GC-MS法测定多种食用油中的多环芳烃

多环芳烃是一类常见的环境有机污染物,随着人们对其毒性研究逐步深入,各国相继制定限量要求。随机选取市面上不同种类的食用油,采用GC-MS法进行多环芳烃的测定,评估其食品安全风险。结果表明, 15种食用油中苯并[a]芘含量在0.00～9.20μg/kg之间,苯并[a]芘、苯并[a]蒽、苯并[b]荧蒽和苯并菲的含量之和在0.00～28.74μg/kg之间, 16种多环芳烃总量在0.00～72.47μg/kg之间。对随机网上购买食品安全风险较高的10份芝麻油进行测定,苯并[a]芘含量在0.00～6.76μg/kg之间,苯并[a]芘、苯并[a]蒽、苯并[b]荧蒽和苯并菲的总量在0.00～9.64μg/kg之间,16种多环芳烃总量在0.00～16.18μg/kg之间。植物油中多环芳烃含量水平相差较大,部分存在一定的食品安全风险,出口企业还应关注苯并[a]芘、苯并[a]蒽、苯并[b]荧蒽和苯并菲含量的水平。     

高效液相色谱-荧光检测法检测植物性食品中14种欧盟优控多环芳烃

目的 建立准确测定蔬菜、水果及粮食中多环芳烃含量,了解河北省内上述食品中14种欧盟优控多环芳烃(苯并(c)芴、苯并(a)蒽、?、5-甲基?、苯并(j)荧蒽、苯并(b)荧蒽、苯并(k)荧蒽、苯并(a)芘、二苯并(a,l)芘、二苯并(a, h)蒽、苯并(g,h,i)苝、茚并(1,2,3-cd)(a)芘、二苯并(a,e)芘、二苯并(a,i)芘、二苯并(a,h)芘)的实际污染状况。方法 样品经环己烷：乙酸乙酯(1:1, V:V)溶液超声提取后,浓缩至近干,经正己烷复溶后通过多环芳烃专用固相萃取柱进行净化处理,洗脱液经浓缩后用乙腈定容,采用液相色谱-荧光检测法进行检测。结果 14种化合物的线性范围为1.00~18.0μg/kg;方法回收率为60.9%~125.4%,相对标准偏差为2.2%~7.6%;苯并(c)芴、苯并(a)蒽、?、5-甲基-1,2-苯并菲、苯并(j)荧蒽、苯并(b)荧蒽、苯并(k)荧蒽、苯并(a)芘、二苯并(a,e)芘、二苯并(a,i)芘、二苯并(a,h)芘检出限为0.15μg/kg;二苯并(a,l)芘、二苯并(a, h)蒽、苯并(g,h,i)苝、茚并(1,2,3-cd)芘检出限为0.3μg/kg。市售的96份样品中, 检出不同种类不同含量的多环芳烃类化合物, 检出率为51.0%。结论 本方法重现性好,检测灵敏度高,可用于水果、蔬菜及粮食中14种多环芳烃的检测。     

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%。     

高效液相色谱法测定烤肉中4种多环芳烃前处理的优化

采用超声辅助法提取、串联固相萃取柱净化、高效液相色谱法(HPLC)分析烤肉中4种多环芳烃(PAH4,即?、苯并[a]蒽、苯并[b]荧蒽、苯并[a]芘)。通过对比固相萃取柱净化效果及回收率、提取剂的提取效果,最终选择ENV柱与SI柱进行串联,正己烷:二氯甲烷(1:1)提取烤肉中PAH4效果更佳,测定结果表明,HPLC法的检出限为0.23～0.32μg/kg,线性范围为5～100μg/L,在3个浓度(2、5μg/L和10μg/L)加标的水平上回收率为77.56%～93.49%,相对标准偏差(RSD,n=6)为0.89%～3.73%。该方法具有前处理简单、快速、线性范围较宽、检测灵敏度高等优点,符合当今食品分析的发展趋势,可广泛应用于烤肉中PAH4的常规监测。     

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。     

气相色谱串联质谱法检测食用植物油中的4种欧盟限量多环芳烃

建立了分子印迹固相萃取(MISPE)气相色谱串联质谱法(GC-MS/MS)检测食用植物油中苯并[a]蒽(BAA)、屈(CHR)、苯并[b]荧蒽(BBF)和苯并[a]芘(BAP)等4种欧盟限量多环芳烃(PAH4)的新方法。以CHR-d12和BAP-d12为内标,样品用正己烷溶解,流过硅胶-分子印迹串联固相萃取小柱,弃去硅胶柱;分子印迹小柱再经正己烷淋洗,二氯甲烷洗脱;洗脱液经氮吹浓缩,GC-MS/MS多反应监测模式进行检测。结果表明,在1~50μg/L浓度范围内4种PAH均有良好的线性(R~20.999),方法检出限为0.21~0.49μg/kg,定量限为0.70~1.63μg/kg;5、10和20μg/kg加标水平的回收率为81.06~111.30%,相对标准偏差为0.86~5.65%。利用本方法对市售26个食用植物油样品进行检测,结果显示,BAA、CHR、BBF和BAP的检出率均为100%;BAP含量为2.04~6.16μg/kg;PAH4含量为9.36~31.38μg/kg。依我国相关限量标准,BAP含量处于较安全水平,但PAH4总量较欧盟限量要求还存在较大差距。     

食用植物油中多环芳烃含量水平调查分析

调查了8类、116个食用植物油样品中的苯并(a)蒽、■、苯并(b)荧蒽和苯并(a)芘的污染情况。采用简单的液-液萃取法进行前处理,GC-MS/MS测定。结果表明:不同品种食用植物油多环芳烃含量差异较大;苯并(a)芘的检出率为85.34%,检出结果范围为0.59~9.75μg/kg;4种多环芳烃总量的检出率为100%,检出结果范围为0.88~59.17μg/kg;苯并(a)芘含量与4种多环芳烃总量成线性关系。     

气相色谱-质谱法评定紫苏油中多环芳烃类不确定度

目的：为降低紫苏油多环芳烃PAH4检测过程的不确定度,提高实验室检验检测结果的准确性。方法：采用气相色谱-质谱法对紫苏油中多环芳烃PAH4测定含量进行不确定度评定,通过建立数学模型,分析测定过程的主要不确定度来源,评估各个分量。结果：该法中苯并[a]蒽含量测定结果（1.14±0.31）μg/kg,k=2;?含量测定结果为（0.47±0.22）μg/kg,k=2;苯并[b]荧蒽含量测定结果为（4.62±0.79）μg/kg,k=2;苯并[a]芘含量测定结果为（3.90±1.19）μg/kg,k=2。结论：该检测方法影响检测结果不确定度的主要因素为标准物质、校准曲线、气相色谱-质谱联用仪及样品处理,其他因素影响相对较小,在检测过程应加以控制。     

HPLC和GC-MS/MS测定食用油中4种多环芳烃的方法比较

分别采用高效液相色谱法(HPLC)和气相色谱-串联质谱法(GC-MS/MS)分析食用油中PAH4即?、苯并[a]蒽、苯并[b]荧蒽、苯并[a]芘的含量。结果表明,HPLC法对食用油中PAH4的线性范围为(0.1~50)μg/L,检出限为(0.1~0.2)μg/kg,检测灵敏度高于GC-MS/MS法。HPLC法对食用油中的PAH_4的加标回收率为83.0%~95.8%,精密度为0.50%~4.48%,准确度和精密度均略高于GC-MS/MS法。相比较而言,HPLC法灵敏、准确、可靠、简便,适合大批量食用油样品中PAH_4的检测。GC-MS/MS法能够去除复杂基质的干扰,防止假阳性的发生。2种方法各有优点,可以为食用油中PAH_4的质量监控与检测提供技术参考。     

气体射流冲击烤制"北京烤鸭"不同加工技术与鸭皮中多环芳烃含量变化的研究

采用气体射流冲击加热新技术烤制"北京烤鸭",在保证烤鸭品质的前提下,改变烤制温度,运用高效液相荧光检测技术研究不同烤制温度的烤鸭鸭皮中高致癌性多环芳烃(PAHs)含量的变化.结果显示,在170、190、2100C三种不同烤制温度下,苯并[a]芘含量在0.13～0.451xg/kg,二苯并[a,h]蒽含量在0.48～2.01μg/kg,7,12一二甲基苯并[a]蒽含量为1.28～3.19μg/kg,苯并[a]芘含量远远低于国家标准5μg/kg.高烤制温度下(210%)各PAHs的产生量要显著高于低温(170、190℃)烤制产生的量,在此技术下低温烤制产品安全性更高于高温烤制产品.     

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.     

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.     

Polycyclic aromatic hydrocarbons in food samples collected in Barcelona, Spain

This study reports on the concentrations of eight polycyclic aromatic hydrocarbons (PAHs) in food samples collected in the city of Barcelona (Catalonia, Spain) from 2003 to 2004. Food samples included meat products, fish (fresh and smoked), other seafood (cephalopods, crustaceans, and bivalves), vegetable oil, and tea. Concentrations of benz[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[g,h,i]perylene, benzo[alpha]pyrene, benzo[e]pyrene, dibenz[a,h]anthracene, and indeno[1,2,3-c,d]pyrene were determined by reversed-phase high-performance liquid chromatography with fluorescence detection. PAHs were detected in most tea samples (94%), which had the highest concentration of total PAHs (mean concentration of 59 microg/kg). Other food groups with a high presence of PAHs were bivalves (present in 34% of the samples; mean value of 2.7 microg/kg) and meat products (present in 13% of the samples; mean value of 1.7 microg/kg). The PAHs detected most frequently were benzo[e]pyrene and benzo[b]fluoranthene. No sample had levels above current regulation standards. Nevertheless, the frequent presence of PAHs in bivalves, tea samples, and meat products, together with the fact that dietary sources are the main exposure to these carcinogenic compounds, suggests the need for some monitoring scheme to follow up on these trends.     

Polycyclic aromatic hydrocarbons (PAH) in chocolate on the German market

Benzo[a]anthracene (BaA), chrysene (CHR), cyclopenta[c,d]pyrene (CPP), 5-methylchrysene (5MC), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[j]fluGoranthene (BjF), benzo[a]pyrene (BaP), dibenzo[a,h]anthracene (DhA), indeno[1,2,3-cd]pyrene (IcP), benzo[g,h,i]perylene (BgP), dibenzo[a,l]pyrene (DlP), dibenzo[a,e]pyrene (DeP), dibenzo[a,i]pyrene (DiP) and dibenzo[a,h]pyrene (DhP), the 15 SCFPAH, assessed to be relevant as well as benzo[c]fluorene (BcL) recommended by the European Food Safety Authority (EFSA), were analysed in different types of chocolate. The sample preparation included accelerated solvent extraction (ASE), size exclusion chromatography (SEC) and solid phase chromatography using small silica gel columns. The individual PAH were separated by gas chromatography using a VF-17ms GC column and detected by high resolution mass spectrometry (HRMS). The investigation of 40 samples of various types of chocolate with different cocoa contents resulted in a median benzo[a]pyrene (BaP) content of 0.22 μg/kg. Furthermore, the results showed a linear correlation between the content of BaP and the sum content of the 16 priority PAH. Therefore, the analysis of BaP as a leading substance seems to be suitable to estimate the PAH contamination in chocolate.     

Polycyclic aromatic hydrocarbons in foods: human exposure through the diet in Catalonia, Spain

The dietary intake of 16 polycyclic aromatic hydrocarbons (PAHs) (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3-c,d]pyrene) by the general population of Catalonia, Spain, was calculated. Concentrations of PAHs in food samples randomly acquired in seven cities of Catalonia from June to August 2000 were measured. Eleven food groups were included in the study. High-performance liquid chromatography was used to analyze PAHs. The dietary intakes of total and carcinogenic PAHs was calculated for five population groups: children, adolescents, male adults, female adults, and seniors. Among the analyzed PAHs, there was a predominance of phenanthrene (16.7 microg/kg) and pyrene (10.7 microg/kg). By food group, the highest levels of total PAHs were detected in cereals (14.5 microg/kg) and in meat and meat products (13.4 microg/kg). The mean estimated dietary intake of the sum of the 16 PAHs was as follows: male adults, 8.4 microg/day; adolescents, 8.2 microg/day; children, 7.4 microg/day; seniors, 6.3 microg/day; female adults, 6.3 microg/day. The calculated daily intake of PAHs would be associated with a 5/106 increase in the risk for the development of cancer in a male adult with a body weight of 70 kg.     

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.     

Comparing d-SPE Sorbents of the QuEChERS Extraction Method and EMR-Lipid for the Determination of Polycyclic Aromatic Hydrocarbons (PAH4) in Food of Animal and Plant Origin

A Quick, Easy, Cheap, Rugged, Effective, and Safe (QuEChERS) method for the determination of benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[a]pyrene (PAH4 including the interfering PAHs triphenylene, cyclopenta[c,d]pyrene, benzo[k]fluoranthene, benzo[j]fluoranthene) was developed and validated with GC-MS/MS in foods of plant and animal origin. PAHs were extracted with acetonitrile, and different clean-ups with various compositions of sorbents, including zirconia-based sorbent (Z-Sep), primary-secondary amine (PSA), anhydrous magnesium sulfate (MgSO₄), octadecylsilane (C18 endcapped), and enhanced matrix removal (EMR)-lipid material, were tested. Another important focus of this study was the separation of critical pairs, which is essential for the qualification and quantification of PAH4. To investigate the developed methods, samples were spiked beneath their maximum levels (MLs) and recoveries and peak shapes were compared. The clean-up with 900 mg MgSO₄ + 150 mg PSA + 150 mg C18 was chosen to be validated in salmon, mussels, shrimps, bacon, cutlets, wheat flour, curry spice powder, infant formula, infant follow-up formula, and infant foods. Recoveries for all analytes were between 75 and 108%, combined with standard deviation between 2 and 20%. Limits of detection (LODs) and limits of quantification (LOQs) were between 0.04 and 0.34 μg/kg and between 0.1 and 1 μg/kg, respectively.     

Trophic dilution of polycyclic aromatic hydrocarbons (PAHs) in a marine food web from Bohai Bay, north China

Trophic transfer of polycyclic aromatic hydrocarbons (PAHs) in aquatic ecosystems is an important criterion for assessing their ecological risk. This study analyzed 18 PAHs in phytoplankton/seston, zooplankton, five invertebrate species, five fish species, and one seabird species collected from Bohai Bay, and trophic transfer of the PAHs was determined in the food web, of which the length was approximately 4 on the basis of stable nitrogen isotope values. The concentrations of PAHs (2-64.5 ng/g wet weight) in the marine ecosystem were moderate compared with other marine organisms worldwide, and the PAH compositions exhibited species-specific profiles that were related to trophic levels in some organisms. Significant negative relationships were also found between trophic levels and lipid-normalized concentrations for 10 PAH compounds (acenaphthylene, anthracene, fluoranthene, pyrene, chrysene, benz[a]anthracene, benzo[b]fluoranthene + benzo[k]fluoranthene, benzo[e]pyrene, benzo[a]pyrene, and perylene), and their trophic magnification factors (TMFs) ranged from 0.11 for fluoranthene to 0.45 for acenaphthylene. These results confirm that PAHs undergo trophic dilution in the marine food web, which is likely to be the combined results of low assimilation efficiencies and efficient metabolic transformation at higher trophic levels.     

Sources, vertical fluxes, and equivalent toxicity of aromatic hydrocarbons in coastal sediments of the Río de la Plata Estuary, Argentina

Settling particles and bottom sediments collected at 1, 2.5, and 4 km off the metropolitan Buenos Aires coast in the Río de la Plata were analyzed to evaluate the sources and toxicity of resolved (PAHs) and unresolved (AROUCM) aromatic hydrocarbons. PAHs (0003-2.1 microg g(-1)) and AROUCM (0.01-78 microg g(-1)) presented the highest concentrations nearthe Buenos Aires port and sewer and decreasing values up- and downstream and along on- and offshore gradients. Sediment traps deployed in the Central area revealed large aromatic fluxes (1.3 +/- 1.5 and 31 +/- 47 mg m(-2) day(-1) for PAHs and AROUCM). The composition of sedimentary PAHs was dominated by uniformly distributed high molecular weight pyrogenic PAHs (53 +/- 11% fluoranthene, pyrene, and heavier PAHs), followed by diagenetically derived perylene more abundant in less polluted sites (29 +/- 15%) and lower molecular weight petrogenic PAHs (18 +/- 7.1% phenanthrene, anthracene, and methylated compounds), which covaried inversely with perylene. PAH diagnostic ratios indicated a stronger influence of petrogenic discharges close to the shore and the prevalence of combustion of fossil fuels and vehicle emissions over wood in offshore sediments. Sediment cores showed sustained hydrocarbon levels with decreasing proportion of petrogenic PAHs and relative enrichment of pyrogenic components and perylene down to 20-cm depth. PAH toxicity assessment by sediment quality guidelines (SQG) and dioxin-equivalent factors (PAH TEQ: 0.08-395 pg g(-1) dw) identified 1-2.5 km sediments close to the port and sewer as the most affected area. According to SQG, dibenz[a,h]anthracene and pyrene were the most critical PAHs, followed by benzo[a]pyrene, benz[a]anthracene, and chrysene. In contrast, PAH TEQs were dominated by indeno[1,2,3-cd]pyrene, benzo[k]fluoranthene, benzo[a]pyrene, perylene, and benz[a]anthracene which accounted for an average 86 +/- 5.7% of total TEQs.