吸附精制对芝麻香油多环芳烃脱除和风味保留的影响

本文研究了吸附精制对芝麻香油中多环芳烃的脱除效果及对芝麻香油感官风味和三种脂类伴随物的影响。结果表明:3种吸附剂对多环芳烃的脱除效果依次为:Norit活性炭→WY2活性炭→活性白土。吸附精制处理后芝麻油样中苯并[a]芘残留量皆不超过我国国标限量(苯并[a]芘小于10μg/kg)。采用油重0.2%的Norit活性炭或0.5%的WY2活性炭可以将芝麻香油中苯并[a]芘和PAH4含量脱除至符合或接近符合出口欧盟的限量要求(苯并[a]芘小于2μg/kg,PAH4小于10μg/kg),吸附精制芝麻香油中苯并[a]芘残留量分别为0.83和1.50μg/kg,PAH4残留量分别为4.85和10.94μg/kg,同时芝麻香油风味的损失很小,维生素E、芝麻素和芝麻林素的保留率较高。综合考虑对芝麻香油中多环芳烃脱除、风味及营养成分保留的综合效果,采用0.5%WY2活性炭进行吸附精制最为合理。     

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。     

冷冻除脂-气相色谱-串联质谱法检测食用植物油中30 种多环芳烃

建立冷冻除脂--气相色谱-串联质谱检测食用植物油中30?种多环芳烃（polycyclic aromatic hydrocarbons,PAH）的方法。选用6?种氘标记PAH为内标,样品经乙腈--丙酮溶液（4∶1,V/V）于离心管中涡旋提取,10?000?r/min离心5?min,－80?℃对油脂冷冻固化,倾出提取液,再经减压浓缩和氮气吹干,以二氯甲烷复溶,气相色谱--串联质谱多反应监测方式进行检测。结果表明,在相应质量浓度范围内30?种PAH均有良好线性（R2＞0.998）,检出限为0.10～1.83?μg/kg,定量限为0.35～6.11?μg/kg,在5、20?μg/kg和50?μg/kg添加水平下的回收率为67.77%～119.28%,相对标准偏差为1.18%～12.47%。采用本方法对市售11?类38?个食用植物油样品的检测显示,萘、1-甲基萘、2--甲基萘、联苯、2,6--二甲基萘、苊烯、苊、2,3,6--三甲基萘、芴、二苯并噻吩、菲、蒽、1-甲基菲、荧蒽、芘、环戊烯[c,d]芘、苯并[a]蒽、屈、苯并[b]荧蒽、苯并[k]荧蒽、苯并[e]芘和苯并[a]芘的检出率均为100%;5--甲基屈、苝、茚并[1,2,3--c,d]芘、二苯并[a,h]蒽、苯并[g,h,i]苝和二苯并[a,l]芘的检出率分别为86.84%、63.16%、81.58%、21.05%、81.58%和26.32%;二苯并[a,e]芘和二苯并[a,h]芘未检出;PAH总量为92.56～905.16?μg/kg,其中苯并[a]芘含量为1.94～7.40?μg/kg,依据食品安全标准限量,PAH处于较安全水平。     

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%。     

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。     

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。     

天然维生素E油中PAH4连续脱除工艺研究北大核心CSCD

建立了一种天然维生素E油连续通过颗粒活性炭的固定床吸附工艺,从而实现有效脱除其中含有的微量多环芳烃(PAHs)。通过单因素实验分别考察了料液比、体系温度、物料在填料中的吸附时间对PAH4(苯并(a)芘、苯并(a)蒽、苯并(b)荧蒽、䓛)脱除效果的影响,并通过正交实验进行了工艺条件优化。同时,考察了PAH4脱除过程对天然维生素E含量的影响。结果表明:以95%乙醇为溶剂,料液比(天然维生素E油与溶剂比)1∶3,体系温度40℃,在以颗粒活性炭为填料的固定床内吸附4 h的条件下,可使天然维生素E油中PAH4的残留量降至7.3μg/kg(其中苯并(a)芘含量为1.8μg/kg),符合欧盟标准要求的苯并(a)芘含量小于或等于2μg/kg,PAH4含量小于或等于10μg/kg的限量标准,且采用该PAH4脱除工艺后维生素E的含量没有受到明显影响。     

液相色谱-串联质谱法检测食用油脂中多环芳烃

建立了有机溶剂萃取、硅胶固相萃取柱净化、液相色谱-串联质谱法(LC-MS/MS法)测定食用油脂中EPA 16种多环芳烃的检测方法。EPA 16种多环芳烃的定量限分别为0.02~0.43μg/kg,回收率为86.5%~104.6%,日内精密度小于6%,日间精密度小于5%。在40个受测油脂样品中,EPA 16种多环芳烃的含量范围为11.68~146.06μg/kg。对照我国GB 2716规定,所有受测样品中苯并(a)芘含量均不超过≤10μg/kg的限量标准。然而,8个油样的苯并(a)芘含量超过了欧盟≤2μg/kg的限量标准,10个油样的PAH4含量超过了欧盟≤10μg/kg的限量标准。     

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。     

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.     

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.     

Concentration profile of selected polycyclic aromatic hydrocarbon (PAH) fractions in some processed meat and meat products

This study investigates the concentration profiles of selected polycyclic aromatic hydrocarbon (PAH) fractions in selected processed meats, in order to evaluate their dietary and health implications. Smoked, grilled and boiled meat products were bought from different locations in Cape Town and Cape Town environs. PAHs were extracted from each meat sample according to standard methods. The concentrations of benzo[k]fluoranthene (BkP), benzo[a]pyrene (BaP), indeno[1, 2, 3-cd]pyrene (IP), and benzo[g, h, i]perylene(BghiP) in the processed meat extracts were determined using a gas chromatograph coupled with flame ionization detector. Total PAH concentrations in smoked, grilled and boiled chicken fillets, pork, and beef stripes were ranged 2.79, 0.99, 2.33 μg/kg; 19.11, 11.17, 15.04 μg/kg; and 14.84, 9.29, 7.20 μg/kg respectively. There were significant differences (p > 0.05) in the concentration levels of PAHs detected in different types, with the highest levels observed in smoked pork meat. The concentration of BkP, BaP, IP and BghiP detected in the various meat samples were below the EU and WHO dietary exposure limit.     

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.     

分散固相萃取-超低温液液微萃取-气相色谱质谱法测定烟熏及烧烤肉制品中16种欧盟优控多环芳烃

建立了分散固相萃取-超低温液液微萃取-气相色谱质谱法测定烟熏及烧烤肉制品中16种欧盟优控多环芳烃的分析方法。样品用乙腈提取、上清液经分散固相萃取净化后在-80℃条件下采用甲苯液液微萃取浓缩,选用DB-EUPAH色谱柱(20 m×0.18 mm×0.14μm)分离,最后经质谱检测定量。结果表明,16种欧盟多环芳烃在5~500μg/L浓度范围内线性关系良好,相关系数均大于0.999,对烟熏和烧烤的肉制品进行3个不同浓度的加标实验,平均回收率为75.2%~114.2%,RSD为1.84%~7.57%(n=6),检出限(S/N=3)为0.1~0.5μg/kg。应用该方法对40批次市售腊肉制品和烤肉制品中多环芳烃进行了检测,发现部分腊肉制品和烤肉制品中多环芳烃含量超过相关标准和法规的限量要求。该检测方法成本低,灵敏可靠,同时符合国家标准和欧盟法规对烟熏及烧烤肉制品中多环芳烃的限量检测要求。     

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.     

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.     

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.     

Gas chromatography-mass spectrometry (GC-MS) method for the determination of 16 European priority polycyclic aromatic hydrocarbons in smoked meat products and edible oils

A gas chromatography-mass spectrometry (GC-MS) method was developed for the analysis of 15 polycyclic aromatic hydrocarbons (PAHs) highlighted as carcinogenic by the Scientific Committee on Food (SCF) plus benzo[c]fluorine (recommended to be analysed by the Joint FAO/WHO Expert Committee on Food Additives (JECFA)) in fat-containing foods such as edible oils and smoked meat products. This method includes accelerated solvent extraction (ASE) and the highly automated clean-up steps gel permeation chromatography (GPC) and solid-phase extraction (SPE). Using a VF-17ms GC column, a good separation of benzo[b]fluoranthene, benzo[j]fluoranthene and benzo[k]fluoranthene was achieved. Furthermore, the six methylchrysene isomers and the PAH compounds with a molecular weight of 302 Daltons in fat-containing foods attained a better chromatographic separation in comparison with a 5-ms column. The reliability of the analytical method for edible oils was demonstrated by the results from a proficiency test. Measurements with GC-high-resolution mass spectroscopy (HRMS) and gas chromatography-mass selective detection (GC-MSD) led to comparable results. A survey of the 16 PAHs in 22 smoked meat products showed concentrations in the range <0.01–19 µg kg^?1. The median concentration for benzo[a]pyrene was below 0.15 µg kg^?1.     

二维液相色谱法测定烧烤肉制品中苯并（a）芘

烧烤肉制品由于富含动物油脂,在炭火高温烧烤熟制品过程中,容易出现苯并（a）芘超标问题,具有较高安全隐患。建立二维液相色谱仪检测烧烤肉制品中苯并（a）芘的方法。第1维为分离、富集柱,采用Inertsil ODS柱（4.6 mm×150 mm,5 μm）,流动相为乙腈-水（85∶15,V/V）,流速1.0 mL/min,可以实现500 μL样品中目标物苯并（a）芘的富集与分离;第2维采用ChromSpher Pi柱（3.0 mm×80 mm,5 μm）,流动相为异丙醇-乙腈（60∶40,V/V）,流速1.2 mL/min,可以有效分离、测定样品中的苯并（a）芘。结果表明：烧烤肉制品中苯并（a）芘在1.0～20.0 ng/mL范围内呈线性关系,其线性回归方程为y=1.847 1x－0.103 3（r=0.999）,检出限为0.08 μg/kg,在1.00、3.00、5.00、10.00 μg/kg加标水平下,加标回收率为97.1%～105.2%,相对标准偏差为1.55%～2.77%。