高效液相色谱法测定卷烟主流烟气中的苯并[a]芘

为了测定卷烟主流烟气中苯并[a]芘,考察了萃取条件、弗罗里硅土净化条件和色谱分离条件,建立了测定卷烟主流烟气中苯并[a]芘的高效液相色谱-荧光检测法,并采用该方法和国标法测定了肯塔基参考卷烟3R4F和国内参比烤烟以及国内50个牌号卷烟样品烟气中的苯并[a]芘。结果表明:①用环己烷超声萃取40 min效果较好;②用Agilent ZORBAX Eclipse PAH作色谱柱,乙腈和水为流动相,梯度洗脱,流速2.0 mL/min,30 min内苯并[a]芘色谱峰可以和杂质峰有效分开;③该法的平均回收率在98.13%～101.36%之间,RSD在1.29%～4.32%之间;④该方法的测定结果与国标法较为一致,二者不存在显著性差异。该方法适合卷烟主流烟气中苯并[a]芘的检测。     

卷烟主流烟气中苯并[a]芘的HPLC测定

先用乙醇 +乙醚混合溶剂萃取卷烟烟气总粒相物 (TPM) ,再用中性氧化铝柱层析 ,然后 ,利用配有ODS -C18色谱柱的高效液相色谱仪 ,在以 90 %甲醇 + 10 %水为流动相 ,流速为 1mL min ,激发波长 2 86nm和发射波长 4 30nm的条件下测定了TPM中的苯并 [a]芘含量。苯并 [a]芘的回收率≥ 91.2 % ,方法的RSD <5 %。并采用该方法测定了 10种不同焦油量卷烟主流烟气中的苯并 [a]芘含量。结果表明 ,就所测定的卷烟而言 ,①在焦油量相近的情况下 ,混合型卷烟烟气中的苯并 [a]芘含量较烤烟型卷烟的低 8.2 9%～ 19.5 9% ;②无论是烤烟型还是混合型卷烟 ,随着卷烟焦油量的降低 ,虽然焦油中的苯并[a]芘总量明显降低 ,但单位量焦油中的苯并 [a]芘含量却明显增大。     

石墨烯纳米材料对卷烟主流烟气苯并[a]芘和苯酚的降低作用研究

研究了石墨烯纳米材料对卷烟主流烟气中苯并[a]芘和苯酚释放量的影响作用。将石墨烯纳米材料用作卷烟滤棒的添加剂制备了石墨烯纳米-醋酸纤维二元复合滤棒并制备卷烟制品,利用气相色谱-质谱联用法和高效液相色谱法,对添加石墨烯纳米材料前后卷烟样品主流烟气中苯并[a]芘和苯酚含量进行检测,结果表明:石墨烯纳米材料对苯并[a]芘和苯酚释放量具有明显的选择性降低作用且时效性较长;石墨烯纳米材料对苯并[a]芘的降低幅度可达31.3%,对苯酚的降低幅度可达32.8%;卷烟的物理指标不因石墨烯的添加发生明显变化,且能够保持卷烟原有的吸味风格。     

卷烟主流烟气中苯并[a]芘分离纯化条件的研究

在JDumont方法的基础上,将其正相NH2Sep-Pak柱替换成商品化的固相萃取小柱,优化了超声提取时间,系统讨论了卷烟总粒相物提取液的酸碱洗涤,固相萃取洗脱流速,以及乙腈反萃取等操作对卷烟主流烟气中苯并[a]芘的分离纯化效果的影响。并利用改进的实验条件,测定了卷烟主流烟气中苯并[a]芘的含量。实验结果表明,苯并[a]芘的分离效果明显改善,测定值与国内报道一致。     

PTV-GC/MS-SIM法检测卷烟烟气中的B[a]P

采用程序升温汽化(programmed temperature vaporization,PTV)大体积进样与气相色谱-质谱选择离子扫描模式(GC/MS-SIM)联用,检测了卷烟主流烟气中苯并[a]芘(benzo[a]pyrene B[a]P),优化了PTV-GC/MS-SIM检测卷烟烟气B[a]P的参数。样品经反相C18固相萃取柱(solid-phase extraction,SPE)纯化后的洗脱液不再需要浓缩,直接应用PTV技术进样,提高了洗脱液的利用率,缩短了分析时间,提高了GC/MS-SIM检测卷烟烟气B[a]P的灵敏度。     

卷烟烟气中稠环芳烃的分析研究

本项研究建立了一种测定卷烟烟气中稠环芳烃的分析方法--气质联用法。优化了方法的前处理过程、仪器分析条件,对分析方法的重复性、回收率、检测限进行了研究。确定了环己烷萃取卷烟烟气总粒相物中的稠环芳烃,萃取液经硅胶固相萃取柱净化,用气相色谱-质谱联用仪定量检测苯并[a]芘、苯并[a]蒽和Chrysene 3种稠环芳烃含量的分析方法。该检测方法设计合理,稳定性和重复性好、准确性和精确性高,具有较好的可操作性和推广性。本项目应用该方法对国内外较有代表性的81种卷烟样品中苯并[a]芘、苯并[a]蒽和Chrysene进行了系统的分析测定,研究了国内外混合型与烤烟型卷烟中苯并[a]芘等稠环芳烃含量分布的规律,讨论了卷烟烟气中苯并[a]芘、苯并[a]蒽和Chrysene之间的含量关系及其与总粒相物、焦油的关系。      

液相色谱串联质谱法测定卷烟主流烟气中的苯并[a]芘

为准确、快速地测定卷烟主流烟气中苯并[a]芘的含量,建立了液相色谱-大气压光电离-串联质谱测定卷烟主流烟气中苯并[a]芘的方法。方法对助剂流速、萃取溶剂、烟支数和色谱质谱测定的条件进行了优化,结果表明,当甲苯流速为80μL/min,环己烷作为萃取溶剂,Agilent PAH(100 mm×2.1 mm,3.5μm)作为色谱柱,95%的乙腈和5%的水为流动相,色谱柱温度为40℃,方法检出限为0.15 ng/m L,苯并[a]芘回收率100%~107%,相对标准偏差小于10%,分析时间为6 min,与现行的GC-MS测定卷烟主流烟气中苯并[a]芘的国家标准方法相比大大缩短了分析时间。该方法具有灵敏度高、分析时间短等优点,可以显著地提高分析的通量。     

抽吸条件对卷烟主流烟气苯并[a]芘释放量影响的研究

在吸烟机上,研究了不同抽吸条件下,卷烟主流烟气中苯并[a]芘以及TPM、烟碱和CO释放量的差异。研究表明减少烟蒂长度、提高抽吸频率、增加抽吸容量均能引起主流烟气苯并[a]芘以及其他有害物质释放量的增加,但并不呈线性。某一抽吸参数的变化,对主流烟气苯并[a]芘释放量的影响最小,对烟碱的影响最大。但相对于标准抽吸条件,如果减少烟蒂长度、高频率、高容量这其中的任何2种或3种吸烟方式同时采用,主流烟气中苯并[a]芘释放量的增加幅度却大于烟碱。      

气质联用法测定卷烟侧流烟气中苯并[a]芘

建立了采用气相色谱/质谱联用法分析卷烟侧流烟气中苯并[a]芘的分析方法.该方法使用配有鱼尾罩的侧流吸烟机抽吸卷烟,鱼尾罩附着的苯并[a]芘采用甲醇洗脱,洗脱液中的甲醇在N2保护下加热至80℃挥发完,然后加入捕集了侧流烟气总粒相物的玻璃纤维滤片,采用环己烷超声萃取苯并[a]芘,萃取液苯并[a]芘浓度采用气相色谱/质谱联用...     

卷烟烟气有害成分联合作用的细胞毒性

为评价卷烟烟气有害成分的细胞毒性及其联合作用,以人支气管上皮细胞(BEASe-2B细胞)为靶细胞,分别用卷烟烟气中5种有害成分4-甲基亚硝基-1-(3-吡啶基)-1-丁酮(NNK)、氨、苯并[a]芘、苯酚和巴豆醛单独及两两联合染毒,用MTT法测定染毒24 h后的细胞存活率,计算细胞的平均半数致死剂量(LC50),用效应图解法对联合作用进行评价.结果显示:①NNK、氨、苯并[a]芘、苯酚和巴豆醛的LC50分别为87.2、395.5、5.4、61.9和6.9 mg/L;②NNK与氨、NNK与苯并[a]芘、NNK与苯酚、NNK与巴豆醛、氨与苯并[a]芘、氨与苯酚、氨与巴豆醛、苯并[a]芘与苯酚、苯并[a]芘与巴豆醛、苯酚与巴豆醛的LC50分别为46.2、10.9、14.1、30.4、76.4、86.1、39.0、6.1、1.1和22.1 mg/L;③(NNK与氨、NNK与苯并[a]芘、NNK与苯酚、苯并[a]芘与苯酚、苯并[a]芘与巴豆醛、氨与巴豆醛存在明显的协同作用,而NNK与巴豆醛、苯并[a]芘与氨、苯酚与氨、苯酚与巴豆醛之间无协同作用.因此,卷烟烟气有害成分的细胞毒性存在明显差异,其联合作用的细胞毒性效应各不相同.     

索氏提取-固相萃取-高效液相色谱法检测烟熏肉制品中苯并(a)芘

采用索氏提取-固相萃取-高效液相色谱法检测清真牛肉香肠中的苯并(a)芘含量,结果表明,该方法操作简单,检测结果准确,可信度高,回收率可以达到91%以上,特别是对于油脂含量较高的食品具有良好的效果,可以推广到其他肉制品中苯并(a)芘的检测。     

超高效液相色谱-三重四极杆质谱法快速测定煎炸过程用油中的苯并[a]芘

建立快速检测煎炸过程用油中苯并[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。样品用乙腈提取后,经EMR-Lipid脂质增强型固相萃取柱净化,以乙腈和水作为流动相进行梯度洗脱,在RRHD SB-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多反应监测(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。结果表明,方法的线性范围为1~200 μg/kg,决定系数R2=0.9997,检出限为0.2 μg/kg,定量限为0.6 μg/kg。平均加标回收率为94.0%~98.7%,相对标准偏差为2.1%~5.6%。20批样品中均检出苯并[a]芘,含量在1.76~6.81 μg/kg之间。该方法前处理简单、基质干扰少、定性定量准确、灵敏度高,适用于煎炸过程用油中苯并[a]芘的测定。     

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.     

内标校准液相色谱荧光法测定食用油中苯并（a）芘

采用内标苯并（b）屈校正,建立了正相固相净化-反相液相色谱-荧光分光光度法测定食用油中苯并（a）芘的方法。正相Plus Silica固相萃取柱作为净化柱,反相C18柱作为分离柱。以苯并（b）屈作为内标,测定了苯并（a）芘的校正因子。使用本方法,苯并（a）芘在液态食用油和固态食用油中的检出限分别为0.01和0.03μg/kg。苯并（a）芘在不同食用油回收率在83%～108%之间,方法的日内精密度和日间精密度分别小于7.7%和13.2%。     

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.     

Development and validation of a HPLC method for the determination of benzo(a)pyrene in human breast milk

A simple analytical procedure was developed for the quantitation of benzo(a)pyrene in human breast milk using solid phase extraction (SPE) combined with high performance liquid chromatography. Before the chromatographic process, SPE, including C18 functional groups in silicagel cartridges, was conducted for sample preparation. A C18 column (100×4.6 mm id, 3 μm particle size) was used with acetonitrile:water (80:20) as the mobile phase at a flow rate 1mL/min at 30°C. Fluorimetric detection was performed for excitation and emission at 290 and 406 nm, respectively. It was observed that the calibration curve was linear over the range of 0.5–80 ng/mL. The limit of detection and limit of quantitation were found to be 0.5 and 1.07 ng/mL, respectively. Intraday and interday relative standard deviation values were less than 5.15%. Moreover, the newly developed method provides a fast, simple, cost effective, and sensitive assay to detect an important carcinogen substance, benzo(a)pyrene, in human breast milk.     

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.