Pollution patterns of polycyclic aromatic hydrocarbons in tobacco smoke

Concentrations of polycyclic aromatic hydrocarbons (PAHs) in tobacco smoke of 12 commercial brand cigarettes were determined in a simulated chamber of 20.25 m3 in size. The total concentrations of 17 PAHs (summation operatorPAHs) in the chamber were 3500 and 1152 ng/m3 in vapor phase and particulate phase, respectively. In vapor phase, the yield of naphthalene (NA) appeared to be the most abundant (2462 ng/cig) followed by fluorene (FLUOR) and acenaphthylene (ACY), while the yield of benzo[ghi]perylene (BP) was the most abundant (259.7 ng/cig) in particulate phase followed by phenanthrene (PHEN) and FLUOR. The proportion of PAHs in particulate phase increased with increasing molecular weight. PAHs with two to six rings accounted for 40.2%, 35.3%, 11.7%, 7.6%, 5.2% of summation operatorPAHs, respectively. There was no obvious correlation between PAHs, benzo[a]pyrene (BaP) concentrations in tobacco smoke and smoking tar contents, nicotine contents. With the source fingerprint of PAHs in tobacco smoke, NA could be regarded as the marker of tobacco smoke source because of its largest contribution to summation operatorPAHs (40.2%), followed by FLUOR (12.7%) and ACY (9.8%). Further study indicated that more than 80% of BaP in indoor air of resident homes in Hangzhou was from tobacco smoke.     

Simultaneous determination of five tobacco-specific nitrosamines in mainstream cigarette smoke by isotope dilution liquid chromatography/electrospray ionization tandem mass spectrometry

Tobacco-specific nitrosamines (TSNAs) have been previously implicated as a source of carcinogenicity in tobacco and cigarette smoke. Accurate quantification of these chemicals is needed to help assess public health risk. We have developed and validated a specific and sensitive method to simultaneously measure five TSNAs in the particulate phase of mainstream tobacco smoke. Cigarette smoke particulate, produced using standardized machine smoking protocols, was collected on a Cambridge filter pad. The particulate matter was extracted using methylene chloride, back extracted into aqueous solution, further purified by solid-phase extraction, and analyzed by liquid chromatography/electrospray ionization tandem mass spectrometry using isotopically labeled analogues as internal standards. Limits of detection for this method ranged from 0.05 to 1.23 ng/mL using an injection volume of 20 microL. A linear calibration range spanning 2.5-2500 ng/mL was adequate to measure TSNA levels in cigarette smoke. The method achieved excellent reproducibility and accuracy. The identity of each TSNA was established by chromatographic retention time, analyte-specific fragmentation patterns, and relative peak area ratios of two product/precursor ion pairs. This new method provides higher sensitivity, specificity, and throughput than earlier methods for TSNA determination.     

Fluorescent approach to quantitation of reactive oxygen species in mainstream cigarette smoke

A novel approach to monitoring of mainstream smoke reactive oxygen species (ROS) has been developed and applied to the quantitation of smoke oxidants. Redox-active fluorescent probe dihydrorhodamine 6G (DHR-6G) was selected as the molecular probe because it is sensitive to typical smoke ROS. The experimental system couples an automatic cigarette smoke machine fiber-optic fluorometer for real-time monitoring of the reaction progress between cigarette smoke and DHR-6G. Quantitation was achieved based on the amount of rhodamine 6G, which is the sole product from DHR-6G oxidation. With the optimization of the trapping efficiency, we detected 391 nmol of ROS/cigarette in the mainstream CS for a standard cigarette 2R4F under standard Federal Trade Commission smoking protocol. Applying this method, we quantified the ROS of selected cigarettes and found that the cigarettes made of burley tobacco have much ( approximately 10 times) higher ROS content in the smoke than that in the tobacco made of bright tobacco. The smokeless cigarette, Eclipse, has comparable ROS with cigarettes made of bright tobacco.     

Supercritical fluid extraction and gas chromatography/mass spectrometry for the analysis of tobacco-specific nitrosamines in cigarettes

A method for measuring four tobacco-specific nitrosamines (TSNAs), an important group of compounds in tobacco products, was developed. These compounds were extracted using supercritical fluid extraction (SFE) and purified by a sodium hydroxide wash of the ethyl acetate eluting solvent and solid-phase extraction. Quantitation was performed using gas chromatography/mass spectrometry (GC/MS). Spiking experiments were carried out to determine the recovery, precision, and limits of detection of this method. The detection limits were 0.04 microgram per sample for N'-nitrosonornicotine and N'-nitrosoanatabine and 0.02 microgram for 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone and N'-nitrosoanabasine. This method was used to measure TSNAs in various brands of cigarette tobacco with excellent reproducibility. The variation of TSNA levels among the cigarettes of different packs and types was significantly smaller than that among different brands. Comparable TSNA levels were obtained with SFE and liquid extraction methods. Signal-to-noise levels were similar for GC/MS and GC/thermal energy analysis when low-level tobacco samples were analyzed.     

烟支内烟丝分布对卷烟烟气的影响

通过对不同规格平准器卷烟机卷制的烟支进行试验对比分析,研究了相同条件下烟支内烟丝分布对卷烟烟气指标以及逐口分析的影响。结果表明,使用6槽和3槽平准器卷烟机卷制的烟支,他们的烟支重量和吸阻均较稳定,但6槽与3槽平准器卷烟机卷制的烟支相比,其烟气中的焦油、烟碱和一氧化碳量更低,卷烟逐口间烟气的焦油、烟碱含量变化更小。     

Solid-phase extraction of pesticides from water: possible interferences from dissolved organic material

A multiresidue analysis for trifluralin, simazine, atrazine, propazine, diazinon, parathion-methyl, alachlor, malathion, parathion, chlorpyrifos, pendimethalin, methidathion, and DEF in water that utilizes liquid-solid extraction (LSE) with octadecyl-bonded silica cartridges (C18BSCs) followed by gas chromatography/mass spectrometric analysis was developed. Recoveries of most pesticides were greater than 80% with C18BSCs from fortified water at concentration levels from about 1 to 500 ppb. Recoveries with C18BSCs, from an optically adjusted humic acid solution (10 ppm dissolved organic carbon) made to simulate a natural water with a high dissolved organic content, ranged from 29 to 153% and in general were lower than recoveries obtained from pure water. 14C-Labeled diazinon and parathion were recovered from the humic acid solution at levels of 57 and 68%, respectively, with C18BSCs; the remainder of the labeled pesticides was found in the cartridge eluents. Partition coefficients with human acid were calculated based on recovery of 14C-labeled pesticides from the C18BSCs.     

Copper Tannic Acid Coordination Nanosheet: A Potent Nanozyme for Scavenging ROS from Cigarette Smoke

The global tobacco epidemic is still a devastating threat to public health. Toxic reactive oxygen species (ROS) in the cigarette smoke cannot be efficiently eliminated by currently available cigarette filters. The resultant oxidative stress causes severe lung injury and further diseases. To tackle this challenge, herein, a novel copper tannic acid coordination (CuTA) nanozyme is reported as a highly active and thermostable ROS scavenger. The CuTA nanozyme exhibits intrinsic superoxide dismutase‐like activity, catalase‐like activity, and hydroxyl radical elimination capacity. These synergistic antioxidant abilities make the CuTA nanozyme a promising candidate for the improvement of commercial cigarette filters. Mouse model results show that commercial cigarettes loaded with CuTA nanozyme efficiently scavenge ROS in the cigarette smoke, reduce oxidative stress–induced lung inflammation, and minimize the resultant acute lung injury. The developed CuTA nanozyme offers an efficient ROS scavenger with multiple antioxidant ability and opens up new opportunities for the modification of cigarette filters to reduce the toxic effects of cigarette smoke.     

地表水中有机磷农残测定的前处理方法比较

分别采用液液萃取法和固相萃取法提取地表水样品中的有机磷农药残留。液液萃取法的方法检出限为0.05~0.2 ng/mL,加标回收率为86%~103%,相对标准偏差为2%~7%;固相萃取法的方法检出限为0.03~0.05 ng/mL,加标回收率为49%~118%,相对标准偏差为5%~18%。液液萃取法处理不同类型基体水样的测试稳定性较好,固相萃取法则对于洁净环境水体中痕量有机磷农药残留的富集更为适用。     

新型图文防伪技术在卷烟包装中的应用

目的研究新型图文防伪技术的基本原理及其在卷烟包装中的实际应用。方法通过对现有3种烟包的主要防伪技术进行对比分析,体现出新型图文防伪技术的优势。对新型图文防伪技术的原理进行全面解析,并在2款卷烟产品上进行试验,分析其在卷烟包装上的可印刷性及印刷后的包装材料在卷包过程中的上机适应性,评估该技术在卷烟包装中成功应用的可能性。结果在改进印刷工艺和指定原纸复合工艺的厂家后可知,新型图文防伪技术在所试验的2款卷烟产品包装上的应用是实际可行的。结论新型图文防伪技术是一种简单有效、易识别、不易模仿的新型防伪手段,其在卷烟包装上的运用是可行,并值得推广的,未来将成为包装防伪领域的主要发展方向。     

Toxic metals distribution in different components of Pakistani and imported cigarettes by electrothermal atomic absorption spectrometer

It was extensively investigated that a significant flux of toxic metals, along with other toxins, reaches the lungs through smoking. In present study toxic metals (TMs) (Al, Cd, Ni and Pb) were determined in different components of Pakistani local branded and imported cigarettes, including filler tobacco (FT), filter (before and after normal smoking by a single volunteer) and ash by electrothermal atomic absorption spectrometer (ETAAS). Microwave-assisted digestion method was employed. The validity and accuracy of methodology were checked by using certified sample of Virginia tobacco leaves (ICHTJ-cta-VTL-2). The percentages (%) of TMs in different components of cigarette were calculated with respect to their total contents in FT of all branded cigarettes before smoking, while smoke concentration has been calculated by subtracting the filter and ash contents from the filler tobacco content of each branded cigarette. The highest percentage (%) of Al was observed in ash of all cigarettes, with range 97.3-99.0%, while in the case of Cd, a reverse behaviour was observed, as a range of 15.0-31.3% of total contents were left in the ash of all branded cigarettes understudy.     

Development of a quantitative method for the analysis of tobacco-specific nitrosamines in mainstream cigarette smoke using isotope dilution liquid chromatography/electrospray ionization tandem mass spectrometry

An improved method has been developed for the determination of the four major tobacco-specific nitrosamines (TSNA) in mainstream cigarette smoke. The new method offers decreased sample preparation and analysis time as compared to traditional methodologies. This method uses isotope dilution liquid chromatography coupled to a tandem mass spectrometer with electrospray ionization and is significantly more sensitive than traditional methods. It also shows no evidence of artifactual formation of TSNA. Sample concentrations were determined for four TSNA in mainstream smoke using two isotopically labeled TSNA analogues as internal standards. Mainstream smoke was collected on an industry standard 44-mm Cambridge filter pad, extracted with an aqueous buffer solution, and analyzed without further sample cleanup. This method has been validated through intra- and interlaboratory studies and has shown excellent recoveries, sensitivity, and repeatability. The limits of detection of each TSNA varied from 0.01 to 0.1 ng/mL, and the linear calibration range of the instrument in sample matrix spanned 0.5-200 ng/ mL, which allowed for the determination of the TSNA levels in cigarettes with a wide range of deliveries. Data are also reported from two commercially available industry reference cigarettes and show excellent agreement and reproducibility over a six-month time period (n > 50).     

A systematic approach to optimize solid-phase microextraction. Determination of pesticides in ethanol/water mixtures used as food simulants

The optimization of solid-phase microextraction (SPME) of several organochlorine and organophosphorus pesticides is presented, and the influence of variables is discussed. The optimized method is applied to several selected ethanol/water mixtures used as food simulants, and the influence of the ethanol content on the SPME performance is also discussed. Detection limits ranging from 0.02 to 0.04 ng/g for water simulant and from 38.7 to 205.5 ng/g for 95% ethanol simulant were obtained. The relative standard deviation (% RSD) was <20% in all cases. The optimized method is compared with classical liquid-liquid extraction (LLE).     

Evaluation of hydrazine reduction by cellulose acetate filters using infrared tunable diode laser spectroscopy

Cellulose acetate (CA) filters have been investigated to determine their hydrazine (N2H4) breakthrough characteristics using a system based on tunable diode laser absorption spectroscopy (TDIAS). The breakthrough mass loading sorption curves for hydrazine were dependent on both the flow rate and the concentration. In experiments using a 4.5 ppmv hydrazine standard, the amounts of hydrazine retained by the CA filter were 4.25 microg at a flow rate of 2.82 L/min and 65 microg at a flow rate of 0.28 L/min. These loadings are much greater than the 31.5 ng/cigarette of hydrazine reported in smoke for unfiltered cigarettes. Further, CA filters exposed to four and eight puffs of smoke actually made the filter more efficient in retaining hydrazine compared to CA filters that had not been exposed to smoke. Therefore, if hydrazine is present in smoke at the levels reported in unfiltered cigarettes, all of the hydrazine would be trapped by the CA filter, and would be unable to break through during smoking. A unique feature of this analytical method is that the instrument does not require calibration after molecular parameters have been determined, in this case from previously acquired quantitative hydrazine FT-IR reference spectra.     

顶空-气相色谱法测定卷烟主流烟气粒相物中吡啶

为研究气相色谱测定卷烟主流烟气粒相物中吡啶含量,采用碳酸钠水溶液作基质校正剂,通过顶空进样、DB-WAXETR色谱柱分离、火焰离子化检测器检测。结果表明:吡啶在0.20~16.20μg/mL质量浓度范围内线性拟合度为0.9998,加标回收率在98.4%~104.7%之间,定量限为0.08μg/支,RSD小于5%,该方法可以快速、准确地测定卷烟主流烟气粒相物中吡啶。     

Trace analysis of antidepressant pharmaceuticals and their select degradates in aquatic matrixes by LC/ESI/MS/MS

Treated wastewater effluent is a potential environmental point source for antidepressant pharmaceuticals. A quantitative method was developed for the determination of trace levels of antidepressants in environmental aquatic matrixes using solid-phase extraction coupled with liquid chromatography-electrospray ionization tandem mass spectrometry. Recoveries of parent antidepressants from matrix spiking experiments for the individual antidepressants ranged from 72 to 118% at low concentrations (0.5 ng/L) and 70 to 118% at high concentrations (100 ng/L) for the solid-phase extraction method. Method detection limits for the individual antidepressant compounds ranged from 0.19 to 0.45 ng/L. The method was applied to wastewater effluent and samples collected from a wastewater-dominated stream. Venlafaxine was the predominant antidepressant observed in wastewater and river water samples. Individual antidepressant concentrations found in the wastewater effluent ranged from 3 (duloxetine) to 2190 ng/L (venlafaxine), whereas individual concentrations in the waste-dominated stream ranged from 0.72 (norfluoxetine) to 1310 ng/L (venlafaxine).     

Determination of nicotine and other minor alkaloids in international cigarettes by solid-phase microextraction and gas chromatography/mass spectrometry

Nicotine, nornicotine, anabasine, and anatabine are the most abundant alkaloids in tobacco. Along with the addictiveness of nicotine, other properties, including their occurrence in tobacco at relatively high concentrations, and as the primary precursors for the highly carcinogenic tobacco-specific nitrosoamines, make these chemicals important from a public health standpoint Therefore, developing a fast and accurate quantitative method to screen large numbers of cigarette samples for these alkaloids was important. This report describes the first use of headspace analysis using solid-phase microextraction combined with gas chromatography/mass spectrometry for the unambiguous detection of tobacco alkaloids. Detection and confirmation of each analyte isestablished by both chromatographic retention times and the ratio of reconstructed ion chromatogram peak areas from characteristic quantitation ion and confirmation ion. Twenty-eight cigarette brands from 14 countries were analyzed. Surprisingly, the minor alkaloids' response factors varied considerably among different styles of cigarettes. Accurate quantification was achieved using a three-point standard addition protocol. The standard addition approach was essential to obtain accurate measurements by minimizing matrix effects that would otherwise have contributed to quantitation bias. Significant differences in the alkaloid profiles were measured in the different cigarette brands. These results strongly suggest that such differences reflect variations associated with blend compositions, tobacco quality, and manufacturing practices.     

论信息防伪在卷烟防伪中的“立体化”应用

目的：——对于烟草行业，防伪的意义不仅在于减少公司经济利益的损失，还在于烟草品牌的保护。方法——利用高科技的信息防伪技术，打击质量或包装十分低劣的假冒卷烟的销售，会使消费者远离这些品牌。在全球范围内，打击假冒和走私卷烟是世界烟草行业共同面临的一个十分重大的问题。对于假冒和走私卷烟的数量，谁也无法给出一个确切的统计数字。据有关专家介绍，早在2000年，仅在中国境内就有1000亿支以上的假冒走私卷烟流入市场，这个数字相当于西班牙等中等产烟国一年合法的卷烟生产量。当年我国共收缴假冒卷烟57万件（合285亿支）。结果--假冒走私卷烟的质量和其假冒的品牌卷烟的包装的质量是无法相比的，但是，随着经济的繁荣，市场的诱惑，假冒走私卷烟也在花价钱追踪正宗厂家包装防伪技术。结论--毫不夸张地说，烟草的品牌保护是烟草公司的生命线。     

卷烟包装痕迹分析

为探索痕迹学理论在卷烟真伪鉴别检验中的应用,对卷烟包装痕迹进行分析,依据痕迹在卷烟真伪鉴别中的适用性将其分成辊压痕迹、擦划痕迹、剪切痕迹、折叠痕迹、热封痕迹和施胶痕迹六类。结果表明：通过分析卷烟包装痕迹,可溯源卷烟采用的包装机组,验证卷烟包装痕迹与包装工艺的相符性。基于痕迹学原理形成的卷烟包装痕迹学理论可作为卷烟真伪鉴别检验的理论依据。     

基于多轴同步控制技术的条烟柔性码垛系统设计

目的 克服原有的刚性吸盘的局限性，提高烟草物流中心的条烟码垛效率。方法 设计一种基于多轴同步控制技术的条烟柔性码垛系统，以SIMATIC S7–1200 PLC为控制核心，通过PROFINET与Kinoc触摸屏进行通信，将9个步进电机驱动器和传感器同PLC外接的输入、输出模块连接。工控机发送的数据经过PLC处理，通过主令同步的方式控制指令，实现柔性吸盘的同步，完成多样化条烟的同时抓取。结果 该控制系统通过搭建的实验平台验证了其稳定性和高效性，该系统可以同时吸附5条高度和宽度不同的条烟，大大提高了条烟码垛机器人的效率。相较于刚性码垛系统，此柔性码垛系统的码垛效率峰值提高了24.9%左右。结论 文中系统的设计提高了条烟的码垛效率，并且提高了烟草包装的智能化水平。     

玻碳掺杂溶胶-凝胶涂层纤维的固相微萃取特性

溶胶-凝胶包埋玻碳制备新型固相微萃取(SPME)材料,并应用于有机磷农药的SPME检测。该材料具有较好的耐热和抗有机溶剂性能。经过实验条件优化,皮蝇磷,毒死蜱,甲基嘧啶磷,乙硫磷线性响应的浓度范围为0.05-180ng·mL-1,喹硫磷的线性范围为0.3-220ng·mL-1,方法检出限分别为5.5-35.8ng·L-1。