Rapid Determination of Benzo[a] pyrene in Edible Vegetable Oil Using a New Type of Solid Phase Extraction Column

研究了Bond Elut ENV新型固相萃取柱在食用植物油中苯并[a]芘快速检测中的应用,建立了快速测定食用植物油样品中苯并[a]芘残留量的固相萃取/液相色谱/荧光检测法.样品用正己烷溶解,固相萃取净化,SUPELCOSILTM LC - PAH(25 cm×4.6 mm,5μm)色谱柱分离,以乙腈-水(95:5)为流动相,荧光检测(λ(n) =297 nm,λem=408 nm),外标法定量.苯并[a]芘的检出限为0.3μg/kg,在1.0 ～50.0 μg/L范围内线性关系良好,相关系数为0.9996,方法的回收率为79％～102％,相对标准偏差不高于9.4％.该方法准确、实用、简便、快速,在食用植物油的苯并[a]芘残留量检测方面有广泛的应用前景.     

固相萃取/高效液相色谱荧光法测定草珊瑚中苯并[α]芘残留

采用固相萃取方法,建立了草珊瑚中苯并[α]芘的高效液相色谱荧光测定方法。以正己烷为提取溶剂对草珊瑚样品进行提取,经中性氧化铝固相萃取柱净化样品后,用高效液相色谱荧光检测器检测,荧光检测器激发波长为370 nm,发射波长为425 nm,流动相为乙腈-水(85∶15),流速为1.0 m L/min。结果表明:苯并[α]芘在0~20 ng/m L浓度范围内线性关系良好,相关系数(r)为0.999 9,定量下限为0.36μg/kg,回收率为84.4%~101.9%,相对标准偏差(RSD)为1.6%~5.6%。该方法准确,灵敏度高,重复性好,适用于植物药材中苯并[α]芘残留的测定。     

固相萃取-高效液相色谱-荧光法测定方便面和烤肠中的苯并[a]芘

建立了固相萃取-高效液相色谱-荧光法检测方便面和烤肠中苯并[a]芘的方法。采用正己烷作为提取溶剂,经苯并[a]芘专用固相萃取柱HiCapt Benzo富集净化,高效液相色谱-荧光法对样品中苯并[a]芘进行分离分析。苯并[a]芘的质量浓度在0.5~20.0μg/kg范围内与色谱峰面积呈良好的线性关系,相关系数R2为0.9997。方便面和烤肠中苯并[a]芘的加标回收率分别为92.2%~98.3%和95.9%~97.9%,日内和日间相对标准偏差分别为3.34%~5.01%和2.11%~4.07%。与传统方法相比,该方法快速简单、有机溶剂消耗少,在油炸烟熏食品的苯并[a]芘分析中具有较大应用前景。     

高效液相色谱-荧光检测法测定螺旋藻中苯并[a]芘残留

建立了高效液相色谱-荧光检测法测定螺旋藻中苯并[a]芘残留的分析方法。螺旋藻样品用正己烷提取,经中性Al2O3固相萃取(SPE)柱净化。用Zorbax Eclipse XDB-C18色谱柱分离,流动相为乙腈-水(85∶15,V/V),流速1.0mL/min,荧光检测器检测。苯并[a]芘的质量浓度在0~20ng/mL范围内线性关系良好,相关系数r=0.9999,检出限为0.12μg/kg,定量限为0.40μg/kg,回收率为96.60%~101.2%,相对标准偏差为1.38%~5.68%。该方法准确,灵敏度高,重复性好,适用于螺旋藻中苯并[a]芘残留的测定。     

冷冻脱脂-分散固相萃取/气相色谱-串联质谱法检测食用植物油中4种多环芳烃

针对食用植物油中欧盟限量4种多环芳烃,建立了冷冻脱脂-分散固相萃取/气相色谱-串联质谱检测方法。以苯并(a)芘-d12(BAP-d12)、屈-d12(CHR-d12)为内标,样品经乙腈-水涡旋提取,冷冻脱脂结合分散固相萃取净化,气相色谱-串联质谱多反应监测(MRM)模式检测。结果显示,4种多环芳烃质量浓度在1～50μg/L范围内线性良好,r>0.999,加标回收率为80.8%～103.8%,相对标准偏差(RSD)为7.4%～13%,方法检出限和定量限分别为0.10～0.15μg/kg和0.33～0.51μg/kg。该方法能够满足食用植物油中欧盟限量4种多环芳烃的检测。     

固相萃取/高效液相色谱法测定饮用水中苯并(a)芘及双酚A

建立了饮用水中苯并(a)芘(Bap)和双酚A(BPA)同时测定的固相萃取/高效液相色谱方法。水样中苯并(a)芘和双酚A经ENVI-18固相萃取小柱富集后,采用C18色谱柱分离,以乙腈-水为流动相,梯度洗脱,荧光检测器检测。结果表明,苯并(a)芘和双酚A在0.1~20.0μg/L浓度范围内线性关系良好,相关系数大于0.999,检出限分别为0.2 ng/L和2.0 ng/L,样品加标回收率为86.1%~101%,相对标准偏差为2.9%~4.6%。该方法灵敏度高,选择性好,方便快捷,适用于饮用水中苯并(a)芘和双酚A的测定。     

超高效液相色谱-大气压化学电离-三重四极杆质谱联用法快速测定食品中苯并[a]芘

建立了快速检测食品中苯并[a]芘的超高效液相色谱-三重四极杆质谱联用(UPLC-MS/MS)分析方法。样品用正己烷提取后,经分子印迹固相萃取柱净化,以甲醇和水作为流动相进行梯度洗脱,在XBridge BEH C18柱上实现分离,大气压化学电离(APCI)-三重四极杆质谱正离子MRM方式检测,以苯并[a]芘-d12作为内标的稳定同位素稀释法定量。方法的线性范围为0.07~50μg/kg,定量限为0.07μg/kg。平均加标回收率为86%~104%,相对标准偏差为2.3%~14%。该方法灵敏、准确,适用于食品中苯并[a]芘的测定,已应用于实际样品的检查。     

固相萃取/高效液相色谱荧光法测定水产品中苯并芘

采用Florisil固相萃取柱纯化样品,建立了高效液相色谱(HPLC)荧光法测定水产品中苯并(a)芘的方法.样品以正己烷为提取剂,净化、蒸发浓缩后用流动相溶解.荧光检测器激发波长297 nm,发射波长405 nm.流动相为V(乙腈):V(水)=75:25,流速1.0 mL/min,外标法定量.苯并(a)芘在0～200 ng/mL浓度范围内线性关系良好,相关系数r=0.99990;在5个空白样品中添加0.5μg/kg浓度水平的标准品,回收率在81.9%～89.5%之间,相对标准偏差为4.1%(n=5);日内、日间精密度分别为0.7%(n=5)、2.4%(n=3);最低检测限为90 ng/kg.     

基质固相分散-高效液相色谱法测定植物油中的痕量苯并［a］芘

苯并[a]芘是一种强致癌物质，它是有机化合物在高温条件下发生聚合反应产生的，主要在垃圾焚烧、高温炼油等过程中产生。其一旦产生就很难分解，因此危害较大。无公害食品植物油的理化指标中规定苯并[a]芘的含量要低于10μg/kg。本文采用基质固相分散萃取技术处理植物油样品，减少了有机溶剂的用量，缩短了分析时间，提高了分析效率。处理后的样品经高效液相色谱法（HPLC）的快速测定，所得结果完全能满足食品检验的需要。     

基质固相分散-高效液相色谱法测定植物油中的痕量苯并[a]芘

苯并[a]芘是一种强致癌物质,它是有机化合物在高温条件下发生聚合反应产生的,主要在垃圾焚烧、高温炼油等过程中产生。其一旦产生就很难分解,因此危害较大。无公害食品植物油的理化指标中规定苯并[a]芘的含量要低于10μg/kg。本文采用基质固相分散萃取技术处理植物油样品,减少了有机溶剂的用量,缩短了分析时间,提高了分析效率。处理后的样品经高效液相色谱法(HPLC)的快速测定,所得结果完全能满足食品检验的需要。1实验部分1.1仪器与试剂W a ters A lliance2695高效液相色谱仪,配四元泵溶剂淋洗系统、自动进样系统、2475荧光检测器。SUPE…     

Determination of Polycyclic Aromatic Hydrocarbons in Airborne Particulate by High Performance Liquid Chromatography

This paper presents a trisolvent ultrasonic extraction and HPLC analysis method for the determination of 11 polycyclic aromatic hydrocarbons in air particulate collected on an air filter by a commercial high volume air sampler. A reverse phase column, Vydac 201 TP, and a gradient mobile phase, acetonitrile/water, were used. The 11 PAHs, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a, h]anthracene, benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and coronene were completely resolved under experimental conditions. All the PAHs except coronene were monitored by fluorescence with λ_ex=270 nm, λ_em>389 nm. Coronene was monitored by UV with λ=300 nm. The methodology was evaluated by spiking SRM 1649 with a PAH standard and then going through different extraction procedures and analyzing the PAH concentrations without clean-up. An external standard method was used for quantitation. The recovery yields for fluoranthene, benz[a]anthracene, benzo[a]pyrene, benzo[ghi]perylene and indeno[l,2,3-cd]pyrene were above 90%. The detection limits of PAH with fluorescence at λ_ex=270 nm, λ_em>389 nm ranged from 5.7 pg to 69.5 pg.     

高效液相色谱-荧光检测法测定橄榄油中4种多环芳烃

建立了高效液相色谱-荧光检测(HPLC-FLD)测定橄榄油中苯并[a]蒽、屈艹、苯并[b]荧蒽、苯并[a]芘4种多环芳烃(PAHs)的分析方法。橄榄油样品经异丙醇稀释,采用具有π-π特异性作用的固相萃取柱净化,Agilent ZORBAX Eclipse PAH色谱柱(100 m m×2.1 m m,1.8μm)分离,以水-乙腈为流动相,梯度洗脱,实现了4种化合物的基线分离,并用基质匹配校准溶液进行外标法定量。4种多环芳烃的线性范围为2.4~40μg/L,相关系数(r)为0.999 0~0.999 9,方法的定量限为0.147~0.413μg/L,加标回收率为95.5%~103.2%,日内和日间精密度(RSD)分别为0.10%~1.69%和2.48%~2.93%(n=5)。该法具有灵敏度高、检出限低、重复性好等特点,适用于橄榄油中4种PAHs快速、准确的定量检测。     

Sensitive and selective determination of metabolically formed trans-dihydrodiols and phenols of benzo[a]pyrene in water and urine samples by HPLC with amperometric detection

A method has been developed to separate hydroxylated metabolites of the carcinogenic polycyclic aromatic hydrocarbon benzo[a]pyrene, i. e. trans-4,5-, 7,8-, 9,10-dihydrodiol and 1-, 3-, 7-, and 9-phenol, by HPLC with amperometric detection employing an isocratic methanol/water eluent (70:30, v/v) containing 0.5 g/L sulfuric acid and 1 g/L lithium perchlorate. Compared with the usually applied fluorescence (λ_ex = 265 nm, λ_em = 460 nm) and ultraviolet (λ = 265 nm) detection, the amperometric technique is about 2–12 times more sensitive for the determination of all metabolites investigated. The method was applied to the determination of the seven metabolites of benzo[a]pyrene in different water samples and in urine after solid-phase extraction (SPE). The results obtained by HPLC with amperometric detection after SPE enrichment from an aqueous extract of a soil sample and from the urine of a rat intragastrically treated with benzo[a]pyrene agreed well with the values determined with fluorescence and/or UV detection.     

Determination of benzo[a]pyrene tetrols by column-switching capillary liquid chromatography with fluorescence and micro-electrospray ionization mass spectrometric detection

The present work displays capillary liquid chromatographic column switching methodology tailored for determination of benzo[a]pyrene tetrol isomers in biological matrices using on-line fluorescence and micro-electrospray ionization mass spectrometric detection. A well-established off-line crude solid phase extraction procedure was used in order to make the method compatible with several biological matrices. The solid phase extraction eluates were evaporated to dryness, redissolved in 1.0 ml methanol:water (10:90, v/v), loaded onto a 0.32 mm I.D. x 40 mm 5 microm Kromasil C(18) pre-column for analyte enrichment and back-flushed elution onto a 0.30 mm I.D. x 150 mm 3.5 microm Kromasil C(18) analytical column. The samples were loaded with a flow rate of 50 microl min(-1) and the tetrols were separated at a flow rate of 4 microl min(-1) with an acetonitrile:10 mM ammonium acetate gradient from 10 to 90%. A sample loading flow rate up to 50 microl min(-1) was allowed. The fluorescence excitation and emission were set to 342 and 385 nm, respectively, while mass spectrometric detection of the benzo[a]pyrene tetrols was obtained by monitoring their [M - H](-) molecular ions at m/z 319. The method was validated over the concentration range 0.1-50 ng ml(-1) benzo[a]pyrene tetrols in a cell culture medium with 100 microl injection volume, fluorescence detection and the first eluting tetrol isomer as model compound, resulting in a correlation coefficient of 0.993. The within-assay (n= 6) and between-assay (n= 6) precisions were determined to 2.6-8.6% and 3.8-9.6%, respectively, and the recoveries were determined to 97.9-102.4% within the investigated concentration range. The mass limit of detection (by fluorescence) was 3 pg for all the tetrol isomers, corresponding to a concentration limit of detection of 30 pg ml(-1) cell culture medium. The corresponding mass spectrometric mass limits of detection were 4-10 pg, corresponding to concentration limits of detection of 40-100 pg ml(-1) cell culture medium.     

Determination of benzo[a]pyrene in edible oils using phase‐transfer‐catalyst‐assisted saponification and supramolecular solvent microextraction coupled to HPLC with fluorescence detection

For the analysis of edible oils, saponification is well known as a useful method for eliminating oil matrices. The conventional approach is conducted with alcoholic alkali; it consumes a large volume of organic solvents and impedes the retrieval of analytes by microextraction. In this study, a low‐organic‐solvent‐consuming method has been developed for the analysis of benzo[a]pyrene in edible oils by high‐performance liquid chromatography with fluorescence detection. Sample treatment involves aqueous alkaline saponification, assisted by a phase‐transfer catalyst, and selective in situ extraction of the analyte with a supramolecular solvent. Comparison of the chromatograms of the oil extracts obtained by different microextraction methods showed that the supramolecular solvent has a better clean‐up effect for the unsaponifiable matter from oil matrices. The method offered excellent linearity over a range of 0.03– 5.0 ng mL⁻¹ (r > 0.999). Recovery rates varied from 94 to 102% (RSDs <5.0%). The detection limit and quantification limit were 0.06 and 0.19 μg kg⁻¹, respectively. The proposed method was applied for the analysis of 52 edible oils collected online in China; the analyte contents of 23 tested oil samples exceeded the maximum limit of 2 μg kg⁻¹ for benzo[a]pyrene set by the Commission Regulation of the European Union.     

全自动固相萃取-气相色谱-串联质谱法测定卷烟主流烟气中的3种多环芳烃

以全自动固相萃取技术净化主流烟气萃取液,建立了卷烟主流烟气中苯并［a］芘、苯并［a］蒽和屈艹 3种多环芳烃的气相色谱-串联质谱(GC-MS/MS)测定方法。以吸烟机抽吸卷烟,并以剑桥滤片捕集卷烟主流烟气,然后以含氘代苯并［a］芘内标的环己烷溶液萃取滤片,萃取液经全自动固相萃取仪净化后以GC-MS/MS分离检测。结果表明,苯并［a］芘、苯并［a］蒽和屈艹 的检出限分别为0.05、0.16和0.23 ng/cig,回收率为91.5%～102.1%,相对标准偏差(RSD)均小于5%。该方法的自动化程度高、操作简便、检出限低、重复性好,适用于卷烟主流烟气中苯并［a］芘、苯并［a］蒽 3种多环芳烃释放量的检测。     

Sensitive and selective determination of metabolically formed trans-dihydrodiols and phenols of benzo[a]pyrene in water and urine samples by HPLC with amperometric detection

A method has been developed to separate hydroxylated metabolites of the carcinogenic polycyclic aromatic hydrocarbon benzo[a]pyrene, i. e. trans-4,5-, 7,8-, 9,10-dihydrodiol and 1-, 3-, 7-, and 9-phenol, by HPLC with amperometric detection employing an isocratic methanol/water eluent (70:30, v/v) containing 0.5 g/L sulfuric acid and 1 g/L lithium perchlorate. Compared with the usually applied fluorescence (λ_ex = 265 nm, λ_em = 460 nm) and ultraviolet (λ = 265 nm) detection, the amperometric technique is about 2–12 times more sensitive for the determination of all metabolites investigated. The method was applied to the determination of the seven metabolites of benzo[a]pyrene in different water samples and in urine after solid-phase extraction (SPE). The results obtained by HPLC with amperometric detection after SPE enrichment from an aqueous extract of a soil sample and from the urine of a rat intragastrically treated with benzo[a]pyrene agreed well with the values determined with fluorescence and/or UV detection. Received: 20 December 1996 / Revised: 10 March 1997 / Accepted: 30 April 1997     

气相色谱法测定地表水中的氯丁二烯

建立固相萃取柱富集–气相色谱法测定地表水中氯丁二烯的方法。采用C18固相萃取小柱对水样进行富集处理,以二氯甲烷作为洗脱液,用带ECD检测器的气相色谱仪测定地表水中氯丁二烯的含量。氯丁二烯的质量浓度在1.0~30.0μg/L范围内与色谱峰面积成良好的线性关系,线性相关系数为0.999 2,方法检出限为0.08μg/L,测定结果的相对标偏差小于2%(n=7),加标回收率为92.3%~97.0%。该方法操作简便、快速,有机试剂用量少,适用于地表水中的氯丁二烯的测定。