GC-MS/MS法检测山茶油中的苯并[α]芘

建立了山茶油中苯并[α]芘含量的液液萃取-气相色谱-三重串联四极杆质谱(GC-MS/MS)的检测方法。样品称量后加入苯并[a]芘-d12同位素内标,采用乙腈提取两次提取,正己烷脱脂净化后,气相色谱-三重串联四极杆质谱分析。采用DB 5-MS毛细管柱分离,串联四级杆质谱多反应监测模式检测,内标法定量。在优化实验条件下,苯并[α]芘的峰面积与其浓度在0.50μg/L-100μg/L范围内呈良好的线性关系,线性回归系数为0.9994,方法的检出限(LODs)为0.25μg/kg,定量限(LOQs)为0.50μg/kg,在加标水平为0.50、1.00、5.00μg/kg时,山茶油样品中苯并[α]芘的平均回收率在92.51-103.70%之间,日内分析的相对标准偏差(RSD,n=6)为3.84-5.80%,日间回收率为94.71-110.83%,相对偏差为5.22-8.92%(n=5)。该方法具有前处理简单、定量准确、灵敏度高的特点,适用于山茶油中苯并[α]芘的快速确认和准确定量。     

冷冻离心净化-高效液相色谱法测定植物油中苯并(a)芘含量

摘要：建立了冷冻离心净化-高效液相色谱测定植物油中苯并（a）芘含量的方法。样品经乙腈-丙酮（体积比4∶ 6）提取,采用冷冻离心净化,Kromasil C18柱分离,在乙腈-水（体积比9∶ 1）为流动相、流速1.0 mL/min、激发波长365 nm、发射波长406 nm条件下,采用荧光检测器检测。结果表明：苯并（a）芘在0.2~20 μg/L范围内线性关系良好（r=0.999 7）;植物油样品中苯并（a）芘低、中、高3个水平的平均加标回收率在81.3%~90.8%之间,相对标准偏差为1.35%~2.97%;检出限和定量限分别为0.13 μg/kg和0.5 μg/kg。该方法准确、简单,适于植物油中苯并（a）芘含量的测定。     

高效液相色谱-荧光法测定油炸型膨化食品中4种多环芳烃

建立了高效液相色谱-荧光法(HPLC-FLD)测定油炸型膨化食品中苯并[a]蒽(BaA)、(CHR)、苯并[b]荧蒽(BbF)、苯并[a]芘(BaP)4种多环芳烃(PAHs)的分析方法。样品经饱和氯化钠分散后,采用正己烷萃取,经BAP-3分子印迹柱净化,Waters PAH C₁₈色谱柱分离,荧光检测器进行测定,外标法定量。在0.5~40 μg/L浓度范围内4种PAHs均有良好的线性(r>0.999),定量限为(LOQ)0.3~0.5 μg/kg。在空白样品中进行1、5、25 μg/kg 3个水平的加标回收实验,方法的平均回收率在90.3%~107.4%之间,精密度在6.5%以下。该方法简单、快速、灵敏、重现性好,可用于油炸型膨化食品中4种PAHs的定量测定。     

QuEChERS EMR-Lipid技术结合LC/MS/MS快速筛查与确证猪肉中55种兽药残留

运用QuEChERS Enhanced Matrix Removal(EMR)-Lipid技术作为前处理方法,通过高效液相-三重四极杆质谱联用技术建立猪肉中55种兽药残留的快速检测方法。样品采用5%甲酸乙腈进行提取,经QuEChERS EMR-Lipid净化,氮吹浓缩后的溶液通过Agilent Eclipse Plus C₁₈(150 mm×3.0 mm,1.8 μm)进行分离,在三重四极杆正离子动态多反应监测模式下进行检测,通过保留时间及离子对丰度比进行快速筛查和确证,并采用基质标准曲线定量。结果表明,55种化合物在30 min内完成分离,在1.25~250 ng/mL范围内线性关系良好,相关系数r≥0.998,定量限均为1 μg/kg,在1~100 μg/kg加标回收中,回收率在60.5%~139.5%,RSD在1.0%~20.1%(n=6)。本方法简单、快捷、高效,适用于猪肉中多兽药残留的快速筛查与确证。     

固相萃取–液相色谱–荧光检测法测定半夏中 苯并[a]芘残留量

目的建立半夏样品中苯并[a]芘残留量的固相萃取-液相色谱-荧光检测法。方法样品用水浸泡后,用正己烷萃取,硅胶固相萃取柱和ENV固相萃取柱净化,分析时采用SUPELCOSILTM LC-PAH(25 cm×4.6 mm,5μm)色谱柱分离,以乙腈-水(85:15=V:V)为流动相,荧光检测激发波长384 nm,发射波长406 nm,外标法定量。结果苯并[a]芘的检出限为0.1μg/kg,在1.0~50.0 ng/m L浓度范围内,苯并[a]芘的线性相关系数为0.9999,线性关系良好,方法回收率在78.0%~102.5%范围内,相对标准偏差低于9.6%。结论该方法准确、实用、简便、快速,在中药材的苯并[a]芘残留量检测方面有广泛应用前景。     

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。     

植物油中苯并(a)芘含量的快速检测方法研究

建立一种快速灵敏测定植物油中苯并(a)芘含量的方法。采用四氢呋喃作为萃取溶剂,样品溶解过0.22 μm滤膜后直接注入高效液相色谱仪进行测定。结果表明：方法在苯并(a)芘质量浓度0.1~20 ng/mL的范围内线性关系良好,相关系数R2为0.999 9,检出限为0.1 μg/kg,定量限为0.3 μg/kg,样品加标回收率在93.5%~102.5%之间。该方法重现性好,灵敏度高,可对6类植物油中苯并(a)芘含量进行测定,具有较强的实际应用价值。     

高效液相色谱-内标法测定香辛料中15种多环芳烃类污染物(PAHs)

该研究建立了高效液相色谱（High Performance Liquid Chromatography,HPLC）同时分析香辛料中15种多环芳烃类污染物（Polycyclic Aromatic Hydrocarbons,PAHs）含量的内标检测方法。样品经氢氧化钠溶解,乙腈萃取,正己烷复溶后,过弗罗里硅土（Florisil）小柱净化浓缩,供HPLC检测,苯并[a]芘-D12作为内标定量。该方法在0~100 ng/mL内线性关系良好,辣椒中PAHs检出限：0.5~3.0 μg/kg;定量限2.0~10.0 μg/kg;花椒中检出限：0.5~1.0 μg/kg;定量限2.0~3.0 μg/kg。在2.0、10.0、50.0 μg/kg 3个浓度水平,辣椒中回收率范围为60.58%~119.48%,相对标准偏差（Relative Standard Deviations,RSD）（n=6）为1.25%~9.61%,花椒中回收率为60.46%~119.24%,RSD（n=6）为1.10%~8.56%。5种地产香辛料中ΣPAHs 含量由高到低为：青花椒（561.2 μg/kg）＞二荆条（448.8 μg/kg）＞红花椒（358.3 μg/kg）＞石柱红（353.6 μg/kg）＞小米辣（243.5 μg/kg）,区县种植基地污染较严重的为璧山、江津和荣昌,ΣPAHs分别为721.5、626.6和621.0 μg/kg,PAHs中污染较严重的化合物为菲、荧蒽和芘,平均含量分别为215.10、80.25和75.35 μg/kg。该研究建立的内标法准确度高,重复性好,适用于香辛料及制品中PAHs检测。     

基于固相萃取技术的液相色谱-串联质谱法快速检测食用油脂中的苯并(a)芘

以键合硅胶的C_(18)填料和弗罗里硅土填料分层装填的复合固相萃取柱为净化技术,建立一种液相色谱-串联质谱(LC-MS/MS)快速检测食用油脂中苯并(a)芘的分析方法。食用油脂无需溶剂提取,直接进入固相萃取柱,乙腈洗脱,氮吹浓缩定容后经液相色谱-联质谱仪检测,内标法定量。考察了固相萃取柱填料类型、填料用量、洗脱溶剂、洗脱体积等因素对提取效率的影响。在优化的条件下,苯并(a)芘线性范围为0.5～10.0 ng/mL,相关系数≥0.999,检出限为0.1 μg/kg,定量限为0.4 μg/kg。样品在0.4、1.0、10.0 μg/kg 3个水平下的加标回收率为77.5%～94.8%,相对标准偏差为0.65%～4.72%。该法操作简便、快速、准确度高,检出限能满足食用油脂中苯并(a)芘残留的检测要求,分析成本低,可为其他产品中的苯并(a)芘测定提供参考。     

高效液相色谱-荧光法测定食用油中 苯并（a）芘残留量

建立了高效液相色谱-荧光法测定食用油中苯并（a）芘残留量的方法。样品经正己烷提取、苯并（a）芘分子印迹柱净化后,进高效液相色谱仪,在RP-C18保护柱Welch C18 色谱柱（250 mm×4.6 mm×5 μm）、88%乙腈-水溶液为流动相、进样量10 μL条件下,用荧光检测器（激发波长384 nm,发射波长406 nm）测定食用油中苯并（a）芘含量。结果表明：该方法的苯并（a）芘线性范围为1～10 ng/mL,相关系数为0.999 91,检出限为0.2 μg/kg,平均加标回收率为94.9%。采用该方法对7种市售食用油中苯并（a）芘进行测定,结果发现,玉米胚芽油、鱼油中未检出苯并（a）芘,黑芝麻油中苯并（a）芘含量为2.780 μg/kg,胡麻籽油中苯并（a）芘含量为0.863 μg/kg,葵花仁油中苯并（a）芘含量为0.238 μg/kg,大蒜油中苯并（a）芘含量为0.410 μg/kg,五味子油中苯并（a）芘含量为0.132 μg/kg,均低于国家规定限量（10 μg/kg）。与国标法相比,该方法操作简便,节约时间,且灵敏度高、回收率稳定,适用于多种食用油中苯并（a）芘残留量的快速检测分析。     

Determination of benzo[a]pyrene in camellia oil via vortex-assisted extraction using the UPLC-FLD method

In this paper, vortex-assisted extraction using the ultraperformance liquid chromatography analysis method was performed to determine benzo[a]pyrene in camellia oil. Optimum results were obtained when 0.5 g of oil sample was used followed by vortex-assisted extraction for 10 min with 25 mL of acetonitrile. Chromatographic separation was performed on an Agilent ZORBAX Eclipse Plus C₁₈ column (2.1mm×100mm, particle size 1.8 μm). The optimum mobile phase comprised 70% acetone and 30% water. The detection limit of benzo[a]pyrene was 0.2 μg/kg. The recoveries were in the range of 81.0–97.0%. The proposed method was simple and fast, and it provided high throughput in the determination of benzo[a]pyrene in an oil matrix sample.     

皂化提取－高效液相色谱法测定油茶籽油中苯并(a)芘残留

建立了一种先皂化油茶籽油,经萃取和净化,高效液相色谱-荧光检测器测定油茶籽油中苯并(a)芘的检测方法.采用2 mol/L氢氧化钾乙醇溶液皂化,石油醚萃取,中性氧化铝净化柱净化后,再在下述条件下测定:多环芳烃(PAH)C18柱,流动相为体积比95∶5的乙腈-0.5％磷酸水溶液,流速1.0 mL/min,荧光激发波长384 nm,发射波长406 nm,柱温30℃.在2.00 ～ 20.0 μg/kg的添加水平,加标回收率在93.0％～110.0％之间,相对标准偏差在2.59％～9.57％,该方法的检出限为0.2 μg/kg.该方法对油茶籽油中苯并(a)芘提取完全,操作简单,重现性好,检测灵敏度高,对阳性样品判断更有优势.     

亚麻籽油中苯并(α)芘的脱除工艺

针对亚麻籽油中苯并（α）芘残留问题,采用了物理吸附法脱除亚麻籽油中的苯并（α）芘。以活性炭与活性白土为吸附剂,通过二者单独作用及其混合使用,比较三种吸附剂对苯并（α）芘的吸附速率,并采用超高效液相色谱-四级杆-飞行时间串联质谱法结合NIST标准图谱库对经脱除装置处理前后的亚麻籽油中不饱和脂肪酸成分含量进行了鉴定分析。结果表明活性白土的固定用量为4%时,苯并（α）芘脱除率将近达到40%;活性炭的用量为2%时,其脱除率达到83%;将二者串联使用时,脱除率可达到96%。另外苯并（α）芘浓度<15 μg/kg时使用活性白土吸附过滤;苯并（α）芘浓度为15~30 μg/kg时使用活性炭吸附过滤;苯并（α）芘浓度>30 μg/kg时使用二者串联吸附过滤,因此物理吸附法去除亚麻籽油中苯并（α）芘效果最好的是将活性白土与活性炭串联处理,其最佳条件为:活性粘土与活性炭串联比例为0.8%+4%,在此条件下去除率可达96%。同时利用吸附剂对亚麻籽油中不饱和脂肪酸并没有造成损失。综上,本文为亚麻籽油中苯并（α）芘的脱除提供了理论依据。     

Analysis of polycyclic aromatic hydrocarbons in vegetable oils combining gel permeation chromatography with solid-phase extraction clean-up.

A semi-automatic method for the determination of polycyclic aromatic hydrocarbons (PAHs) in edible oils using a combined gel permeation chromatography/solid-phase extraction (GPC/SPE) clean-up is presented. The method takes advantage of automatic injections using a Gilson ASPEC XL sample handling system equipped with a GPC column (S-X3) and pre-packed silica SPE columns for the subsequent clean-up and finally gas chromatography-mass spectrometry (GC-MS) determination. The method was validated for the determination of PAHs in vegetable oils and it can meet the criteria for the official control of benzo[a]pyrene levels in foods laid down by the Commission of the European Communities. A survey of 69 vegetable oils sampled from the Danish market included olive oil as well as other vegetable oils such as rapeseed oil, sunflower oil, grape seed oil and sesame oil. Levels of benzo[a]pyrene in all the oils were low (<0.2-0.8 microg kg(-1)), except for one sample of sunflower oil containing 11 microg kg(-1) benzo[a]pyrene.     

大豆油中苯并（a）芘含量的监测分析

通过对大豆油加工厂的106个大豆油样品进行苯并（a）芘含量的检测,结果表明：未检出苯并（a）芘的样品数量占37.8%;检出0~1μg/kg苯并（a）芘的样品数量占43.4%;检出1~2μg/kg苯并（a）芘的样品数量占7.5%;检出2~10μg/kg苯并（a）芘的样品占11.3%;一级大豆油中的苯并（a）芘含量低于三级大豆油。     

Polycyclic aromatic hydrocarbons in frying oils and snacks

The high incidence of lung cancer observed among Chinese women has been associated with exposure to fumes from cooking oil. Polycyclic aromatic hydrocarbons (PAHs) are a class of potentially mutagenic substances emitted from cooking oils heated at high temperatures. The objective of this study was to investigate whether deep frying with different oils under different conditions leads to the development of PAHs either in the oil or in the fried product (snacks). PAH analysis was carried out with solid-phase extraction followed by reverse-phase high-performance liquid chromatography and spectrofluorometric detection. Different oils were used to fry chips and extruded snacks in different industrial plants (continuous frying) at temperatures between 170 and 205 degrees C, and peanut oil was used to fry French fries and fish (discontinuous frying) at temperatures between 160 and 185 degrees C. No appreciable differences in PAH load was observed in the same oil before and after frying. Both before and after frying, the benzo[a]pyrene concentration in oils ranged from trace to 0.7 ppb. All the analyzed samples, including oils from fried snacks, had benzo[a]pyrene concentrations well below the 2 ppb limit recently proposed by the European Community.     

QuEChERS结合超高效液相色谱-串联质谱法同步测定鱼肉制品中24种磺胺类抗生素

采用QuEChERS结合超高效液相色谱-串联质谱（ultra performance liquid chromatography-tandem mass spectrometry,UPLC-MS/MS）法建立了同时测定鱼肉制品中磺胺二甲嘧啶、磺胺脒、结晶磺胺等24种磺胺类抗生素的分析方法。通过对色谱、质谱条件和QuEChERS前处理技术的优化,确定了最佳的实验条件。样品采用乙腈超声提取,上清液经C₁₈和无水硫酸镁净化,过0.20 μm滤膜后经UPLC-MS/MS检测。以乙腈?0.1%甲酸水溶液为流动相,经Eclipse XDB-C₁₈色谱柱（4.6 mm × 100 mm,1.8 μm）进行分离,在电喷雾电离源（electrospray ionization source,ESI）正离子模式下,进行多反应监测（multiple reaction monitoring,MRM）,基质匹配外标法定量。结果表明,在各自线性范围内24种磺胺类抗生素具有良好的线性关系,相关系数（r）大于0.999,在5、10、50 μg/kg 3个加标浓度水平下的平均加标回收率为80.0%~116.4%,相对标准偏差（relative standard deviation,RSD）为0.8%~9.4%（n=7）。方法检出限为0.01~0.48 μg/kg,定量限为0.02~1.59 μg/kg,所测样品均未检出磺胺类抗生素。该方法简单快速、选择性好、灵敏度高,适用于鱼肉制品中24种磺胺类抗生素的高通量检测。     

Relationship between total polar components and polycyclic aromatic hydrocarbons in fried edible oil

ABSTRACT

Deep-fried dough sticks (a Chinese traditional breakfast) were fried individually in peanut, sunflower, rapeseed, rice bran, soybean and palm oil without any time lag for 32 h (64 batches fried, each for 30 min) and fried oil samples were obtained every 2 h. The frying-induced changes in the levels of total polar compounds (TPC) and polycyclic aromatic hydrocarbons (PAHs) were investigated by edible oil polar compounds (EOPC) fast separation chromatographic system and gas chromatography-mass spectrometry (GC-MS), respectively. The correlations were analysed of TPC with benzo[a]pyrene (BaP), TPC and PAH4 (benzo[a]anthracene, chrysene, benzo[b]fluoranthene and benzo[a]pyrene) as well as TPC with PAH16 (USEPA 16 PAHs). The results revealed that the levels of TPC and PAHs in fried oil considerably increased with frying time, and the type of oil affected their formation, which could inform the choice of oil for frying. The total BaP equivalents (∑BaPeq) concentrations in fresh oil and in oil whose TPC exceeded 27% were 2.14–13.48 and 5.78–10.80 μg kg^–1, respectively, which means that the carcinogenic potency of frying oil was more pronounced than that of fresh oil. In addition, the TPC concentration was significantly correlated with the concentrations of the sum of the 16 PAHs, PAH4 and BaP, so that the levels of PAHs could be predicted according to the levels of TPC in fried oil. In European standards, the rejection point for TPC in frying oil should be recalculated when considered PAHs. In all, the concentration of PAHs is a vital factor for ensuring the safety of frying oil.