烟熏肉制品中的多环芳香烃

综述了烟熏肉制品中的多环芳烃的产生过程,并对烟熏肉制品中多环芳烃存在的问题和发展趋势进行了展望。     

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 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.     

Polycyclic aromatic hydrocarbons (PAHs) in meat products and estimated PAH intake by children and the general population in Estonia

The concentrations of benzo[a]pyrene and 11 other polycyclic aromatic hydrocarbons (PAHs) were analysed from 322 commercial, cured meat products and 14 home-grilled meat samples as part of the Estonian food safety monitoring programme during 2001-2005. The maximum acceptable concentration of 5 µg kg^-1 for benzo[a]pyrene was exceeded in 3.4% of samples. The highest PAH concentrations were detected in home-grilled pork samples. Using of disposable grilling unit resulted in 1.6 times higher PAH concentrations compared to the traditional wood-burning grill. The average intake of benzo[a]pyrene and sum of 12 PAHs from meat products was estimated for children (age 1-16 years) on the basis of an individual food consumption questionnaire and, for the general population, based on national food consumption data. The highest total PAH concentrations detected were 16 µg kg^-1 in smoked meat and ham, 19 µg kg^-1 in smoked sausage and 6.5 µg kg^-1 in smoked chicken samples. Since smoking and grilling are prevalent meat-cooking methods in Estonia, the impact of meat products is assessed to be significant in overall PAH intake.     

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。     

含螺旋藻产品中多环芳烃污染状况研究

目的 建立气相色谱-串联质谱法(gas chromatography-mass spectrometry, GC-MS/MS)测定含螺旋藻产品中多环芳烃残留量的方法, 并以此法探究市售含螺旋藻产品中以苯并(a)蒽、?、苯并(b)荧蒽和苯并(a)芘为代表的多环芳烃污染状况。方法 样品采用正己烷提取, 经QuEChERS净化, 选择DB-5 MS毛细管色谱柱, 在多反应监测(multiple reaction monitoring, MRM)模式下采用基质匹配外标法定量。采用4种多环芳烃化合物(polycyclic aromatic hydrocarbons, PAH)总量(PAH4)和苯并(a)芘进行双指标分析, 并结合摄入量对市售含螺旋藻产品中多环芳烃污染情况进行分析。结果 4种化合物在1~32 μg/L的范围内具有良好的线性关系, 相关系数r2>0.995, 方法定量限4 μg/kg, 平均回收率为64.1%~102%, 相对标准偏差(relative standard deviations, RSD)为2.2%~6.4% (n=6)。75个受试样本的多环芳烃检出率为76%, 检出的4种多环芳烃含量范围为4.1~916.0 μg/kg。在苯并(a)芘含量大于50 μg/kg时, 苯并(a)芘含量与PAH4含量之间呈现明显的正相关, 但在低于50 μg/kg时, 两者未显示出相关性。结论 建立的方法准确度高, 灵敏度好, 适用于含螺旋藻产品中多环芳烃的检测。实际样品的测定结果显示, 市售含螺旋藻产品中存在高水平多环芳烃污染的情况, 可能对服用者产生安全风险。样本中苯并(a)芘与PAH4总量之间存在一定相关性, 在高污染水平两者相关性趋明显, 在低污染水平苯并(a)芘不宜作为螺旋藻中多环芳烃污染的唯一指标。建议食品安全相关部门应加强风险防控, 制定合理的控制规范、设立恰当的指标限量。     

烧烤肉制品加工中多环芳烃和杂环胺形成途径及其防控方法研究进展

烧烤肉制品因具有独特的色泽、香气和口感受到消费者的喜爱,但传统烤制通常是在高温条件下进行,肉制品在高温下会发生脂肪裂解、美拉德反应等生成多环芳烃、杂环胺等有害物质。该文综述了烧烤肉制品中多环芳烃、杂环胺等有害物质形成途径、影响因素、抑制方法的研究进展,主要阐述了烧烤肉制品通过HAVA机理和Diels-Alder机理形成多环芳烃,通过自由基途径及美拉德反应形成杂环胺,并为此提出合理控制烤制温度和烤制时间,合理选择烤制技术,添加外源物质抑制有害物质的生成等防控方法,为优化烧烤肉制品加工工艺,促进肉制品行业的绿色安全发展提供理论基础。     

烘烤对肉制品中多环芳烃和杂环胺含量的影响

烘烤是肉制品加工中重要的工艺之一,但经烘烤的肉制品中含有多环芳烃、杂环胺等有害物质,对消费者的健康造成很大的威胁.介绍了多环芳烃、杂环胺及其对人体的危害,重点阐述了烘烤对肉制品中多环芳烃和杂环胺含量的影响及其控制方法.     

Optimisation of microwave assisted extraction (MAE) for polycyclic aromatic hydrocarbon (PAH) determination in smoked meat

A rapid extraction method involving microwave assisted extraction (MAE), followed by sample clean-up on a silica cartridge, reversed-phase high performance liquid chromatography (RP-HPLC) and spectrofluorimetric detection, was optimised for polycyclic aromatic hydrocarbon (PAH) determination in smoked meat. Compared to solvent extraction assisted by sonication, MAE, carried out with n-hexane on 2g of lyophilised sample at 115°C for 15min, allowed to obtain better extraction efficiencies. Limits of quantification (LOQ, s/n=10) lower than 0.2μg/kg wet weight were found for all PAHs, except for Fl (0.3μg/kg), P (0.6μg/kg) and IP (0.4μg/kg). The optimised procedure, that presented good analytical performances (with recoveries ranging from 77% to 103%, and precision within 10% for most of the PAHs), was applied to determine PAH content in different smoked meat products from the Italian market.     

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.     

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。     

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。     

Reducing polycyclic aromatic hydrocarbons (PAHs) in olive pomace oil using short-path molecular distillation

ABSTRACT

Bleached olive pomace oil (BOPO) was distilled using a short-path molecular distillation unit to determine the impacts of distillation conditions on the removal of 15 PAHs from the list of 16 EPA-priority pollutant PAHs. The removal of PAHs was achieved at elevated temperatures (110–230°C) and pressures (0.05, 0.5, 5 mbar). The oil was also deodorised at 230°C under 0.5, 1 and 5 mbar pressures to determine the effect of pressure during deodorisation on the removal of PAHs. High-performance liquid chromatography (HPLC) with fluorescence detector (HPLC-FLD) was used for quantifying PAH concentrations in oil samples. PAH concentrations in BOPO were considerably reduced after molecular distillation and both temperature increment and pressure decrease were effective for the removal of PAHs from olive pomace oil. When above 190°C, BaP could be reduced to <2 µg/kg at all pressures. Distillation at 230°C under 0.05 mbar absolute pressure reduced the sum of four PAHs (BaP, Chr, BaA, BbF) to 7 µg/kg, which meets the acceptable levels established by the European Union (10 µg/kg). Deodorisation effectiveness was increased by decreasing absolute pressure, particularly for light PAHs.     

Effects of meat preheating and wrapping on the levels of polycyclic aromatic hydrocarbons in charcoal-grilled meat

The contamination of polycyclic aromatic hydrocarbons PAHs by thermally treated high-protein foods, such as charcoal-grilled meat products, is due to the generation by direct pyrolysis of food nutrients and the direct deposition of PAHs from smoke produced through incomplete combustion of the thermal agents. This study investigated the effects on the PAH (BaP, BbFln and Fln) contents by using two different types of treatments, preheating (steam and microwave) and wrapping (aluminium and banana leaf) of the meat samples prior to charcoal grilling. PAHs were extracted through tandem solid-phase extraction. The results showed that the applied preheating and wrapping treatments on the samples strongly affect the PAHs levels in the charcoal-grilled meat. No carcinogenic PAHs (BaP and BbFln) were detected in the samples after steam and microwave preheating or aluminium wrapping treatments. Significant reductions of Fln content, of up to 46% and 81% in beef and chicken samples, respectively, were observed in the study.     

Determination of polycyclic aromatic hydrocarbons in smoked fishery products from different smoking kilns

The levels of 13 polycyclic aromatic hydrocarbons (PAH) were determined by an HPLC method with fluorescence and UV detection and by a GC/MS technique in smoked fishery products from modern smoking kilns with external smoke generation and from traditional smoking kilns. The average benzo(a)pyrene (BaP) concentration of all 35 samples from commercial smoking kilns with external smoke generation was 0.1 g/kg (wet weight) and the sum of the carcinogenic compounds determined in the study, i.e. benz(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenz(a,h)anthracene and indeno(1,2,3-c,d)pyrene did not exceed 4.5 g/kg (wet weight). The BaP levels of the 27 smoked fish samples from traditional kilns ranged from 0.2 g/kg to 4.1 g/kg, with a mean value of 1.2 g BaP/kg. The average concentration of the sum of the carcinogenic compounds was 9.0 g/kg. Large variations were found in the content of the non-carcinogenic PAHs phenanthrene, anthracene, fluoranthene and pyrene in all samples from both types of smoking kilns.     

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.     

Benzo[a]pyrene and total polycyclic aromatic hydrocarbons (PAHs) levels in vegetable oils and fats do not reflect the occurrence of the eight genotoxic PAHs

Concentrations of polycyclic aromatic hydrocarbons (PAHs) were determined in 115 samples of olive oil (extra virgin olive oil, virgin olive oil, olive oil, pomace olive oil and blended olive oil), cooking oil (corn oil, sunflower oil, sesame oil, palm olein oil, soya oil, canola oil, mustard oil, peanut oil and mixed vegetable oil) and fat (butter and table margarine) collected from retail stores in Kuwait. Carcinogenic benzo[a]pyrene (BaP) was detected in 43% of the samples analyzed. Benz[a]anthracene and chrysene were detected in 37 and 45% of the samples, respectively, that did not contain BaP. Of the individual non-carcinogenic PAHs, naphthalene showed the highest mean concentration (14 µg kg^?1), while for the carcinogenic PAHs, BaP (0.92 µg kg^?1) and chrysene (0.87 µg kg^?1) showed the highest mean values. Approximately 20% of the samples within the olive oil and cooking oil sub-categories exceeded the EU maximum tolerable limit for BaP, with the highest level of 6.77 and 11.1 µg kg^?1, respectively. For the fat sub-category, 9% of the samples exceeded the tolerance limit, with the highest level of 3.67 µg kg^?1. The Kuwaiti general population's dietary exposure to the genotoxic PAHs (PAH8: benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenz[a,h]anthracene and benzo[ghi]perylene) was estimated to be 196 ng day^?1 (3.3 ng kg^?1 bw day^?1, assuming an average adult body weight of 60 kg). Results indicated that PAH8 and BaP_eq (total sum benzo[a]pyrene equivalents) are more reliable measures of the concentrations of other carcinogenic PAHs in oil and fat samples, while BaP and PAHs alone are not good indicators of the occurrence or degree of contamination by carcinogenic PAHs in these food products.     

Factors affecting elimination of polycyclic aromatic hydrocarbons from smoked meat foods and liquid smoke flavorings

This review deals with effects of environmental and physicochemical factors affecting polyaromatic hydrocarbon (PAH) elimination from smoked meat products and liquid smoke flavoring (LSF). In the introductory part, some essential information are aimed at principles of food smoking and PAH formation during smoke generation as a result of incomplete wood combustion. Also, an application of alternative technology for food aromatization using LSF is briefly mentioned. Similarly, latest European legislation, biological effects, and analytical aspects of PAHs are mentioned concisely. The main part is devoted to physicochemical factors affecting the PAH content in smoked meat products, such as light, additional cooking, and packaging, which are able to decrease considerably PAH content in some meat products. The most important effect on PAH concentration decrease in LSF has low-density polyethylene (LDPE) package due to sorption processes on a surface of the plastic with subsequent diffusion into the plastic bulk. A less effective material is polyethylene terephthalate (PET), when only a surface adsorption process comes into account. Moreover, this process is affected also by other compounds presented in liquid media able to compete for the adsorption center on the PET surface.     

A GC/MS method for the determination of carcinogenic polycyclic aromatic hydrocarbons (PAH) in smoked meat products and liquid smokes

A GC/MS method for the determination of ten polycyclic aromatic hydrocarbons (PAH) with four to six condensed aromatic carbon rings (including the six carcinogenic PAH) in smoked meat products and liquid smokes has been developed. The method implies accelerated solvent extraction (ASE), gel permeation chromatography for efficient lipid removal without saponification and ¹³C-labelled PAH for quantification. The calibration curves showed a good linearity for all PAH in the concentration range 0.01–10,000 ppb, the repeatabilities (RSDs, n=6) of different PAH ranged from 3 to 12%. Using this method, the analysis of a standard reference material of the National Institute of Standards and Technology (mussel tissue, SRM 2977) resulted in a good accordance between measured and certified PAH concentrations. The determination of PAH contents in 26 samples of smoked meat products and liquid smokes further confirmed the analytical power of the new method and gave a first insight into the specific PAH patterns.     

Effect of fuel and kiln type on the polycyclic aromatic hydrocarbon (PAH) levels in smoked shrimp,a Beninese food condiment

Smoked shrimp is a food condiment widely used in Beninese local cooking practices. A previous study revealed that this product is highly contaminated with polycyclic aromatic hydrocarbons (PAH). The present study explored possibilities to reduce PAH levels in shrimp smoked using cottage industry smoking techniques with barrel and chorkor kilns, by replacing wood by charcoal from Acacia auriculiformis and Mangifera indica, as fuels. Results showed that only shrimp smoked using acacia charcoal in a chorkor kiln had PAH levels (benzo[a]pyrene = 5 µg kg^?1 and sum of benzo[a]pyrene, chrysene, benzo[a]anthracene and benzo[b]fluoranthene = 28 µg kg^?1) in accordance with a European standard of 5 and 30 µg kg^?1, respectively, and suitable physicochemical characteristics for good storage (moisture content = 11.9% ± 1.5%; water activity = 0.46 ± 0.03). However, further investigations still needs to be done to reduce the duration of product contact with combustion gasses in order to reduce the PAH content of smoked shrimp to safer levels, largely below standards.