of benzo[a]pyrene content from smoked food products in Korea

The content of benzo[a]pyrene (BaP) was evaluated from 100 smoked food products commonly consumed in Korean market with HPLC. Analysis method for BaP content on smoked food products was evaluated and validated. For validation, the efficiency of saponification time and solid phase extraction cartridges were evaluated. During 1–4 h of saponification, recovery of BaP was ranged from 90.17 to 98.87%. Among the 5 tested cartridges including florisil, silica gel, and alumina cartridges (acidic, basic, and neutral), the most efficient cartridge was florisil cartridge and the recovery of BaP was 98.87%. Limit of detection and limit of quantification was 0.03 and 0.09, respectively. As a result of BaP content analysis from smoked food products, the average BaP content was 0.45 μg/kg and the highest content of BaP was 2.87 μg/kg detected in smoked salmon product.     

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.